(Engineering Materials) Mahmood Aliofkhazraei (Auth.) - Nanocoatings - Size Effect in Nanostructured Films-Springer-Verlag Berlin Heidelberg (2011)

Engineering Materials
For further volumes:

http://www.springer.com/series/4288
Mahmood Aliofkhazraei
Nanocoatings
Size Effect in Nanostructured Films
123
Dr. Mahmood Aliofkhazraei
Materials Engineering Department
Tarbiat Modares University
Jalal Ale Ahmad Highway
14115 Tehran
Iran
e-mail: maliofkh@gmail.com
ISSN 1612-1317 e-ISSN 1868-1212
ISBN 978-3-642-17965-5 e-ISBN 978-3-642-17966-2
DOI 10.1007/978-3-642-17966-2
Springer Heidelberg Dordrecht London New York
Ó Springer-Verlag Berlin Heidelberg 2011
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is
concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcast-
ing, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this
publication or parts thereof is permitted only under the provisions of the German Copyright Law of
September 9, 1965, in its current version, and permission for use must always be obtained from
Springer. Violations are liable to prosecution under the German Copyright Law.
The use of general descriptive names, registered names, trademarks, etc. in this publication does not
imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
Cover design: deblik, Berlin
Printed on acid-free paper
Springer is part of Springer Science+Business Media (www.springer.com)

Preface
In recent years, nanostructured coatings are used on surface of different parts with
the aim of increasing their resistance against erosion, corrosion etc. The scale of
nanomaterials should be classified from 1–100 nm which means clusters or
(atomic) nuclear pellet with no less than 100 nm, fibers less than 100 nm in
diameter and films thickness less than 100 nm. In this range nanomaterials show
specific properties which they did not show for bigger dimensions such as
micrometers. This effects which have came from size of nanomaterials are known
as ‘‘size effect’’. Today, with the development and expansion of nanotechnology,
nanostructured coatings are widely used in military, aerospace, electronic and
magnetic industries, etc. due to having appropriate and unique properties such as
magnetic properties, corrosion resistance, high hardness and wear strength. They
have been developed remarkably in recent two decades. These coatings improve
properties of substrate. Hence, coatings resistant against erosion and corrosion,
self-lubricant system and hard coatings can be produced. Increased attention to
size effect in nanostructures during recent years can be seen in Fig. 1.
In comparison with coatings with micrometer-ranged thickness, nanostructured
coatings usually enjoy better and appropriate properties. Strength and resistance
Fig. 1 Comparison among number of journal articles about size effect of nanostructures iden-
tified on February 25, 2011 using the Scopus search engine. The key words used were (‘‘size
effect’’ + nano) just in title, abstract and keywords
v
vi Preface
against erosion are of the properties which have been taken into consideration.
Transparency is of paramount importance in application of nanometer-ranged
coatings. These coatings enjoy unique magnetic properties and are used with the
aim of producing surfaces resistant against erosion, lubricant system, cutting tools,
manufacturing hardened sporadic alloys, being resistant against oxidation and
corrosion. This book reviews researches around fabrication and classification of
nanostructured coatings with focus on size effect in nanometric scale. Size effect
on electrochemical, mechanical and physical properties of nanocoatings discussed
through different chapters of the book while different examples and figures were
used for better discussion.
February 2011 Mahmood Aliofkhazraei

Contents
1 Synthesis, Processing and Application

of Nanostructured Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 What is Nanotechnology? . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 The Role of Size Effect in Nanotechnology . . . . . . . . . . . . . . 1
1.3 Nanoparticles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.4 Production of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.5 Applications of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . 4
1.6 Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.7 Production and Application of Thin Films . . . . . . . . . . . . . . . 6
1.7.1 Introduction to Sol–gel Method . . . . . . . . . . . . . . . . . 6
1.7.2 Sol–gel Chemical Reaction . . . . . . . . . . . . . . . . . . . . 10
1.7.3 The Effect of Catalyst Hydrolysis . . . . . . . . . . . . . . . 11
1.7.4 Electric Precipitation . . . . . . . . . . . . . . . . . . . . . . . . 11
1.7.5 The Rotate Coating . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.7.6 Scattering Coating . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.7.7 Self Layout . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.7.8 Plasma Polymerization . . . . . . . . . . . . . . . . . . . . . . . 12
1.7.9 Annealing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.7.10 Heating Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.8 Applications of Nanostructured Coatings . . . . . . . . . . . . . . . . 15
1.9 Coating and Surface Engineering . . . . . . . . . . . . . . . . . . . . . . 17
1.10 Coating Issues and Applications . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2 Size Dependency in Nanostructures . . . . . . . . . . . . . . . . . . . . . . . 29

2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.2 Nanocomposites and Their Production Methods. . . . . . . . . . . . 29
2.2.1 Thermal Spraying Nano-Composites . . . . . . . . . . . . . 29
2.2.2 Transitional Metal Nitride Coatings . . . . . . . . . . . . . . 33
vii
viii Contents
2.2.3 Super Rough and Super Hard

Nanocrystalline Coatings. . . . . . . . . . . . . . . . . . . . . . 35
2.2.4 Nanocomposite Coatings. . . . . . . . . . . . . . . . . . . . . . 37
2.3 Electrochemistry Role in Production of Nano-Coatings. . . . . . . 46
2.3.1 Electro-Deposition Using Porous Templates . . . . . . . . 46
2.3.2 Nano-Coatings Properties . . . . . . . . . . . . . . . . . . . . . 47
2.4 Mechanical Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.5 Corrosion Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.6 Hydrogen Transition and Sensitivity. . . . . . . . . . . . . . . . . . . . 54
2.7 Magnetic Characteristics and Ionic Conductivity . . . . . . . . . . . 55
2.8 Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.9 Nanocoatings Applications . . . . . . . . . . . . . . . . . . . . . . . . . . 58
2.9.1 Structural Applications . . . . . . . . . . . . . . . . . . . . . . . 59
2.9.2 Functional Applications . . . . . . . . . . . . . . . . . . . . . . 59
2.9.3 Classification of Applications . . . . . . . . . . . . . . . . . . 60
2.10 Key Points for Development . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.10.1 Environment and Stability. . . . . . . . . . . . . . . . . . . . . 60
2.10.2 Weight and Volume Reduction . . . . . . . . . . . . . . . . . 63
2.10.3 Smart Layers and Structures . . . . . . . . . . . . . . . . . . . 63
2.10.4 Processes’ Understanding . . . . . . . . . . . . . . . . . . . . . 63
2.10.5 Training . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.11 Surface Engineering Share in Key Industry Sections . . . . . . . . 64
2.12 Estimation of Corrosion and Erosion Costs . . . . . . . . . . . . . . . 64
2.13 Surface Engineering in Automobile Industry . . . . . . . . . . . . . . 65
2.14 Surface Engineering in Power Generation Industry . . . . . . . . . 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3 Characterization of Nanostructured Coatings . . . . . . . . . . . . . . . . 77

3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.2 Definition of Nanostructured Materials . . . . . . . . . . . . . . . . . . 78
3.3 Thermodynamics of Nanostructured Materials . . . . . . . . . . . . . 83
3.4 Interfaces Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.5 Interface Traction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.6 Additional Free Energy on a Solid with
Nanometric Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.7 Interface Stresses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.8 Chemical Equilibrium in Curved Interface . . . . . . . . . . . . . . . 91
3.9 Influential Interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.10 Phase Interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.11 Measurement of Thermal and Electrochemical Properties . . . . . 93
3.12 Condensed and Compressed Metals . . . . . . . . . . . . . . . . . . . . 94
3.13 Methods for Production of Nanostructured Materials . . . . . . . . 95
3.14 Nano-Technological Compatibility in Coating . . . . . . . . . . . . . 98
3.15 Improvement of Coating Quality Using Nanotechnology . . . . . 99
Contents ix
3.16 Abrasion, Scratch, and Corrosion Resistant Coatings . . . . . . .. 99

3.16.1 Coatings Resistant Against Scratch, Abrasion,
Corrosion, and Environmental Agents . . . . . . . . . . .. 99
3.16.2 Nano-Metric Abrasion, Scratch, and Corrosion
Resistant Coatings . . . . . . . . . . . . . . . . . . . . . . . . .. 100
3.16.3 Using Alumina as a Scratch and Abrasion Resistant
Coating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3.16.4 Designing Light Resistant Panels for Plane Body. . . . . 101
3.16.5 Ceramics Reinforced by Carbon Nano-Tubes . . . . . . . 101
3.17 Nano-Coating Resistant Against Corrosion . . . . . . . . . . . . . . . 102
3.18 Using Nano-Particles for Coating in Transportation
Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.19 Coating Applications in Defense and Aerospace Industries . . . . 103
3.20 Using Ceramic Nano-Coatings in US Navy . . . . . . . . . . . . . . . 103
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
4 Size Effect in Electrochemical Properties

4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.2 Thermodynamic Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . 113
4.3 Classical Nucleation Theory . . . . . . . . . . . . . . . . . . . . . . . . . 115
4.4 Atomic Nucleation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . 116
4.5 Kinetics of Formation of Nucleuses
in Electro-Crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.6 Electrode Surface Energy State . . . . . . . . . . . . . . . . . . . . . . . 119
4.7 Nucleus Situation on Electrode Surface . . . . . . . . . . . . . . . . . 120
4.8 Growth of 3-D Nano-Nucleuses . . . . . . . . . . . . . . . . . . . . . . . 122
4.9 Metal Ion Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.10 Double-Layer Structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.10.1 Helmholtz-Perrin Model . . . . . . . . . . . . . . . . . . . . . . 125
4.10.2 Gouy-Chapman Model . . . . . . . . . . . . . . . . . . . . . . . 125
4.10.3 Stern-Graham Model . . . . . . . . . . . . . . . . . . . . . . . . 126
4.11 Determining Stages for Rate of Electrode Reactions . . . . . . . . 126
4.12 Concentration Over-Potential. . . . . . . . . . . . . . . . . . . . . . . . . 127
4.13 Charge Transfer Over-Potential . . . . . . . . . . . . . . . . . . . . . . . 128
4.14 Crystallization Over-Potential . . . . . . . . . . . . . . . . . . . . . . . . 128
4.15 Ohm or Resistance Over-Potential . . . . . . . . . . . . . . . . . . . . . 128
4.16 Pulse Electrochemical Deposition Method. . . . . . . . . . . . . . . . 129
4.17 Charging and De-Charging of Double Layer in Pulse
Electroplating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
4.18 Nanostructured Coating Properties . . . . . . . . . . . . . . . . . . . . . 132
4.18.1 Mechanical Properties. . . . . . . . . . . . . . . . . . . . . . . . 132
4.18.2 Catalyst Properties . . . . . . . . . . . . . . . . . . . . . . . . . . 133
x Contents
4.18.3 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . 133

4.18.4 Anti-Corrosive Properties . . . . . . . . . . . . . . . . . . . . . 133
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
5 Size Effect in Mechanical Properties

5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.2 Nanocomposite Coating Production Method . . . . . . . . . . . . . . 150
5.3 Provision of Nanocomposite Coatings with Plating Method . . . 151
5.4 Plating of Nickel-Alumina Nanocomposite Coating . . . . . . . . . 152
5.5 Effects of Participation of Alumina Nanoparticle
in Nickel Coating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 153
5.6 Plating of Nickel-Alumina Nanocomposite Coating . . . . . . ... 153
5.7 Size Effect in Mechanical Properties of Two Dimensional
Nano-Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 154
5.8 Studying Effective Factors on Simultaneous Deposition
of Alumina Nanoparticles with Nickel . . . . . . . . . . . . . . . ... 162
5.8.1 Effect of Density of Alumina Nanoparticles
in Electrolyte Bath . . . . . . . . . . . . . . . . . . . . . . . . . . 162
5.8.2 Effect of Electroplating Current Density . . . . . . . . . . . 162
5.8.3 Distribution of Alumina Nanoparticles . . . . . . . . . . . . 164
5.8.4 Effect of Density of Nickel Ions in Plating Bath . . . . . 166
5.8.5 Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
5.8.6 Pulse Current Effect . . . . . . . . . . . . . . . . . . . . . . . . . 169
5.9 Size Dependency of Tensile and Fatigue Strength
in Ultra-Thin Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 171
5.10 Application of Coating for Strength Enhancement . . . . . . . ... 173
5.11 Nano-Coating Use in Dressing Industry . . . . . . . . . . . . . . ... 173
5.11.1 Making WC/Co–Ni Nano-Coating
Using Electrodeposition . . . . . . . . . . . . . . . . . . . ... 174
5.11.2 Using (Me-Ti1-xAlxN)/(a-Si3N4)
Nanocomposite Coatings. . . . . . . . . . . . . . . . . . . ... 174
5.12 Size Dependency in Nanocomposite Layers . . . . . . . . . . . ... 175
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 179
6 Size Effect in Physical and Other Properties

6.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6.2 Silicides Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.2.1 SALICIDE Process . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.2.2 Necessary Conditions for Formation of Silicides . . . . . 190
Contents xi
6.2.3 Transition from TiSi2 to NiSi . . . . . . . . . . . . . . . ... 191

6.2.4 NiSi Salicide Technology (Self-Aligned
Nickel Silicide) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
6.3 Size Effect in Sensing Characterization . . . . . . . . . . . . . . . . . 192
6.4 NiSi Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6.4.1 NiSi Transition to NiSi2 in Dual Ni-Si System . . . . . . 195
6.4.2 Pt Effect in Increasing Thermal Stability . . . . . . . . . . 195
6.4.3 Pd Effect in Thermal Stability . . . . . . . . . . . . . . . . . . 198
6.4.4 Ge Effect in Thermal Stability. . . . . . . . . . . . . . . . . . 199
6.4.5 Co and Ir Effects in Thermal Stability . . . . . . . . . . . . 200
6.4.6 Capsulation and NiSi Thermal Stability . . . . . . . . . . . 200
6.5 Size Effect in Optical Properties of Nanostructured Films. . . . . 201
6.6 Optical Coatings: Using Ultraviolet Light Block Layers . . . . . . 208
6.7 Surface Improvement for Making Fog and Vapor
Resistant Layers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
6.8 Production of Pieces with Nano-Coating. . . . . . . . . . . . . . . . . 209
6.9 Self-Cleaning Glasses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
6.10 Medical and Hygienic Applications . . . . . . . . . . . . . . . . . . . . 210
6.10.1 Inorganic Materials Nano-Coating for Medical
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 210
6.10.2 Using Nano-Particle Masks . . . . . . . . . . . . . . . . . ... 210
6.10.3 Application of Hydroxyapatite Nano-Coating
to Design Prosthesis . . . . . . . . . . . . . . . . . . . . . . . . . 211
6.10.4 Using Nanocomposite Coating for Food Packaging . . . 211
6.10.5 Antipollution Materials in Shipping Industry . . . . . . . . 212
6.10.6 Nano-Coating Use Against SARS Virus . . . . . . . . . . . 212
6.10.7 Application of Ag Nanoparticles
as Antibacterial Coating . . . . . . . . . . . . . . . . . . . ... 213
6.10.8 Using TiO2 Nano-Particles to Decrease
Environmental Contaminations . . . . . . . . . . . . . . ... 213
6.11 Electrical and Electronic Applications . . . . . . . . . . . . . . . ... 213
6.11.1 Production of Transparent Conductor Coatings
by Carbon Nano-Tubes . . . . . . . . . . . . . . . . . . . . ... 213
6.11.2 Application of Nano-Coating on Solar Cells . . . . . ... 214
6.11.3 Nano-Coating of Nickel Particles by Oxides . . . . . ... 215
6.11.4 Using Polarizer Nano-Layers to Produce
LCD Monitors . . . . . . . . . . . . . . . . . . . . . . . . . . ... 215
6.11.5 Produce of Electrically Conductive Transparence
Nano-Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . ... 215
6.11.6 Increase of Data Storing Capacity with Magnetic
Nano-Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 216
xii Contents
6.12 Lubricating and the Other Applications . . . . . . . . . . . . . . . . . 216

6.13 Ag-Polluted SnO2 Particles . . . . . . . . . . . . . . . . . . . . . . . . . . 216
6.14 Development of Nano-Coating for Surface Lubrication. . . . . . . 216
6.15 Size Dependency in Nanocomposite Layers . . . . . . . . . . . . . . 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Chapter 1
Synthesis, Processing and Application
of Nanostructured Coatings
1.1 What is Nanotechnology?
Nanotechnology is a general term identified by advanced technology in the nano

field. The scale of nano is usually from 1 to 100 nm [1–3]. First idea of nanotech-
nology appeared in 1959 (where the technology was not identified by the specific
name yet) Richard Feynman proposed the idea of ‘‘There’s plenty of room at the
bottom’’ in his hypothesis. Feynman argued that in the near future the molecules and
atoms can directly be manipulated. The word ‘‘nanotechnology’’ first came to
existence by Professor Norio Taniguchi in 1974. He used the word for accurate
materials with high tolerance in nanometer limits. In 1986 K. Eric Drexler redefined
the word in his book ‘‘Engines of creation: The coming era of nanotechnology’’. He
has profoundly discussed nanotechnology in his thesis and explored the issue in
‘‘Nanosystems Molecular Machinery and Computation’’ [4–14].
Application of nanotechnology rooted in basic elements. Each one has specific
characteristics which creates remarkable attributes in various fields. Application of
nanoparticle in producing simple medicine and bandages with no need to renewal,
diagnosing early cancer cells and analyzing environment pollutants are the
examples of nanotechnology [15–24].
1.2 The Role of Size Effect in Nanotechnology
Nanomaterials are the new materials that their basic construction has formed by
nanometric scale engineering. On such scale the specific or completely different
material indicates the possibility to create more accurate new materials and
devices with vast capacities. The scale of nanomaterials should be classified from
1 to 100 nm which means clusters or (atomic) nuclear pellet with no less than
100 nm, fibers less than 100 nm in diameter and films thickness less than 100 nm.
In this range nanomaterials show specific properties which they did not show for
M. Aliofkhazraei, Nanocoatings, Engineering Materials, 1

DOI: 10.1007/978-3-642-17966-2_1, Springer-Verlag Berlin Heidelberg 2011
2 1 Synthesis, Processing and Application of Nanostructured Coatings
bigger dimensions such as micrometers and bigger. This effects which have came
from size of nanomaterials are known as ‘‘size effect’’ [25–35]. Eleven items all
identify in nanomaterials field are as follow:
1. Nanostructured materials
2. Nanoparticle/nanocomposite
3. Nano-capsule
4. Nano-porous materials
5. Nanofibers
6. Fullerenes
7. Nanowires
8. Single wall/multi walled carbon nanotubes
9. Molecular electricity
10. Quantum dots
11. Thin films
Ohno et al. [36] studied the size effect of TiO2–SiO2 nano-hybrid particles.
They described the effect of drying process on the preparation of TiO2–SiO2 nano-
hybrid particles. The hybrid sol was prepared by sol–gel process with controlled
chemical modification (CCM) to attain the TiO2 nano-coating on the SiO2 nano-
sphere. The hydrolysis reaction of titanium alkoxide was controlled by RA
([CH3COOH]/[Ti]), and RW ([H2O]/[Ti]). The hybrid particles were dried by
under the super critical drying to suppress the hard agglomeration of the as-
prepared nano-hybrid sol. As a result, the hard agglomeration of the primary
particles was successfully suppressed to obtain TiO2–SiO2 nano-hybrid particles
with controlled chemical modification of titanium alkoxide. The quantum size
effect of nano-hybrid particles was confirmed by the band gap energy shift, using
ultraviolet–visible spectroscopy (UV–vis). Figure 1.1 illustrates the ultraviolet–
visible spectrum (UV-S) for the obtained TiO2–SiO2 nano-hybrid particles and that
Fig. 1.1 The ultraviolet–

visible spectrum (UV-S) for
the obtained TiO2–SiO2
nano-hybrid particles (the
dotted line) and that of the
anatase crystals without the
quantum size effect (the black
line), reprinted with kind
permission from Tomoya
Ohno [36]
1.2 The Role of Size Effect in Nanotechnology 3
of the anatase crystals without the quantum size effect. Size effect can be seen in
all of properties of materials.
1.3 Nanoparticles
These materials are the grains with the scale less than 100 nm, comparing to
bigger clusters. Nanoparticles have new qualities in them which it’s specified
features are covers size, distribution, shape, phase and etc. Nanoparticles can be
constructed from a wide range of materials generally metallic oxide ceramics,
metals, silicates and non-oxide ceramics. The scientists hope to use nanoparticles
in fabrication of ideal materials with desired mechanical, electrical, magnetic or
optical characteristics and progress their capacities. In the case that this prospect
occurs, it will affect positive impact on environment and low budget achievements
such as the influence of nanotechnology on medical systems [25, 37–45].
Figure 1.2 is an example of scanning electron microscope (SEM) and transmission
electron microscope (TEM) images of silicon nitride (Si3N4) nanoparticles [46].
Fig. 1.2 a Scanning electron

microscope and
b transmission electron
microscope images of silicon
nitride (Si3N4) nanoparticles
with average size of 72 nm
[46]
Most of the possible capacities that can be found in nanoparticles are connected to
the list below:
• Specific high space area (high surface to volume ratio)
• Electrical and magnetic attributes (advanced electromagnetic elements)
• Optical properties (attract or repel some wavelengths that can be manipulated,
interaction with ligands and external disturbances)
• Chemical elements (increased chemical reaction)
1.4 Production of Nanoparticles
Production of nanoparticles is achievable through following solutions:

• Solid state method (grinding, milling, mechanical alloying methods)
• Commercial methods [Chemical vapor deposition (CVD), Physical vapor
deposition (PVD)]
• Chemical synthesis/dissolution methods (sol–gel, chemical collide)
• Methods of gas phase pyrolysis of flame, electro-explosion, plasma synthesis,
laser abrasion
According to previous researches chemical activities are currently considered
as the best method to produce nanoparticles [47–56].
1.5 Applications of Nanoparticles
High volumes of nanoparticles can be applied in detergents, cosmetics, pesticides,

environmental modification, catalysts, lubricants, sealants, adhesives and coatings
fields. The coatings obtained by nanoparticles are remarkable category in current
and future applications. By these coatings, a profound level of material properties
can be used such as scratch resistance, optical features (transparency or adjusted
reflection) and also self cleaning properties [57–64].
1.6 Thin Films
Scientists apply the thin films by using different materials with thicknesses less
than 100 nm. The basic advantage of thin films as any other coating is that it can
transfer material properties to the surface so it is possible to use materials with
their basic characteristics. The substrate material and thin film create a system with
different enhanced properties. Nanotechnology creates instrument for control of
three key parameters for thin films: (a) Chemical composition (crystalline structure
1.6 Thin Films 5
in nanometer range), (b) Thickness and (c) Surface geometry (including thin films
patterns on nanoscale) [65–74].
The most prominent properties of these materials are as follow:
Optical properties: Including optical entrapment, transparency, opaque, flo-
rescence, waveguides, light valves, anti reflection and etc. [75–88].
Mechanical properties: Including resistance to abrasion and wear, stiffness, anti
scratch, strain-to-failure and etc. [89–95].
Electronic properties: Potential energy, binding energy, conduction, insulation
and etc. [96–111].
Chemical properties: water repellence, anti fog, chemical barriers, being
chemically neutral, oxygen and moisturizing shields on polymers, antimicrobial
surface and etc. [88, 112–116].
Magnetic properties: saving data [117–126].
Thermal properties: application of thin film in multiple layers as an obstacle to
prevent expansion of atomic vibration which produce thermal transmission but
permits the flow of electrons so they can be use in thermoelectric tools [127–130].
It is not strange that many scientists performed their research on thin films.
These materials have vast capacities. For example they can be used in electronic
industry as a light barrier in producing semi-conductor wafers or as metallic
dielectrics (with low dielectrics constant) in integrated circuits and also in organic
light emitting indicators or as anti corrosive coating. Organic thin films can be
created in low temperatures (comparing to ceramic/mineral materials) so less
complicated processes are achievable and can be controlled like sol–gel.
The list of production and precipitation methods of thin films and the coatings
are very vast which includes following items:
• Chemical vapor deposition (CVD)
• Psychical vapor deposition (PVD)
• Sol–gel
• Electronic precipitation/electronic coating
• Electrodeposition
• Rotating coating
• Spray coating
• Self assembling
These processes act completely different from each other. Some of them pro-
duce thin films and also raw materials in atmospheric pressure like sol–gel
(rotating coating is the common method) while others processes like PVD and
CVD can provide thin films with very high quality under low pressure conditions.
According to researches, the preparation of substrate is not necessary for some
materials like carbon and some of the metals. However such preparation is nec-
essary for many substrates. Preparation of substrate includes extensive methods
such as cleaning, surface chemical modification and also using thin films under
main film for the required stickiness. The necessity of clean surface for coating
should not be ignored. Cleaning for the thinner coatings is harder and also has
significant importance.
1.7 Production and Application of Thin Films
Currently different processes are applied for production of thin nanostructured

films. Chemical vapor deposition (CVD) includes heating material (converting it
to gas phase) and its deposition on the surface. In this method the speed of
precipitation is low and the process needs higher temperatures. In most cases
vacuum chamber is required. According to researches, this method is expensive
for coating of large surfaces. Physical vapor deposition (PVD) includes trans-
forming raw material to gas phase (resistive heating, electron beam etc.) and then
deposition on the surface. There are different methods for disposition of material
as thin films. Thermal evaporation, magnetron sputtering and laser pulsed
deposition which are probably the high consumed methods. In this method
controlling on nanoscale is still under limitation and achieving required specifi-
cations needs expensive substrates (unusual single crystal) which cause growth of
thin film in specific orientation and with special structure. The process requires
huge investment and to cover large surfaces (like wafers in semi-conducting
industry), the expensive instrument is needed for the process. In fact this method
needs vacuum chamber which limits the coating surface. As the aim of this
chapter is not complete discussion of all fabrication methods, one of the most
usual methods for fabrication of nanostructured films, sol–gel method, will be
discussed here [131–133].
1.7.1 Introduction to Sol–gel Method
The aim of sol–gel method is to perform chemical process in low temperature for
producing objects, films, fibers, particles or composites with suitable form and
surface. Traditional production processes of ceramics leads to fabrication of
materials which has micro-structures with dimensions in 1–100 lm. Sol–gel
process can change this limitation to dimensions in 1–100 nm and in molecular
level. These materials usually have uniform chemical and physical properties.
Sol is constant suspension from rigid Colloid ingredient or polymer which
placed in one liquid. These particles can be crystalline or amorphous. Sols are
diffused chloride particle in ointment on 1–100 nm dimension which due to it’s
miniscule size and constant moving they stay floating. Gel is rigid network con-
nected with pores under micrometer dimension and polymer chains with
approximately more than 1 lm length. In Colloid gel the network is created by
amalgamation of Colloid particle while the polymer gel has a under structure in
other words polymer unites creates gel. In most sol–gel systems creation of gel
occurs by covalence combination and gel is not reversible which means it can not
turn into sol position again. If the gel has combination other than covalence it can
be reverse [65, 134–141].
1.7 Production and Application of Thin Films 7
In fact sol–gel procedure is a mineral network synthesis by chemical reactions

in lotion on low temperature which is placed in lotion due to its formless size (in
first stages) against crystallization. It is necessary to explain some key words and
regular process.
Gel’s categories are as:
1. Hydro gel: these gels usually produce in water environment, the expression
Hydro gel is a gel sols filled by water it is also called Equagel.
2. Alco gel: Is the gel which it’s sols filled by alcohol, gels which drays by alco-
gel has ample sols and maintains it’s water structure and would have less
fraction when it gets dry.
3. Gasro gel: It is a gel which has lost all the liquids inside sols and has compact
structure and it’s crinkles are more visible than in Hydro gel, it specific surface
has also condensed.
4. Aero gel: It is a dry gel. The liquid in the gel has gone out and has left no place
for compact or change in gel’s structure. This kind of gel mostly created by
heating the gel in 0 h temperature so there will be no maintenance between
liquid and gas and gel will complete by high quality surface and keeping the
structure in Hydro gel form, the following picture explain different postures of
gel.
As an example, different types of silica gel are as:
(A) Hydro gel (B) gasro gel (c) aero gel (d) gasro gel with medium density
Different process of sol–gel:
1. The process of Elcho oxide orbit
2. The process of Colloid orbit
The most common methods of sol–gel process in producing mineral materials
like glasses, Catalyst bases and advanced ceramics are Elcho oxide orbit. This
method was set according to Elcho oxides in chemistry where sol created by base
material of Elcho oxide resolved in water and so the Hydrolysis and density of the
base material has turned sol to gel which construct mineral network under dry
condition.
The following equation indicates the basic sub reactions that transform base
material of Elcho oxide into gel and finally mineral network. In hydrolysis reaction
Elcho oxide turns into mineral types solvable in alcohol.
MðORÞm þ H2 O ! MðORÞm1 ðOHÞ þ ROH

MðORÞm1 ðOHÞ þ H2 O ! MðORÞm2 ðOHÞ2 þ ROH
In densing reaction the activated types are reacting together and polymer net-
work include M–O–M combination (with one Elcho oxide) or M–O–M (with
different types of Elcho oxide) start to generate in salve:
M OH þ HO M ! M O M þH2 O
M OH þ ROM ! M O M þR OH
In this reaction M can be Si, Al, Ti, Zn, Sn, Pb, Ta, Cu, Ni, Co … etc. and R is a
Alkyl group like Methyl, Ethyl, Isopropyl, Butyl and etc.
The process of Colloid orbit follows the base of Colloid chemistry to produce
Colloid particle in Ionic and non Ionic in non aqua environment. In this method sol
created by scattered Colloid particle in a liquid environment usually water. The
sol’s viscosity increases by losing the liquid turn into hard gel. Therefore the
mineral network created by separate particle design and transformation of solution
into gel. Currently the two pointed methods used in sol–gel process however the
Elcho oxide method is more common and most of the works in this field performed
by Elcho oxide as a pre material because Elcho oxide is a suitable source for
mineral monomers and in the Elcho oxide method the speed of main reaction can
be controlled by chemical patterns like controlling the speed of Hydrolysis reac-
tion. Hence chemical process of sol–gel according to Elcho oxide can be easily
controlled like onus on the surface or absorbed items on the surface of particle in
addition the method of Elcho oxide has the possibility to provide specific pro-
duction with high purity level in low temperature.
Process of sol–gel used to produce various materials from Elcho oxide to pre
material categorized by series of constant stages. Each stage is a bridge and
functions between last and next one. The stages are as follows:
1. Mixing
2. Forming
3. Gelation
4. Aging
5. Drying
6. Dehydration or chemical stabilization
7. Densification and sintering
The process of sol–gel first discovered in early 19th century and it began to
widespread in early 1940s. Sol–gel is a moist chemical method in which it’s pre
material with M(OR) structure is turned into a mineral network which includes one
metal oxide. In process of sol–gel the primary material is dissolve in a solution
(considering the conditions of reactive of a sol or a gel) it precipitate. Sol–gel
process consists of 4 stages: hydrolysis, densification, particle polymerization,
particle growth and accumulation and creating network. The result of this process
depends on different factors that affect the speed of Hydrolysis and density. Some
items are more effective:
Catalyst nature and thickness toward molar ratio of primary material to water,
temperature, pH, initial material to produce sol usually mineral metal salts or the
organic metal compound like Alco oxides. The metal used in pre material
production can be a middle metal like Ti, Zr, V, Zn, Al or even a metal network
like Si. In one process of sol–gel the pre material is exposed in series of
Hydrolysis reaction and polymerization to create a Colloid suspension or a sol.
The sol process generates the possibility to construct different forms of ceramic
material.
Thin films can be produce by rotate coating or floating coating on a sub layer.
When the sol is purred in a mold it forms a moist gel with drying and heating
procedure the gel is turned into glass particle or compact ceramics. If gel’s liquid
has moved out in a critical condition a high porosity material with extra density
called Aero gel is formed. By maintaining the sol viscosity in ideal amplitude it
can produce ceramic yarn sol. Infinitesimal and constant ceramic powders can also
be produced by precipitate, scattering pyrolysis or immolation methods.
Nano particle process into sol–gel has the ability to produce cheap pieces which
is a complex of Nano silica particle and other additives put into a container, then
it’s necessary that moist gel is being dried to control and prevent cracks so the
result can be transform to transparent glass. By the help of sol–gel process the
ceramic or glass material can be constructed in different forms, ultra small powder
or spherical, thin film coating, ceramic yarn, mineral curtain micro holes, one
piece ceramic and glasses.
This method can also produce different nano constructions like nano particle,
nano porous material or nano yarn. Mean while it can be used to produce Thin film
with different methods (like coating, floating). Although the method is a solid
process but there are some technical obstacles : cracks and wrinkle of main part of
process which is usually hard to control (especially with low density material and
thin films with high thickness) how ever using organic mineral complex formula
can solve the problem. Also there are lots of parameters which have simultaneous
effect on final product.
When the solvent pours out of the cavity on the time of its dryness leads to
forces and contraction of gel’s network. Xerogel is the result of dryness. Com-
paring to basic gel Xerogel has less volume due to stress in the dryness procedure
integrated gel is broken and turns to powder. When the wet gel is dried up in a
situation that network cavity has not changed the volume so the result of dried gel
is equals to wet gel which is called Aero gel since there is no contraction in this gel
it has very low density and porous yet it has no stress of contraction. Constancy or
sol’s coalescence in process of sol–gel is very important and the construction of
gel’s network is related to basic form of assembled particle [142–144].
The constancy of a Colloid sol depends on Zeta potential so whenever the Zeta
potential is more sol will have more constancy. For a potential it has equal surface,
barrier and defense force for larger particle. The difference between gravity and
defensive force with measures cause the augmentation of particle and dominancy
of gravity on the defense force and consistency of the sol. Basically the coales-
cence of sol particle is the result of following items:
1. Reduction of surface potential by change in pH
2. Increasing electro lit thickness in the solvent in some cases the coalescence
colloid can be spread which called Peptide process. Overall the sols can be
categorized in 2 groups
1. Mono depress colloid sols
In this type of sols all particles have equal size and form due to huge desire
to agglomeration the creation of this sol is very hard.
2. Micro molecule or polymer sols

In this system particle growth generates with creation of polymer, these
polymers joined each other and entrap the solvent and finally create a semi
solid body called gel. This kind of sols usually can be obtained by Argo no
metallic in alcohol soluble.
Figure 1.3 is an example of condensed nanostructured cerium oxide sol–gel
thin film that illustrates presence of cracks [145].
1.7.2 Sol–gel Chemical Reaction
1. Hydrolysis: Generated by dissolving salt in water, metal cation shapes water

complex. In this condition transfer of electron double from water molecule to
empty medium metal cation orbital. Hydrogen onus increased and water mol-
ecule obtains acidic quality. According to water acidic capacity, it can have
different types of hydrolysis reactions. Overall the increase of bridges of
metallic ions by exeo and hydro exeo ligands and increase of hydrogen in the
ligands simplifies the hydrolysis process.
2. Condensation: This reaction is generated by two different mechanism of
friendly core which depends on metal coordination number. Condensation
created by substitute reaction of friendly core which means by the time the
coordination number is not available the possibility of adding the friendly core
exist.
3. Olation: A condensation process that hydro oxide bridges created between two
metals.
4. Oxolation: A condensation reaction that oxygen bridges created between two
metals [146–149].
Fig. 1.3 SEM images of cerium oxide treated specimens after a 30 min and b 60 min of
immersion in CeCl3 solution [145]
1.7.3 The Effect of Catalyst Hydrolysis
The use of acid catalysts or alkali can have impact on hydrolysis and condensation
speed so it can alter the final product. By giving their H+ the acids increase the
Alco oxide speed in the Hydrolysis reaction. But by reducing the pH the Con-
densation reaction reduces as well. Adding alkali can either increase or decrease
Hydrolysis which depends on types of Alco oxide but the speed of Condensation
increase without considering the kind of material and therefore the density of
chains will enhance. Gels that created by Acid catalysts have longer time to
transform into jelly condition and have less density that face much contraction
while Gels that created by catalysts alkali will have less contraction in the process
of drying due to it’s high density.
1.7.4 Electric Precipitation
The electric precipitation is a coating process based on electro circuit mostly used
to produce metal coating. The precipitation occurs by negative onus of sub layers
of the coating and floating it in a metal salt solvable. The metal salt ions have
positive onus and the absorption of sub layer. While these ions touch the sub layer
it obtains electron and creates metal coating chemically consistence by revival of
procedure. Although this method has usage in copper coating or some solvent, this
is not compatible to environment and is usually it is a toxic that irritates the skin
for example toxic material like chromate should have alternative like coating and
thin film.
1.7.5 The Rotate Coating
In this method while the sub layer is rotating liquid is pouring inside the centre and
by using centrifuge force it will covers the sub layer surface. About 100 percent of
liquid removes out from outside surface. With increase in sub layers like wafers
the process of rotating face technical problem. Impracticality of sub layers/big
pressure room s/braking the sub layer and corner defects in addition to De-wetting
are the main problems of creating steady thin films. Although this process is on the
production line but it requires more solvent and high purity materials, also these
limitations would waste big amount of material.
1.7.6 Scattering Coating
Two main methods exist: plasma scattering coating, thermal scattering coating. In
thermal scattering coating (also called plasma arc plating, plasma arc spraying,
plasma coating) the powder material enters to the gas circuit pit of a plasma gun.
This powder material will spray on the coating surface after the melting. Thermal
spray coating includes heating material (in form of powder or wire) and speeding
up to high pace by gas circuit. The particles collide into sub layer surface and
change the form and finally freeze. The pace of collision is main element which
affects the coating features. Controlling three variants (material, heating and
speed) is necessity for obtaining reliable and repeatable which match the expected
features [150–156].
1.7.7 Self Layout
Self lay out created under proper condition by molecule and atomic design which
occurs in chemical and physical process. It leads to self organization of atoms and
molecules in suitable location with proper construction. The layout of thin films
(mostly in single layers) and on sub layer surfaces which simplify molecules
growth and organization. According to scientists the method is one the rare down
to up methods which pass its infancy and considering many coatings before
entering the industrial phase the basic science should develop. Also there is a vast
confinement in the materials that can be utilized in self layout construction still
there is large area to be discovered. The idea of multiple layers with same action
adds another aspect to the issue.
One of the technical problems insisted by many specialist is molecule activity
which becomes polymerize easily under effect of moisture and create blocks on the
surface and reduce the film reaction. The fact that chemical formulation and
surface pattern of self layout layers are suitable for specific sub layer and leads to
progress in specific usage which also become very expensive. The patterned sub
layers that direct the de coring process or effect growth of thin films is an obstacle
which will be appear by start of industrialized process.
1.7.8 Plasma Polymerization
Plasma polymerization use source of plasma to exit gas, the eviction has the
necessary energy to activate or analysis gas and liquid monomer which usually
include vinyl group so the polymerization process starts. The plasma polymeri-
zation method profits from AC/RF/MW/DC and pulse methods, the method leads
to steady thin polymer films with extensive width connections and heat resistance.
By choosing certain kind of monomer and energy density for each monomer the
chemical form and structure of thin film can be alter in a wide range. The speed of
plasma polymer precipitation is identified by the following parameters: geometry
system, primary monomer reaction, the pace of monomer circuit, gas pressure,
conjoined frequency, signal and finally the sub layer temperature.
Most serious obstacles like temporary constancy (thermal, mechanical, optical

and electricity) or chemical and physical unevenness prevent wider applications.
Some process has the capacity to improve adhesiveness, coincide shine or pre-
cipitation by energetic ions or electronic ray or X-ray. Due to polymer precipi-
tation coating larger 3D pieces will usually face problem in the reaction position
although the issue leads to waste of material, the loss is less dangerous than
material waste from moist chemical process that aims for evening the surface. So
there should be better understating of precipitation concerning the structure of
plasma polymer film and the effects of aging and possibility of removing.
The process of polishing is necessary after fixing the film by wet method or sol–
gel or rotate coating. In other occasions polishing after thin film function as an
important phase in the production (like thermal oxidation for obtaining SiO2 thin
film or glazing with UV for improving thin film adhesiveness by creating width
union). Commonly, most after production processes that have been used many
years in the industry includes following items:
1. Re-decoction
2. Thermal oxidation
3. UV production
According to scientists the first method is the most common way for after
production [157–169].
1.7.9 Annealing
Annealing is a heating treatment which has an altered material in it’s structure

which leads to change in it’s features like constancy and steadiness. This process
includes two phases: slow heating and cooling. The heating treatment usually leads
to alteration in crystal structures of atoms. This alteration includes crystal defects
removal which ends by basic changes in primary features like electric aspect of
material. The main processes are gas annealing and vacuum annealing. The vac-
uum annealing will cause adhesive improvement, solidity stretchiness and electric
treatment and material pit. Although annealing is developed process but it still
needs growth in mechanism and structure control and morphology. Understanding
the effect of annealing on thin film features especially thin polymer films has
significant importance.
High temperature of the process and long period for (slow cooling) prevents any
economical advantages of this process. Some scientists believe that researches
should focus on removing the annealing procedure. They also underline lack of
adjustment with specific material and lack of confidence on repeatability of
annealing process. Figure 1.4 illustrates an example for cross-section of SEM
images of the ceria films which were obtained by sol–gel methods and heat treated
at different temperatures [170].
Fig. 1.4 Cross-section of SEM images of the ceria films which were obtained by Sol–gel
methods and heat treated at different temperatures a 150C b 250C c 300C and d 400C [170]
1.7.10 Heating Oxidation
The thermal oxidation is method used under high temperature (about

700–1,300C) to increase growth rate of oxide layer. The high temperature is used
to enhance the speed of oxidation process (the method used by many materials like
silicon that have natural low rate on oxidation). In this process the raw material of
sub layer has been put in oxidizing environment (oxygen needs dry environment
for oxidation and water for moist oxidation). This action leads to replacement of
raw material with exponential oxide. The oxide growth rate directly depends on
pressure and temperature. There are two obstacles in this method lack of confi-
dence in process repetition and the need to observe the process implementation.
Ultraviolet–visible decoction can be used for drying coating (from solid to
liquid) and creating joint width between sub layer and coating. Excessive areas of
materials from metal papers to polymer films are suitable for UV decoction. There
two parameters in this process: UV intensity and time of decoction. It is possible
that we require different time lines or intensity for various decoction phases. By
the time UV is used for joint width the material has two parts. The adhesive resin
and optical debut (it has been molded by resin earlier). Optical debut only react to
resin when the UV light absorbed suitable (intensity and wave length).
According to scientists when we use UV to create joint width the key issue is
the pressure on the length of decoction process in the film. The proper solvable,
needs conjoining elements (generate joint width) with low wrinkling or no wrin-
kling and specific tests. The other issue is the problem of decoction of complex 3D
pieces with UV, removing shadow regions (with no light) is very hard. According
to scientists view this process is standardized and perfectly applies in its restricted
area but the required instruments to solve problem of under 100 nm is very
expensive. Observing the decoction process is a possible solution for the sug-
gestive obstacles. The following items are the most important applications of thin
films and coatings.
• Thin film transistor (TFT)
• Electronic instrument with extensive surface (like displayers)
• Solar pills (for example thin films under sub layer of polymer glass)
• Navigator of wave papers (for evenness of optical pieces)
• M-RAM
• Micro electronic memory systems (MEMS)
• Friction reduction surfaces
• Insulator windows
• Self cleansing surfaces
Other applications of thin films are anti scratch coating (in auto pieces and
optical components), electro chromic glasses (tungsten oxide layers), anti reflex
coating, anti fog mirrors (by using titanium oxide on the glass), environment
friendly coatings, un-adhesive material and super conductors (micro wave filters or
campers of wrong circuits) [171–182].
1.8 Applications of Nanostructured Coatings
Nowadays, nanotechnology is rapidly developing and promoting the quality of

many products. Industries are making efforts to use these created opportunity to
enhance their products efficiency and quality, as well as decreasing their products’
price. With no doubt, the future belongs to those companies and industries which
invest in this area and extensively apply it. As this is a fairly new emerging
technology, it may enable many industries of our country to invest in this field and
realization using this technology’s outcomes and advantages. Nano-structured
coating is one of most effective broadly used applications of nano-technology. In
most cases, nano-structured coatings characteristics have a significant improve-
ment in comparison with traditional ones. Some of these characteristics are:
increase of hardness, wear strength, abrasion, decadence, environmental pollu-
tions, and etc.
This section attempts to point out some of most important uses of nano-
structures which are currently applied or will be in an upcoming future. Various
sections mostly focus on applicable cases for indoor industry. Furthermore, in
some parts the important applications of nano-structured coatings have been

noticed. The section includes different parts. At first it deals with competence and
applications of coating and surface engineering. The next, discuss the ways to
enhance coating quality using nano-structured coatings and capabilities of nano-
structured coatings—compared with traditional coatings. Other parts are dedicated
to different applications of nano-structured coatings. The categorized applications
include: scratch resistant coatings, abrasion and corrosion, optical coatings,
medical and hygienic applications, electrical and electronic applications, and the
other applications. It must also be added that at final part of this section some
materials with extended applications, namely nano-particles, are introduced with
in addition to their characteristics. Next chapters focus on scratch and wear
resistant coatings. Here, some cases have been mentioned, including: manufac-
turing panels for plane body, using nano-structured coatings in transportation,
military gears, and etc. Also, nano-composite coatings are briefly discussed at this
section. At next part, optical layers have been studied. Most noticeable applica-
tions of nano-structured optical coatings are for making lightproof ultra violet
layers, fog and vapor resistant layers, and self-cleaning glasses. Hygienic and
medical applications are introduced in the next part. Throughout this part the
following cases were studied: Application of nano-particles in microbial and viral
anti-pollution masks, nano-structured coatings for making prosthesis, using nano-
structured coatings in food packaging, anti-pollution materials in shipping indus-
try, nano-particle silver coatings (as a protective agent against bacterial activities),
and using TiO2 nano-particles for reducing environmental pollutions.
It seems that materials such as TiO2 and Ag nano-particles are currently
available for many indoor industries. These materials fairly low prices make them
handy for mass uses. Also, TiO2 particles can be commercially provided in a
commercial scale. Electrical and electronic applications are also a big share of
nanoparticles uses. The use of carbon nano-tubes, nano-structured coatings in solar
cells, coating with nano-structured oxides, polarizers, and transparent conductive
magnetic layers have been previously investigated. Using some of these applica-
tions for indoor industry requires high quality applied technology. It seems that
some of applications are not technically approved. Using nano-structured materials
for coatings process must be available and economically justified. Hence,
regarding vastness of transparent conductive coatings applications, this point is of
great importance. Some applications of nano-structured coatings to use in lubri-
cators are also separately studied.
Currently, it seems to be a vital issue to concentrate on nano-structured coatings
for investments and applying in some industries. Among most important industries
which can easily harness nano-structured coatings, one can name automobile
industry, glasswork industry, packaging industry, making toiletries, and transpor-
tation and military industry. Nano-particles of some materials are of great interests
for nano-structured coatings. Todays, they are widely used in some practices. Some
of most important practices of nano-particles are: TiO2, CuO2, ZnO2, and Al2O3.
Metallic nano-particles such as Ag, also, will be vastly used in an upcoming future.
1.8 Applications of Nanostructured Coatings 17
Some of applied nano-particles characteristics, compared with those of traditional

ones, are also introduced in last section [183–194].
1.9 Coating and Surface Engineering
During production, packaging, and finally preparing in markets, all applied

products needed form require coating. Coatings are used to enhance resistance
against different environmental agents such as various types of corrosion, create
new compatibility in surfaces (e.g. in optical layers), increase hardness, and
improve some physical features such as magnetic and electrical ones. Practice of
coating to deal with corrosion, by its own, is enough to highlight importance of
using coatings. In many developed countries damages induced from corrosion is
from 3.5 to 5% of gross product. Regarding to importance and broad applications
of coating, applied methods in this field are permanently developing and the latest
technology is applied in this field.
Among main objectives of this field, which are of great interest for a long time,
one can name:
• Promoting coating quality, including increase of lifetime and etc.
• Lowering costs for production, repair, and maintenance
• Adapting with environment
Todays, considering development of nano-technology and its practice in dif-
ferent fields, coating can be regarded among most active industries. However,
before advancements in nano-technology field, micrometric and nanometric layers
were used for coating and then the present issues for application of nano-tech-
nology in the other fields, were rarely seen in coating area. With respect to
importance of coating in various industries, particularly in key industries, first of
all we will preview applicable cases and associated problems with coating and
then we will pay to nano-coating applications.
1.10 Coating Issues and Applications
Coating is among main parts of surface engineering. Surface engineering is an

important technology and competition of various industries depends on sponsoring
of this part for them. Besides, as it will be discussed, coating is an economically
vital issue. Considering this, in many countries surface engineering share in key
industry sectors is defined and some of future questions and different predictions
are answered. Discussed topics are similar for many countries. Then, regarding
available reports in this field, upcoming developments of surface engineering
markets and plans in England are studied. In 1995, England market for surface
engineering exceeded 10 billion pounds, where 4.5 billion pounds of these figure
was expended on coating for improvement and enhancement of surface properties

and resistance against corrosion. This figure has caused a 95.5 billion pounds value
effect on amounts of different products. Mentioned values for 2005 are estimated
21.3 and 14.3 billion pounds, respectively. In a more clear fashion, most growth is
for aerospace, agriculture, automobile, electronic consumers, and electronic sec-
tions. This concludes that surface engineering does define differences between
products in terms of function quality and current costs.
Surface engineering involves simultaneous designing and building of surface
and substrate as a system, through promoting their efficiency in term of economic
viewpoint. Main objective of surface engineering is proportional changing of
different technologies to obtain considered surface features in designing to reach a
particular application, with very convenient cost and quality. Surface engineering
can serve in a way that conveys technology and specialty between final consumers.
References
1. Bernand-Mantel, A., Bouzehouane, K., Seneor, P., Fusil, S., Deranlot, C., Brenac, A., Notin,
L., Morel, R., Petroff, F., Fert, A.: A versatile nanotechnology to connect individual nano-
objects for the fabrication of hybrid single-electron devices. Nanotechnology 21 (2010)
2. Stone, D., Harper, B.J., Lynch, I., Dawson, K., Harper, S.L.: Exposure assessment:
recommendations for nanotechnology-based pesticides. Int. J. Occup. Environ. Health 16,
467–474 (2010)
3. Wickson, F., Grieger, K., Baun, A.: Nature and nanotechnology: science, ideology and
policy. Aust. J. Emerg. Technol. Soc. 8, 5–23 (2010)
4. Quandt, A., Özdoğan, C.: Biominerals and graphene—basic aspects of nanoscience.
Commun. Nonlinear Sci. Numer. Simul. 15, 1575–1582 (2010)
5. Zhu, T., Li, J.: Ultra-strength materials. Prog. Mater. Sci. 55, 710–757 (2010)
6. Mirkovic, T., Zacharia, N.S., Scholes, G.D., Ozin, G.A.: Fuel for thought: chemically
powered nanomotors out-swim nature’s flagellated bacteria. ACS Nano 4, 1782–1789
(2010)
7. Taraphdar, C., Chattopadhyay, T., Roy, J.N.: Mach-Zehnder interferometer-based all-
optical reversible logic gate. Opt. Laser Technol. 42, 249–259 (2010)
8. Jones, R.: Feynman’s unfinished business. Nat. Nanotechnol. 4, 785 (2009)
9. Segal, M.: Surely you’re happy, Mr Feynman!. Nat. Nanotechnol. 4, 786–788 (2009)
10. Remin, P., Ferreira, R., Montenegro, J.M., Suau, R., Pérez-Inestrosa, E., Pischel, U.:
Reversible molecular logic: a photophysical example of a Feynman gate. ChemPhysChem
10, 2004–2007 (2009)
11. Ball, P.: Feynman’s fancy Richard Feynman’s famous talk on atom-by-atom assembly is
often credited with kick-starting nanotechnology. Fifty years on, Philip Ball investigates
how influential it really was. Chem. World 6, 58–62 (2009)
12. Pitkethly, M.: Nanotechnology: past, present, and future. Nano Today 3, 6 (2008)
13. Pierotti, M.A., Lombardo, C., Rosano, C.: Nanotechnology: going small for a giant leap in
cancer diagnostics and therapeutics. Tumori 94, 191–196 (2008)
14. Grimes, M., Kobrin, B.: Surface engineering for microfabrication. Solid State Technol. 51,
28–31 (2008)
15. Fadeel, B., Kagan, V., Krug, H., Shvedova, A., Svartengren, M., Tran, L., Wiklund, L.:
There’s plenty of room at the forum: potential risks and safety assessment of engineered
nanomaterials. Nanotoxicology 1, 73–84 (2007)
References 19
16. Toumey, C.: The man who understood the Feynman machine. Nat. Nanotechnol. 2, 9–10
(2007)
17. Devreese, J.T.: Importance of nanosensors: Feynman’s vision and the birth of
nanotechnology. In: Materials Research Society Symposium Proceedings, pp. 78–88. (2006)
18. Junk, A., Riess, F.: From an idea to a vision: there’s plenty of room at the bottom. Am.
J. Phys. 74, 825–830 (2006)
19. Mansoori, G.A., Soelaiman, T.A.F.: Nanotechnology—an introduction for the standards
community. J. ASTM Int. 2, 17–38 (2005)
20. Gröning, P.: Nanotechnology: an approach to mimic natural architectures and concepts.
Adv. Eng. Mater. 7, 279–291 (2005)
21. Ghosh, T.: The base of molecular nanotechnology and its implication in textiles. Colourage
52, 39–43 (2005)
22. Peterson, C.L.: Nanotechnology: from Feynman to the grand challenge of molecular
manufacturing. IEEE Technol. Soc. Mag. 23, 9–15 (2004)
23. Yamada, N.: Quasi-distribution of tunneling time. Acta Phys. Hung. Ser. A Heavy Ion Phys.
19, 329–332 (2004)
24. Gabrys, B.J., Pesz, K., Bartkiewicz, S.J.: Brownian motion, molecular motors and ratchets.
Phys. A Stat. Mech. Appl. 336, 112–122 (2004)
25. Banerjee, R., Katsenovich, Y., Lagos, L., McIintosh, M., Zhang, X., Li, C.Z.:
Nanomedicine: magnetic nanoparticles and their biomedical applications. Curr. Med.
Chem. 17, 3120–3141 (2010)
26. Varnavski, O., Ramakrishna, G., Kim, J., Lee, D., Goodson Iii, T.: Optically excited
acoustic vibrations in quantum-sized monolayer-protected gold clusters. ACS Nano 4,
3406–3412 (2010)
27. Pattantyus-Abraham, A.G., Kramer, I.J., Barkhouse, A.R., Wang, X., Konstantatos, G.,
Debnath, R., Levina, L., Raabe, I., Nazeeruddin, M.K., Grätzel, M., Sargent, E.H.:
Depleted-heterojunction colloidal quantum dot solar cells. ACS Nano 4, 3374–3380 (2010)
28. Kreimeyer, A.: Size does matter. OECD Observer (2010)
29. Oviedo, O.A., Mariscal, M.M., Leiva, E.P.M.: Theoretical studies of preparation of core-
shell nanoparticles by electrochemical metal deposition. Electrochim. Acta 55, 8244–8251
(2010)
30. De Julin Fernndez, C., Mattei, G., Paz, E., Novak, R.L., Cavigli, L., Bogani, L., Palomares,
F.J., Mazzoldi, P., Caneschi, A.: Coupling between magnetic and optical properties of stable
Au-Fe solid solution nanoparticles. Nanotechnology 21 (2010)
31. Keten, S., Xu, Z., Ihle, B., Buehler, M.J.: Nanoconfinement controls stiffness, strength and
mechanical toughness of b-sheet crystals in silk. Nat. Mater. 9, 359–367 (2010)
32. Robertson, C.G., Hogan, T.E., Rackaitis, M., Puskas, J.E., Wang, X.: Effect of nanoscale
confinement on glass transition of polystyrene domains from self-assembly of block
copolymers. J. Chem. Phys. 132 (2010)
33. Miloshev, N., Miloshev, G.: Effect of small particle sizes on the equilibrium crystal shape
and the work of nucleus formation. Comptes Rendus de L’Academie Bulgare des Sciences
63, 211–220 (2010)
34. Peng, Y., Wang, Y., Yang, Y., Dlott, D.D.: Simulation of the absorption spectra of
nanometallic Al particles with core-shell structure: size-dependent interband transitions.
J. Nanopart. Res. 12, 777–787 (2010)
35. De Paoli Lacerda, S.H., Park, J.J., Meuse, C., Pristinski, D., Becker, M.L., Karim, A.,
Douglas, J.F.: Interaction of gold nanoparticles with common human blood proteins. ACS
Nano 4, 365–379 (2010)
36. Ohno, T., Tagawa, S., Itoh, H., Suzuki, H., Matsuda, T.: Size effect of TiO2–SiO2 nano-
hybrid particle. Mater. Chem. Phys. 113, 119–123 (2009)
37. Ko, S.H., Pan, H., Hotz, N., Grigoropoulos, C.P.: Large area flexible electronics fabrication
by selective laser sintering of nanoparticles with a scanning mirror. In: Materials Research
Society Symposium Proceedings, pp. 7–12. (2010)
38. Murzin, D.Y.: Kinetic analysis of cluster size dependent activity and selectivity. J. Catal.
276, 85–91 (2010)
39. Soria, J., Sanz, J., Sobrados, I., Coronado, J.M., Hernández-Alonso, M.D., Fresno, F.:
Water–hydroxyl interactions on small anatase nanoparticles prepared by the hydrothermal
route. J. Phys. Chem. C 114, 16534–16540 (2010)
40. Miyazaki, A., Ito, Y., Enoki, T.: Classes of nanomagnets created from alkanethiol-coated Pt
or Pd nanoparticles and their alloys with Co. Eur. J. Inorg. Chem. 4279–4287 (2010)
41. Hai, P.N., Ohya, S., Tanaka, M.: Long spin-relaxation time in a single metal nanoparticle.
Nat. Nanotechnol. 5, 593–596 (2010)
42. Tang, W., Lu, W., Luo, X., Wang, B., Zhu, X., Song, W., Yang, Z., Sun, Y.: Particle size
effects on La0.7Ca0.3MnO3: size-induced changes of magnetic phase transition order and
magnetocaloric study. J. Mag. Mag. Mater. 322, 2360–2368 (2010)
43. El Nimr, M.K., Moharram, B.M., Saafan, S.A., Assar, S.T.: Particle size distribution,
magnetic permeability and dc conductivity of nano-structured and bulk LiNiZn–ferrite
samples. J. Magn. Magn. Mater. 322, 2108–2112 (2010)
44. Cheng, R., Zhou, W., Wang, J.L., Qi, D., Guo, L., Zhang, W.X., Qian, Y.: Dechlorination of
pentachlorophenol using nanoscale Fe/Ni particles: role of nano-Ni and its size effect.
J. Hazard. Mater. 180, 79–85 (2010)
45. Chen, W., Kimel, A., Kirilyuk, A., Rasing, T.: Apertureless SNOM study on gold
nanoparticles: experiments and simulations. Phys. Status Solid (B) Basic Res. 247,
2047–2050 (2010)
46. Khazrayie, M.A., Aghdam, A.R.S.: Si3N4/Ni nanocomposite formed by electroplating:
effect of average size of nanoparticulates. Transactions of Nonferrous Metals Society of
China (English Edition), vol. 20, pp. 1017–1023. (2010)
47. Tomenson, J.A., Morfeld, P.: Multiple errors made by authors result in a huge
overestimation of potential exposure to particles in the size range 10–30nm in TiO2
nanoparticle production facilities. J. Hazard. Mater. 183, 954–955 (2010)
48. Landi, G.T., Santos, A.D.: High-density gas aggregation nanoparticle gun applied to the
production of SmCo clusters. J. Mater. Sci. 45, 4906–4911 (2010)
49. Knieke, C., Steinborn, C., Romeis, S., Peukert, W., Breitung-Faes, S., Kwade, A.:
Nanoparticle production with stirred-media mills: opportunities and limits. Chem. Eng.
Technol. 33, 1401–1411 (2010)
50. Hu, P., O’Neil, W., Hu, Q.: Synthesis of 10 nm Ag nanoparticle polymer composite pastes for
low temperature production of high conductivity films. Appl. Surf. Sci. 257, 680–685 (2010)
51. Marin-Flores, O., Turba, T., Ellefson, C., Scudiero, L., Breit, J., Norton, M.G., Ha, S.:
Nanoparticle molybdenum dioxide: a new alternative catalytic material for hydrogen
production via partial oxidation of jet-a fuels. J. Nanoelectron. Optoelectron. 5, 110–114
(2010)
52. Zhang, Y.T., Guo, Y., Wang, D.W., Feng, Y., Ma, T.C.: Fe nanoparticle production by an
atmospheric cold plasma jet. Chin. Phys. Lett. 27 (2010)
53. Shah, V., Dobiášová, P., Baldrian, P., Nerud, F., Kumar, A., Seal, S.: Influence of iron and
copper nanoparticle powder on the production of lignocellulose degrading enzymes in the
fungus trametes versicolor. J. Hazard. Mater. 178, 1141–1145 (2010)
54. Patel, N., Fernandes, R., Guella, G., Miotello, A.: Nanoparticle-assembled Co–B thin film
for the hydrolysis of ammonia borane: a highly active catalyst for hydrogen production.
Appl. Catal. B Environ. 95, 137–143 (2010)
55. Iwuchukwu, I.J., Vaughn, M., Myers, N., O’Neill, H., Frymier, P., Bruce, B.D.: Self-
organized photosynthetic nanoparticle for cell-free hydrogen production. Nat. Nanotechnol.
5, 73–79 (2010)
56. Delaportas, D., Svarnas, P., Alexandrou, I., Siokou, A., Black, K., Bradley, J.W.: Gamma-
Al2O3 nanoparticle production by arc-discharge in water. J. Phys. D Appl. Phys. 42 (2009)
57. Ding, J., Gao, Q., Luo, D., Shi, Z.G., Feng, Y.Q.: n-Octadecylphosphonic acid grafted
mesoporous magnetic nanoparticle: preparation, characterization, and application in
magnetic solid-phase extraction. J. Chromatogr. A 1217, 7351–7358 (2010)
References 21
58. Zalba, S., Navarro-Blasco, I., Moreno, D., Garrido, M.J.: Application of non-aggressive
sample preparation and electrothermal atomic absorption spectrometry to quantify platinum
in biological matrices after cisplatin nanoparticle administration. Microchem. J. 96,
415–421 (2010)
59. Hoertz, P.G., Chen, Z., Kent, C.A., Meyer, T.J.: Application of high surface area tin-doped
indium oxide nanoparticle films as transparent conducting electrodes. Inorg. Chem. 49,
8179–8181 (2010)
60. Feng, S., Ren, Z., Wei, Y., Jiang, B., Liu, Y., Zhang, L., Zhang, W., Fu, H.: Synthesis and
application of hollow magnetic graphitic carbon microspheres with/without TiO2
nanoparticle layer on the surface. Chem. Commun. 46, 6276–6278 (2010)
61. Oh, J.H., Lee, J.S.: Salt concentration-induced dehybridisation of DNA–gold nanoparticle
conjugate assemblies for diagnostic applications. Chem. Commun. 46, 6382–6384 (2010)
62. Frasconi, M., Tortolini, C., Botrè, F., Mazzei, F.: Multifunctional Au nanoparticle
dendrimer-based surface plasmon resonance biosensor and its application for improved
insulin detection. Anal. Chem. 82, 7335–7342 (2010)
63. George, C., Kuriakose, S., Prakashkumar, B., Mathew, T.: Synthesis, characterisation and
antibacterial applications of water-soluble, silver nanoparticle-encapsulated-cyclodextrin.
Supramol. Chem. 22, 511–516 (2010)
64. Wang, J., Munir, A., Zhu, Z., Zhou, H.S.: Magnetic nanoparticle enhanced surface plasmon
resonance sensing and its application for the ultrasensitive detection of magnetic
nanoparticle-enriched small molecules. Anal. Chem. 82, 6782–6789 (2010)
65. Mechiakh, R., Sedrine, N.B., Chtourou, R., Bensaha, R.: Correlation between
microstructure and optical properties of nano-crystalline TiO2 thin films prepared by sol–
gel dip coating. Appl. Surf. Sci. 257, 670–676 (2010)
66. Khaleeq-Ur-Rahman, M., Bhatti, K.A., Rafique, M.S., Anjum, S., Latif, A., Anjum, M.,
Ahsan, A., Ozair, H.: Morphological and structural analysis of nano-structured gold thin
film on silicon by pulsed laser deposition technique. Vacuum 85, 353–357 (2010)
67. Li, C., Li, Z., Zhu, H., Wang, K., Wei, J., Li, X., Sun, P., Zhang, H., Wu, D.: Graphene
nano-‘‘patches’’ on a carbon nanotube network for highly transparent/conductive thin film
applications. J. Phys. Chem. C 114, 14008–14012 (2010)
68. Han, X., Wang, L., Liu, P., Yue, Y., Yang, M., Sun, J., Zhang, Z.: Dynamic atomic
mechanisms of plasticity of Ni nanowires and nano crystalline ultra-thin films. In: Materials
Science Forum, pp. 2293–2296. (2010)
69. Wu, C.W., Lee, J.L., Lin, Y., Shen, Y.K.: Surface modification of plastic thin film using
anodic aluminum oxide template for nano imprint. In: Key Engineering Materials,
pp. 711–716. (2010)
70. Sasikumar, D., Ganesan, S.: Effect of temperature and current density in electrodeposited
Co–W magnetic nano thin film. Dig. J. Nanomater. Biostruct. 5, 477–482 (2010)
71. Wu, F., Fang, L., Zhou, K., Pan, Y.J., Peng, L.P., Huang, Q.L., Yang, X.F., Kong, C.Y.:
Effect of thickness on the properties of Ga-doped Nano-ZnO thin films prepared by RF
magnetron sputtering. J. Supercond. Nov. Mag. 23, 905–908 (2010)
72. Xiong, L., Liu, F., Wang, J., Man, W., Weng, J., Liu, C.: Plasma processing of boron-doped
nano-crystalline diamond thin film fabricated on poly-crystalline diamond thick film.
Plasma Sci. Technol. 12, 433–436 (2010)
73. Fang, L., Yang, X.F., Peng, L.P., Zhou, K., Wu, F., Huang, Q.L., Kong, C.Y.:
Thermoelectric and magnetothermoelectric properties of In-doped Nano-ZnO thin films
prepared by RF magnetron sputtering. J. Superconduct. Nov. Mag. 23, 889–892 (2010)
74. Mukherjee, N., Mondal, A.: Comparative study on the properties of galvanically deposited
nano- and microcrystalline thin films of PbSe. J. Elec. Mater. 39, 1177–1185 (2010)
75. Schulz, B., Täuber, D., Friedriszik, F., Graaf, H., Schuster, J., Von Borczyskowski, C.:
Optical detection of heterogeneous single molecule diffusion in thin liquid crystal films.
Phys. Chem. Chem. Phys. 12, 11555–11564 (2010)
76. Li, T.D., Inigo, A.R., Fann, W., White, J.D., Huang, Y.F., Wei, P.K.: Development of a
controlled environment near-field optical microscope for organic thin film studies. J. Chin.
Chem. Soc. 57, 469–477 (2010)
77. Wang, Y., Zhao, N., Zhang, M., Zhao, X.: Optical waveguide and nonlinear properties of
Bi3NdTi3O12 thin films. J. Wuhan Univ. Technol. Mater. Sci. Ed. 25, 743–746 (2010)
78. Hegab, N.A., El-Mallah, H.M.: Optical properties of As36Te42Ge10Si12 thin films. Acta
Phys. Polonica A 118, 637–642 (2010)
79. Suthan Kissinger, N.J., Suthagar, J., Saravana Kumar, B., Balasubramaniam, T., Perumal,
K.: Effect of substrate temperature on the structural and optical properties of nanocrystalline
cadmium selenide thin films prepared by electron beam evaporation technique. Acta Phys.
Polonica A 118, 623–628 (2010)
80. Basova, T., Hassan, A., Yuksel, F., Gurek, A.G., Ahsen, V.: Optical detection of
pentachlorophenol in water using thin films of octa-tosylamido substituted zinc
phthalocyanine. Sens. Actuators B Chem. 150, 523–528 (2010)
81. Kim, I.Y., Kim, K.J., Shin, J.H.: Preventing optical deactivation of nanocluster Si sensitized
Er using nanometer-thin SiNx/SiO2:Er heterolayer thin film. J. Appl. Phys. 108 (2010)
82. Liu, C., Morko, H.: Regrowth of ZnO thin film with high surface flatness and enhanced
optical properties on annealed buffer layers by rf sputtering deposition. Superlattices
Microstruct. 48, 502–508 (2010)
83. Mohamed, S.H., Raaif, M.: Effects of thickness and rf plasma oxidizing on structural and
optical properties of SiOxNy thin films. Surf. Coat. Technol. 205, 525–532 (2010)
84. Bourgoin, J.P., Allogho, G.G., Haché, A.: Thermal conduction in thin films measured by
optical surface thermal lensing. J. Appl. Phys. 108 (2010)
85. Mahmoud, W.E., Al-Ghamdi, A.A.: Synthesis of CdZnO thin film as a potential candidate
for optical switches. Opt. Laser Technol. 42, 1134–1138 (2010)
86. Tong, G.B., Muhamad, M.R., Rahman, S.A.: Optical properties of annealed Si:H thin film
prepared by layer-by-layer (LBL) deposition technique. Phys. B Condens. Matter 405,
4838–4844 (2010)
87. Fu, C.F., Chen, X.M., Li, L., Han, L.F., Wu, X.: Effects of the Cr doping on structure and
optical properties of ZnO thin films. Optoelectron. Lett. 6, 37–40 (2010)
88. Cao, M., Sun, Y., Wu, J., Chen, X., Dai, N.: Effects of cadmium salts on the structure,
morphology and optical properties of acidic chemical bath deposited CdS thin films.
J. Alloys Compd. 508, 297–300 (2010)
89. Nathanael, A.J., Mangalaraj, D., Ponpandian, N.: Controlled growth and investigations on
the morphology and mechanical properties of hydroxyapatite/titania nanocomposite thin
films. Compos. Sci. Technol. 70, 1645–1651 (2010)
90. Chou, H.S., Huang, J.C., Chang, L.W.: Mechanical properties of ZrCuTi thin film metallic
glass with high content of immiscible tantalum. Surf. Coat. Technol. 205, 587–590 (2010)
91. Haseeb, A.S.M.A., Hasan, M.M., Masjuki, H.H.: Structural and mechanical properties of
nanostructured TiO2 thin films deposited by RF sputtering. Surf. Coat. Technol. 205,
338–344 (2010)
92. Chawla, V., Jayaganthan, R., Chandra, R.: Influence of sputtering pressure on the structure
and mechanical properties of nanocomposite Ti–Si–N thin films. J. Mater. Sci. Technol. 26,
673–678 (2010)
93. Yen, C.Y., Jian, S.R., Lai, Y.S., Yang, P.F., Liao, Y.Y., Jang, J.S.C., Lin, T.H., Juang, J.Y.:
Mechanical properties of the hexagonal HoMnO3 thin films by nanoindentation. J. Alloys
Compd. 508, 523–527 (2010)
94. Rathod, V.T., Mahapatra, D.R., Jain, A., Gayathri, A.: Characterization of a large-area
PVDF thin film for electro-mechanical and ultrasonic sensing applications. Sens. Actuators
A Phys. 163, 164–171 (2010)
95. Choi, Y.H., Bulliard, X., Benayad, A., Leterrier, Y., Mnson, J.A.E., Lee, K.H., Choi, D.,
Park, J.J., Kim, J.: Design and fabrication of compositionally graded inorganic oxide thin
films: mechanical, optical and permeation characteristics. Acta Mater. 58, 6495–6503
(2010)
References 23
96. Vosgueritchian, M., Lemieux, M.C., Dodge, D., Bao, Z.: Effect of surface chemistry on
electronic properties of carbon nanotube network thin film transistors. ACS Nano 4,
6137–6145 (2010)
97. Ohsawa, T., Iwaya, K., Shimizu, R., Hashizume, T., Hitosugi, T.: Thickness-dependent
local surface electronic structures of homoepitaxial SrTiO3 thin films. J. Appl. Phys. 108
(2010)
98. Karamat, S., Rawat, R.S., Ghaffari, M., Lee, P., Tan, T.L.: Electronic, structural and
magnetic characterization of bulk (ZnO)1-x(MnO2)x system and their PLD synthesized thin
films at room temperature. J. Phys. Conf. Ser. 200 (2010)
99. Luo, C.W., Lo, H.P., Su, C.H., Wu, I.H., Chen, Y.J., Wu, K.H., Lin, J.Y., Uen, T.M., Juang,
J.Y., Kobayashi, T.: Doping dependence of the ultrafast electronic dynamics of Y1-x Prx Ba2
Cu3O7-d thin-film superconductors from femtosecond optical spectroscopy. Phys. Rev.
B Condens. Matter Mater. Phys. 82 (2010)
100. Lee, J.S., Nakamura, M., Okuyama, D., Kumai, R., Arima, T., Kawasaki, M., Tokura, Y.:
Competing electronic orders in anisotropically strained (Pr0.6 Ca0.4)1-x (La0.6
Sr0.4) x MnO3 thin films. Phys. Rev. B Condens. Matter Mater. Phys. 82 (2010)
101. El Amrani, A., Hijazi, F., Lucas, B., Bouclé, J., Aldissi, M.: Electronic transport and optical
properties of thin oxide films. Thin Solid Films 518, 4582–4585 (2010)
102. Chu, C.H., Da Shiue, C., Cheng, H.W., Tseng, M.L., Chiang, H.P., Mansuripur, M., Tsai,
D.P.: Laser-induced phase transitions of Ge2Sb2Te5 thin films used in optical and electronic
data storage and in thermal lithography. Opt. Express 18, 18383–18393 (2010)
103. Van Der Laan, G., Chopdekar, R.V., Suzuki, Y., Arenholz, E.: Strain-induced changes in the
electronic structure of MnCr2O4 thin films probed by X-ray magnetic circular dichroism.
Phys. Rev. Lett. 105 (2010)
104. Haupricht, T., Sutarto, R., Haverkort, M.W., Ott, H., Tanaka, A., Hsieh, H.H., Lin, H.J.,
Chen, C.T., Hu, Z., Tjeng, L.H.: Local electronic structure of Fe2+ impurities in MgO thin
films: temperature-dependent soft x-ray absorption spectroscopy study. Phys. Rev.
B Condens. Matter Mater. Phys. 82 (2010)
105. Macmanus-Driscoll, J.L.: Self-assembled heteroepitaxial oxide nanocomposite thin film
structures: designing interface-induced functionality in electronic materials. Adv. Funct.
Mater. 20, 2035–2045 (2010)
106. Kanai, K., Miyazaki, T., Wakita, T., Akaike, K., Yokoya, T., Ouchi, Y., Seki, K.: Lateral
inhomogeneity in the electronic structure of a conjugated poly(3-hexylthiophene) thin film.
Adv. Funct. Mater. 20, 2046–2052 (2010)
107. Maruyama, Y., Motohashi, S., Tanaka, M., Ogata, H., Zhou, B., Kobayashi, A., Shoda, M.,
Bandow, S., Iijima, S.: Some electronic properties and morphological features of hybrid
material DNASWCNT thin films. Solid State Commun. 150, 1584–1586 (2010)
108. Wang, S.J., Wong, T.I., Chen, Q., Yang, M., Wong, L.M., Chai, J.W., Zhang, Z., Pan, J.S.,
Feng, Y.P.: Feng, Atomic and electronic structures at ZnO and ZrO2 interface for
transparent thin-film transistors. Phys. Status Solid (A) Appl. Mater. 207, 1731–1734 (2010)
109. Latteyer, F., Peisert, H., Göhring, N., Peschel, A., Chassé, T.: Vibrational and electronic
characterisation of Staphylococcus aureus wall teichoic acids and relevant components in
thin films. Anal. Bioanal. Chem. 397, 2429–2437 (2010)
110. Shin, H., Sim, B., Lee, M.: Laser-driven high-resolution patterning of indium tin oxide thin
film for electronic device. Opt. Lasers Eng. 48, 816–820 (2010)
111. Tahir, D., Kwon, H.L., Shin, H.C., Oh, S.K., Kang, H.J., Heo, S., Chung, J.G., Lee, J.C.,
Tougaard, S.: Electronic and optical properties of Al2O3/SiO2 thin films grown on Si
substrate. J. Phys. D Appl. Phys. 43 (2010)
112. Asenjo, B., Guilln, C., Chaparro, A.M., Saucedo, E., Bermudez, V., Lincot, D., Herrero, J.,
Gutirrez, M.T.: Properties of In2S3 thin films deposited onto ITO/glass substrates by
chemical bath deposition. J. Phys. Chem. Solids 71, 1629–1633 (2010)
113. Park, T.J., Kim, J.H., Jang, J.H., Lee, J., Lee, S.W., Kim, U.K., Seo, M., Jung, H.S., Lee, S.Y.,
Hwang, C.S.: Optimized electrical properties and chemical structures of SrTiO3 thin films on
Si using various interfacial barrier layers. J. Electrochem. Soc. 157, G216–G220 (2010)
114. Guneri, E., Ulutas, C., Kirmizigul, F., Altindemir, G., Gode, F., Gumus, C.: Effect of
deposition time on structural, electrical, and optical properties of SnS thin films deposited
by chemical bath deposition. Appl. Surf. Sci. 257, 1189–1195 (2010)
115. Wang, L., Chen, C., Tang, Z., Lu, C., Yu, B.: Dependence of Zr content on electrical
properties of Bi3.15Nd0.85Ti3–xZrxO12 thin films synthesized by chemical solution
deposition (CSD). Vacuum 85, 203–206 (2010)
116. Ubale, A.U.: Effect of complexing agent on growth process and properties of nanostructured
Bi2S3 thin films deposited by chemical bath deposition method. Mater. Chem. Phys. 121,
555–560 (2010)
117. Mohan, S., Taen, T., Yagyuda, H., Nakajima, Y., Tamegai, T., Katase, T., Hiramatsu, H.,
Hosono, H.: Transport and magnetic properties of Co-doped BaFe2As2 epitaxial thin films
grown on MgO substrate. Supercond. Sci. Technol. 23 (2010)
118. Brunken, H., Somsen, C., Savan, A., Ludwig, A.: Microstructure and magnetic properties of
FeCo/Ti thin film multilayers annealed in nitrogen. Thin Solid Films 519, 770–774 (2010)
119. Belmeguenai, M., Zighem, F., Chauveau, T., Faurie, D., Roussigá, Y., Chérif, S.M., Moch,
P., Westerholt, K., Monod, P.: Structural, static and dynamic magnetic properties of
Co2MnGe thin films on a sapphire a-plane substrate. J. Appl. Phys. 108 (2010)
120. Sugai, I., Sakai, S., Matsumoto, Y., Naramoto, H., Mitani, S., Takanashi, K., Maeda, Y.:
Composition dependence of magnetic and magnetotransport properties in C60–Co granular
thin films. J. Appl. Phys. 108 (2010)
121. Kim, C.O., Kim, S., Oh, H.T., Choi, S.H., Shon, Y., Lee, S., Hwang, H.N., Hwang, C.C.:
Effect of electrical conduction properties on magnetic behaviors of Cu-doped ZnO thin
films. Phys. B Conden. Matter 405, 4678–4681 (2010)
122. Hu, Y.C., Hou, D.L., Gao, W.X., Zhang, Q., Ma, L., Zhen, C.M., Tang, G.D.: Study of the
local micro-structure and magnetic and transport properties of CrxGe1-x thin films. J. Mag.
Mag. Mater. 322, 3902–3906 (2010)
123. St, K., Wesselinowa, J.M.: Electric field control of magnetic properties in multiferroic thin
films. Phys. Status Solid (B) Basic Res. 247, 2284–2289 (2010)
124. Krishnappa, M.R.M., Rajasekaran, N., Ganesan, S., Emerson, R.N.: Influence of organic
additive thiourea on the properties of hard magnetic CoMnP thin film alloys
electrodeposited from chloride bath. J. Optoelectron. Adv. Mater. 12, 1863–1868 (2010)
125. Gredig, T., Gentry, K.P., Colesniuc, C.N., Schuller, I.K.: Control of magnetic properties in
metallo-organic thin films. J. Mater. Sci. 45, 5032–5035 (2010)
126. Lu, W., Wang, Y., Yan, B., Suzuki, T.: Magnetic properties and first-order magnetic phase
transition in single crystal FeRh thin film. J. Mater. Sci. 45, 4919–4923 (2010)
127. Karaagac, H., Parlak, M.: Investigation of physical properties of quaternary AgGa
o.5Ino.5Te2 thin films deposited by thermal evaporation. J. Alloys Compd. 503, 468–473
(2010)
128. Mavrokefalos, A., Lin, Q., Beekman, M., Seol, J.H., Lee, Y.J., Kong, H., Pettes, M.T.,
Johnson, D.C., Shi, L.: In-plane thermal and thermoelectric properties of misfit-layered
[(PbSe) 0.99] x (WSe2) x superlattice thin films. Appl. Phys. Lett. 96 (2010)
129. Nagase, K., Kubo, S., Nakagawa, M.: Resist properties of thin poly(methyl methacrylate)
and polystyrene films patterned by thermal nanoimprint lithography for au
electrodeposition. Jpn. J. Appl. Phys. 49, 06GL051–06GL055 (2010)
130. Ouni, B., Ouerfelli, J., Amlouk, A., Boubaker, K., Amlouk, M.: Structural, mechanical and
opto-thermal properties of non-crystalline SbxOy thin films. J. Non Cryst. Solids 356, 1294–
1299 (2010)
131. Gaikwad, R.S., Chae, S.Y., Mane, R.S., Cai, G., Han, S.H., Joo, O.S.: Large area (9*9 cm2)
electrostatically sprayed nanocrystalline zincite thin films for hydrogen production
application. Int. J. Hydrogen Energy 35, 6549–6553 (2010)
132. Maggioni, G., Carturan, S., Quaranta, A., Vomiero, A., Tonezzer, M., Della Mea, G.:
Production and characterization of thin film materials for indoor optical gas sensing
applications. J. Phys. Conf. Ser. 41, 531–534 (2006)
References 25
133. Zhang, Y., Gao, J., Meng, G., Liu, X.: Production of dense yttria-stabilized zirconia thin
films by dip-coating for IT-SOFC application. J. Appl. Electrochem. 34, 637–641 (2004)
134. Huang, L., Wang, F., Luan, Z., Meng, L.: Pyrite (FeS2) thin films deposited by sol-gel
method. Mater. Lett. 64, 2612–2615 (2010)
135. Yakuphanoglu, F.: Nanocluster n-CdO thin film by sol-gel for solar cell applications. Appl.
Surf. Sci. 257, 1413–1419 (2010)
136. Kakati, N., Jee, S.H., Kim, S.H., Oh, J.Y., Yoon, Y.S.: Thickness dependency of sol-gel
derived ZnO thin films on gas sensing behaviors. Thin Solid Films 519, 494–498 (2010)
137. Carvalho, D.M., MacIel Jr, J.L.B., Ravaro, L.P., Garcia, R.E., Ferreira, V.G., Scalvi,
L.V.A.: Numerical simulation of the liquid phase in SnO2 thin film deposition by sol-gel-
dip-coating. J. Sol Gel Sci. Technol. 55, 385–393 (2010)
138. Veberš, A., Kunej, S., Cerc Korošc, R., Suvorov, D.: The effects of solvents on the
formation of sol-gel-derived Bi12SiO20 thin films. J. Eur. Ceram. Soc. 30, 2475–2480 (2010)
139. Kim, C.Y., Sekino, T., Niihara, K.: Optical, mechanical, and dielectric properties of Bi1/
2Na1/2TiO3 thin film synthesized by sol-gel method. J. Sol Gel Sci. Technol. 55, 306–310
(2010)
140. Xu, J.B., Shen, B., Zhai, J.W.: Dielectric, ferroelectric and optical properties of BaZr
0.2Ti0.8O3 thin films prepared by sol-gel-hydrothermal process. J. Sol Gel Sci. Technol. 55,
343–347 (2010)
141. Longley, J.E., Chaudhury, M.K.: Determination of the modulus of thin sol-gel films using
buckling instability. Macromolecules 43, 6800–6810 (2010)
142. Perez, J., Vilarinho, P.M., Kholkin, A.L., Almeida, A.: Sol-gel reaction stability studied:
influence in the formation temperature and properties of ferroelectric thin films. Mater. Res.
Bull. 44, 515–521 (2009)
143. Long, J.W., Qadir, L.R., Stroud, R.M., Rolison, D.R.: Spectroelectrochemical investigations
of cation-insertion reactions at sol-gel-derived nanostructured, mesoporous thin films of
manganese oxide. J. Phys. Chem. B 105, 8712–8717 (2001)
144. Rivera, D., Harris, J.M.: In situ ATR-FT-IR kinetic studies of molecular transport and
surface binding in thin sol-gel films: reactions of chlorosilane reagents in porous silica
materials. Anal. Chem. 73, 411–423 (2001)
145. Hasannejad, H., Aliofkhazraei, M., Shanaghi, A., Shahrabi, T., Sabour, A.R.: Nanostructural
and electrochemical characteristics of cerium oxide thin films deposited on AA5083-H321
aluminum alloy substrates by dip immersion and sol-gel methods. Thin Solid Films 517,
4792–4799 (2009)
146. Jeong, H., Lee, W.E., Kwak, G.: Enhancements in emission and chemical resistance of
substituted acetylene polymer via in situ sol-gel reaction in film. Macromolecules 43,
1152–1155 (2010)
147. Lao, J., Nedelec, J.M., Moretto, P., Jallot, E.: Micro-ion beam analysis of physico-chemical
reactions at the interface between sol-gel derived glass particles in the SiO2–CaO system
and biological fluids. Surf. Interface Anal. 40, 162–166 (2008)
148. Mutlu, I.H., Acun, H., Celik, E., Turkmen, H.: Preparation of YBa2Cu3O7-x
superconducting solutions and films from alkoxide-based precursors using sol-gel method
and investigation of their chemical reaction mechanisms. Phys. C Superconduct. Appl. 451,
98–106 (2007)
149. Jallot, E., Nedelec, J.M., Grimault, A.S., Chassot, E., Grandjean-Laquerriere, A.,
Laquerriere, P., Laurent-Maquin, D.: STEM and EDXS characterisation of physico-
chemical reactions at the periphery of sol-gel derived Zn-substituted hydroxyapatites during
interactions with biological fluids. Colloids Surf. B Biointerfaces 42, 205–210 (2005)
150. Sun, X., Wang, H., Zhang, H.: Scattering of gaussian beam by a conducting spheroidal
particle with confocal dielectric coating. J. Infrared Millim. Terahertz Waves 31,
1100–1108 (2010)
151. Jonsson, A., Roos, A., Jonson, E.K.: The effect on transparency and light scattering of dip
coated antireflection coatings on window glass and electrochromic foil. Sol. Energy Mater.
Sol. Cells 94, 992–997 (2010)
152. Schroder, S., Herffurth, T., Trost, M., Duparré, A.: Angle-resolved scattering and
reflectance of extreme-ultraviolet multilayer coatings: measurement and analysis. Appl.
Opt. 49, 1503–1512 (2010)
153. Wang, M., Zhang, H., Han, Y., Li, Y.: Scattering of shaped beam by a conducting infinite
cylinder with dielectric coating. Appl. Phys. B Lasers Opt. 96, 105–109 (2009)
154. Kostanski, L.K., Pope, M.A., Hrymak, A.N., Gallant, M., Whittington, W.L., Vesselov, L.:
Development of novel tunable light scattering coating materials for fiber optic diffusers in
photodynamic cancer therapy. J. Appl. Polym. Sci. 112, 1516–1523 (2009)
155. Li, Y., Chi, W., Sampath, S., Goland, A., Herman, H., Allen, A.J., Ilavsky, J.: Process-
controlled plasma-sprayed Yttria-stabilized zirconia coatings: new insights from ultrasmall-
angle X-ray scattering. J. Am. Ceram. Soc. 92, 491–500 (2009)
156. Eldridge, J.I., Spuckler, C.M.: Determination of scattering and absorption coefficients for
plasma-sprayed yttria-stabilized zirconia thermal barrier coatings. J. Am. Ceram. Soc. 91,
1603–1611 (2008)
157. Chen, R.T., Muir, B.W., Such, G.K., Postma, A., McLean, K.M., Caruso, F.: Fabrication of
asymmetric ‘‘janus’’ particles via plasma polymerization. Chem. Commun. 46, 5121–5123
(2010)
158. Guo, R., Talma, A.G., Datta, R.N., Dierkes, W.K., Noordermeer, J.W.M.: Novel surface
modification of sulfur by plasma polymerization and its application in dissimilar rubber–
rubber blends. Plasma Chem. Plasma Process. 30, 679–695 (2010)
159. Hua, X., Zhang, T., Ren, J., Zhang, Z., Ji, Z., Jiang, X., Ling, J., Gu, N.: A facile approach to
modify polypropylene flakes combining O2-plasma treatment and graft polymerization of l-
lactic acid. Colloids Surf. A Physicochem. Eng. Aspects 369, 128–135 (2010)
160. Huang, C., Liu, C.H., Hsu, W.T., Chou, T.H.: Chamberless plasma polymerization of
fluorocarbon thin films. J. Non Cryst. Solids 356, 1791–1794 (2010)
161. Jimenez, M., Bellayer, S., Duquesne, S., Bourbigot, S.: Improvement of heat resistance of
high performance fibers using a cold plasma polymerization process. Surf. Coat. Technol.
205, 745–758 (2010)
162. Paosawatyanyong, B., Kamphiranon, P., Bhanthumnavin, W.: Coating of polythiophene by
microwave plasma polymerization process. In: Key Engineering Materials, pp. 493–498.
(2010)
163. Saxena, S., Ray, A.R., Mindemart, J., Hilborn, J., Gupta, B.: Plasma-induced graft
polymerization of acrylic acid onto poly(propylene) monofilament: characterization. Plasma
Process. Polym. 7, 610–618 (2010)
164. Seo, H.S., Ko, Y.M., Shim, J.W., Lim, Y.K., Kook, J.K., Cho, D.L., Kim, B.H.:
Characterization of bioactive RGD peptide immobilized onto poly(acrylic acid) thin films
by plasma polymerization. Appl. Surf. Sci. 257, 596–602 (2010)
165. Shao, Z., Ogino, A., Nagatsu, M.: Pre- and post-plasma treatments of polyethylene glycol
polymerization on polymer surface for immobilization of L-cysteine. J. Photopolym. Sci.
Technol. 23, 561–565 (2010)
166. Shi, L., Liu, Y., Wang, L.: Solvent effects in the polyethylene terephthalate surface
modification by cold argon plasma-induced grafting polymerization of methacrylic acid.
J. Appl. Polym. Sci. 117, 1460–1468 (2010)
167. Sun, J., Yao, L., Gao, Z., Peng, S., Wang, C., Qiu, Y.: Surface modification of PET films by
atmospheric pressure plasma-induced acrylic acid inverse emulsion graft polymerization.
Surf. Coat. Technol. 204, 4101–4106 (2010)
168. Tiwari, A., Kumar, R., Prabaharan, M., Pandey, R.R., Kumari, P., Chaturvedi, A., Mishra,
A.K.: Nanofibrous polyaniline thin film prepared by plasma-induced polymerization
technique for detection of NO2 gas. Polym. Adv. Technol. 21, 615–620 (2010)
169. Zhou, J., Shao, H., Tu, J., Fang, Y., Guo, X., Wang, C.F., Chen, L., Chen, S.: Available
plasma-ignited frontal polymerization approach toward facile fabrication of functional
polymer hydrogels. Chem. Mater. 22, 5653–5659 (2010)
170. Hasannejad, H., Shahrabi, T., Rouhaghdam, A.S., Aliofkhazraei, M., Saebnoori, E.:
Investigation of heat-treatment and pre-treatment on microstructure and electrochemical
References 27
properties of cerium nano-oxide films on AA7020-T6 by sol-gel methods. Appl. Surf. Sci.
254, 5683–5690 (2008)
171. Galant, C., Fayolle, B., Kuntz, M., Verdu, J.: Thermal and radio-oxidation of epoxy
coatings. Prog. Org. Coat. 69, 322–329 (2010)
172. Ma, K., Schoenung, J.M.: Influence of cryomilling on microstructure, phase stability and
oxidation behavior of NiCrAlY bond coat in thermal barrier coatings: experimentation and
mechanistic investigation. In: Materials Science Forum, pp. 1940–1943. (2010)
173. Mei, H., Cheng, L.F., Liu, Y.N., Zhang, L.T.: Effect of pre-oxidation treatment on the
thermal shock resistance of thermal barrier coatings in a combustion gas environment. In:
Materials Science Forum, pp. 1924–1927. (2010)
174. Mège-Revil, A., Steyer, P., Cardinal, S., Thollet, G., Esnouf, C., Jacquot, P., Stauder, B.:
Correlation between thermal fatigue and thermomechanical properties during the oxidation
of multilayered TiSiN nanocomposite coatings synthesized by a hybrid physical/chemical
vapour deposition process. Thin Solid Films 518, 5932–5937 (2010)
175. Sniezewski, J., Le Maoult, Y., Lours, P.: Oxidation and spallation of FeCrAl alloys and
thermal barrier coatings: in situ investigation under controlled temperature gradient. Mater.
High Temp. 27, 101–108 (2010)
176. Braun, R., Schulz, U., Leyens, C., Hovsepian, P.E., Ehiasarian, A.P.: Oxidation and fatigue
behaviour of c-TiAl coated with HIPIMS CrAlYN/CrN nanoscale multilayer coatings and
EB-PVD thermal barrier coatings. Int. J. Mater. Res. 101, 648–656 (2010)
177. Li, Z., Bao, R., Zhang, J., Fei, B.: Oxidation study of APS thermal barrier coatings in
elevated temperatures. In: Advanced Materials Research, pp. 1546–1549. (2010)
178. Subanovic, M., Song, P., Vassen, R., Naumenko, D., Singheiser, L., Quadakkers, W.J.:
Corrigendum to ‘‘Effect of exposure conditions on the oxidation of MCrAlY-bondcoats and
lifetime of thermal barrier coatings’’ [Surface & Coatings Technology. Volume 204 (2009)
p. 820–823 (doi: 10.1016/jsurfcoat.2009.09.056)]. Surf. Coat. Technol. 204, 1868 (2010)
179. Gheno, T., Monceau, D., Oquab, D., Cadoret, Y.: Characterization of sulfur distribution in
Ni-based superalloy and thermal barrier coatings after high temperature oxidation: a SIMS
analysis. Oxid. Met. 73, 95 (2010)
180. Busso, E.P., Evans, H.E., Qian, Z.Q., Taylor, M.P.: Effects of breakaway oxidation on local
stresses in thermal barrier coatings. Acta Mater. 58, 1242–1251 (2010)
181. Tien, S.K., Lin, C.H., Tsai, Y.Z., Duh, J.G.: Oxidation behavior, microstructure evolution
and thermal stability in nanostructured CrN/AlN multilayer hard coatings. J. Alloys Compd.
489, 237–241 (2010)
182. Taylor, M.P., Jackson, R.D., Evans, H.E.: The effect of bond coat oxidation on the
microstructure and endurance of a thermal barrier coating system. Mater. High Temp. 26,
317–323 (2009)
183. Khan, T.I., Saha, G., Glenesk, L.B.: Nanostructured composite coatings for oil sand’s
applications. Surf. Eng. 26, 540–545 (2010)
184. Floroian, L., Sima, F., Florescu, M., Badea, M., Popescu, A.C., Serban, N., Mihailescu, I.N.:
Double layered nanostructured composite coatings with bioactive silicate glass and
polymethylmetacrylate for biomimetic implant applications. J. Electroanal. Chem. 648,
111–118 (2010)
185. Zeller, A., Musyanovych, A., Kappl, M., Ethirajan, A., Dass, M., Markova, D., Klapper, M.,
Landfester, K.: Nanostructured coatings by adhesion of phosphonated polystyrene particles
onto titanium surface for implant material applications. ACS Appl. Mater. Interfaces 2,
2421–2428 (2010)
186. Polcar, T., Vitu, T., Cvrcek, L., Novak, R., Vyskocil, J., Cavaleiro, A.: Tribological
behaviour of nanostructured Ti–C:H coatings for biomedical applications. Solid State Sci.
11, 1757–1761 (2009)
187. Vallauri, D., Grassini, S., DeBenedetti, B., Alexandra, R.: Fabrication and characterisation
of nanostructured coatings by magnetron sputtering for wear resistant applications this
paper is dedicated to prof. Enrico evangelista in the occasion of his 70th birthday.
In: Materials Science Forum, pp. 3–12. (2009)
188. Souza, F.L., Lopes, K.P., Nascente, P.A.P., Leite, E.R.: Nanostructured hematite thin films
produced by spin-coating deposition solution: application in water splitting. Sol. Energy
Mater. Sol. Cells 93, 362–368 (2009)
189. Wang, L., Nie, X., Housden, J., Spain, E., Jiang, J.C., Meletis, E.I., Leyland, A., Matthews,
A.: Material transfer phenomena and failure mechanisms of a nanostructured Cr–Al–N
coating in laboratory wear tests and an industrial punch tool application. Surf. Coat.
Technol. 203, 816–821 (2008)
190. Vladescu, A., Kiss, A., Braic, M., Cotrut, C.M., Drob, P., Balaceanu, M., Vasilescu, C.,
Braic, V.: Vacuum arc deposition of nanostructured multilayer coatings for biomedical
applications. J. Nanosci. Nanotechnol. 8, 733–738 (2008)
191. Lima, R.S., Marple, B.R.: Thermal spray coatings engineered from nanostructured ceramic
agglomerated powders for structural, thermal barrier and biomedical applications: a review.
J. Therm. Spray Tech. 16, 40–50 (2007)
192. Kim, G.E., Walker, J.: Successful application of nanostructured titanium dioxide coating for
high-pressure acid-leach application. J. Therm. Spray Tech. 16, 34–39 (2007)
193. Pei, Y.T., Galvan, D., De Hosson, J.T.M., Cavaleiro, A.: Nanostructured TiC/a–C coatings
for low friction and wear resistant applications. Surf. Coat. Technol. 198, 44–50 (2005)
194. Nikolić, L.M., Radonjić, L., Srdić, V.V.: Effect of substrate type on nanostructured titania
sol-gel coatings for sensors applications. Ceram. Int. 31, 261–266 (2005)
Chapter 2
Size Dependency in Nanostructures
2.1 Introduction
Nanostructures are some 0, 1, 2 or 3 dimensional materials which are mostly

composed of one dimensional and zero dimensional nanomaterials such as nano-
powders, nano-particles, nano-wires, and etc. Nanostructures consist of two-
dimensional nano-materials arrangement or thin layers, called nano-coatings or
nanostructured coatings. For instance, nano-powders can be served as raw mate-
rials to produce nano-coatings in processes such as thermal spraying (plasma
spraying and high velocity oxygen fuel spraying) [1–8]. In this chapter, at first,
various types of nanostructures (especially nanocoatings) and their producing
methods, including thermal spraying coatings, transitional metal nitride coatings,
super-hard coatings, multi-layers, nano-composite and environmental coatings will
be analyzed. Then, the role of electrochemistry in production of nano-composites
and also electrodeposited coatings characteristics will be explained, and finally
nano-composites application will be examined. Finally the effect of size on the
properties of nanostructures will be discussed.
2.2 Nanocomposites and Their Production Methods
2.2.1 Thermal Spraying Nano-Composites
Thermal spraying involves particles quick surface melting and freezing. Thermal
spraying nano-composites are of higher abrasive resistance in comparison with
micro-coatings. For their high hardness, thermal stability, cosmetic appearance,
and chemical neutrality, transitional metal nitride coatings are of a great interest
among researchers. In normal circumstances, these coatings are produced through
chemical vapor deposition (CVD) and physical vapor deposition (PVD), although
their nano-structural coatings can be obtained using ion beam. Mentioned

DOI: 10.1007/978-3-642-17966-2_2, Ó Springer-Verlag Berlin Heidelberg 2011
30 2 Size Dependency in Nanostructures
nano-coatings are of a great hardness. This increase in hardness of multi-layers and

multi-grids (two-layers) are more intense. Spraying of transition metal nitride
nano-particles in an amorphous nitride matrix gives a rise to development of grains
with dimensions lower than one nanometer, which makes them efficient for uses
such as enhancement of abrasive resistance in copper cutting tools.
Thermal spraying method is a suitable method for production of hard coatings
on selected matrixes. Coating material is heated in a gaseous environment and is
sprayed toward matrix surface in melted drops form, in a high velocity. Due to
hits, the drops are settled in a homogenous form on the surface and convey their
initial heat to cold matrix and rapidly change into solid state. Applicable raw
materials in these methods include powder, rod, and wire. Regarding these
materials and efficiency of regarded coatings, there are different processes based
on thermal spraying, such as plasma spraying, high velocity oxy fuel (HVOF),
flame spraying, and etc.
In traditional plasma spraying, there is a high-temperature plasma jet in the gun.
Powder particles, with dimension of several microns are injected into plasma jet,
which changes them into a melted state. Then this combination is sprayed toward
matrix. For quick heating and accelerating to coating process, combustion process
is fairly common in HVOF method. Gaseous fuels, such as acetylene, propane,
propylene or hydrogen, are mixed with oxygen. Then this gaseous combination is
combusted, and produces a flame with approximate velocity of 2,000 m/s. powder
particles inter into a combustion container, which involves a noble gas such as Ar,
and are heated. Then particles are accelerated within a fluid under supersonic
velocity toward matrix. Micro-crystalline ceramic and metallic coatings are
obtained through low pressure plasma and HVOF spraying.
During last decades, availability of different processes for providing nano-
powders, including aerosol process, sol–gel process, chemical production, alloying,
and mechanical grinding have made some progresses in producing nano-coatings.
Thermal spraying methods, using nano-powders, give rise to production of coatings
with higher hardness, strength, and abrasive resistance, in comparison with tradi-
tional method. It is revealed that HVOF and metallic and ceramic nano-powders
plasma spraying is a useful method for creating nano-structured coatings. Since its
higher velocity, drops moving, and lower thermal energy quantities, HVOF,
compared with plasma spraying, produces a more compacted structure and higher
cohesion between coating and matrix [9–12].
Oxide ceramics such as alumina, chromia, titania, and zirconia, are widely used
as surface coating materials for improvement of abrasive resistance, wearing, and
cavity. Coatings made from zirconia are used for cylinder head and piston crown at
internal combustion engines to improve thermal efficiency, output force, and fuel
efficiency. These coatings involve cavities which are characteristics of plasma-
sprayed coatings. Nano-crystalline zirconia coatings show lower porosity (8%) in
comparison with micro-crystalline coating (12%). TEM test exhibits fine structure
of nano-crystalline coating’s at presence of co-axis grains (60–120 nm) and
columnar grains (150–350 nm). Fine co-axis grains are cooled because of
homogenous germination of mentioned melt, while columnar grains growth is due
2.2 Nanocomposites and Their Production Methods 31
to heterogeneous germination in boundaries, where there is a higher cooling

gradient. For efficient melting of nano-zirconia source at plasma jet, boundaries are
very thin and their interface is fairly narrow. This leads to an improvement of
cohesion between coating and matrix, then nano-zirconia coatings indicate lower
abrasion rate, compared with its micro micro-coatings (Fig. 2.1).
Over the past few years, hydroxyapatite (HAP) has been introduced as a porous
layer on metallic substrates to provide easier in-growth of bony tissues. Dey et al.
[13] studied the size effect on these kinds of coating that were fabricated by
microplasma spray. The excellent biocompatibility and bio-stability of HAP layers
have become well established and the usages of this material for prosthetic
applications have been rapidly popularized recently. Plasma spraying (PS) with a
high power (e.g. 20–40 kW) is the most popular and commercially accepted
method of coating. However, due to the high temperature of plasma jet, the
degradation of HAP occurred during spraying, which involved the formation of
unwanted tetracalcium phosphate (TTCP), tricalcium phosphate (TCP) and cal-
cium oxide phases. In addition, due to the rapid cooling of sprayed particles,
amorphous calcium phosphate also appears in the HAP coatings on Ti6Al4V
substrates. The degree of crystallinity (Xc) of PS-HAP coatings usually lied less
than 70%. To tackle these problems, recently the microplasma spraying (MPS)
process with a low power (e.g. 1–4 kW) has been used because it can provide a
higher degree of crystallization, e.g. Xc * 90% and phase purity than those
provided by conventional plasma spraying method. Dey et al. [13] used the
metallic substrate from a surgical grade, biocompatible austenitic stainless steel
(SS316L). The choice was done in accordance to better corrosion resistance
properties, mechanical properties and lower cost of SS316L than those of the
conventional Ti6Al4V alloy.
The stability and reliability of the coated implant in vivo depend mainly upon
the local mechanical properties of the layer. Dey et al. [13] used a low plasmatron
power (*1.5 kW), i.e. microplasma was used to coat HAP on SS316L and the
local mechanical properties, e.g. nano-hardness (H) and Young’s modulus (E) of
the MPS-HAP coating were examined by the well established nanoindentation
technique. The local mechanical properties, e.g. H and F of HAP and/or HAP
Fig. 2.1 Changes of abrasion

with applied load for plasma-
sprayed zirconia coating
a micro-crystalline coating,
b nano-crystalline coating
composite coating as well as global mechanical properties, e.g. microhardness

have not been discussed to a great detail in literature. Most of the researchers used
nanoindentation data with a Berkovich indenter for plasma sprayed HAP coating
on Ti6Al4V substrate. The reported values on H and E spanned a range of &4–5
and 83–123 GPa, respectively as one profiled from the coating-substrate interface
to the free coating side across the coating cross-section. The nanoindentation data
revealed further, that Young’s modulus value of amorphous zone was much lower
than that of the crystalline zone of HAP coating. On the other hand, for HAP
coating fabricated by using Nd-YAG laser on titanium, the nanoindentation
measurements with a Vicker’s diamond pyramidal indenter along the coating
cross-section showed that both H and E values were lower at the coating side than
at the coating-substrate interface. Nano-hardness and Young’s moduli data have
also been reported for functionally graded coating (FGC) of HAP/glass composite
and HAP/a-TCP composite. Others have evaluated Vicker’s microhardness and
nano-hardness of different composite coating systems, e.g. (a) plasma sprayed 50
vol.% HAP/50 vol.% Ti6Al4V composite coating on Ti6Al4V substrate, (b)
plasma sprayed HAP/YSZ/Ti6Al4V composite coating, (c) HAP/carbon nanotube
(CNT) composite coating and (d) biomimetic HAP coating deposited on Ti6Al4V
and Ti13Nb11Zr alloy substrates. Most of these reports involve a Ti6Al4V or Ti or
Ti alloy substrate and thus the amount of information on micro- or nano-
mechanical properties of microplasma sprayed HAP coating on SS316L substrate
is almost insignificantly small.
Dey et al. [13] prepared phase pure and flowable HAP granule from the con-
ventional wet chemical route. HAP coatings of thickness near 200 lm were pre-
pared by microplasma spraying on SS316L substrates. The degree of
crystallization for MPS-HAP was found to be high (near 91%). The statistical
validity of their data was established through the application of Weibull statistics,
because of the porous and heterogeneous nature of the coating. For both H and E
values of the coating, the values of the Weibull modulus (‘‘m’’) showed an overall
increasing trend with respect to load although some occasional deviations were
observed. Such deviations might have risen due to the presence of pores and cracks
in different layers of the coating. It was assumed that higher scatter of data at lower
load could be linked to stochastic nature of interaction between the indenter that
penetrated a very shallow depth and the flaws that scale with the size/depth of the
indentation and which possessed a highly statistical size distribution in the surface
and in the close vicinity of sub-surface region. At higher load, it was suggested
that due to a larger indentation zone of influence, an averaging out effect of
indenter-flaw interaction predominated to affect a reduction in data scatter. At a
low load of 10 mN, the coating demonstrated a hardness value of about 5 GPa at a
depth of about 170 nm which dropped by 60%, e.g. near 2 GPa at a depth of about
3 microns for a higher load of 1,000 mN. These data recommended the presence of
a strong indentation size effect in the nano-hardness behaviour of the coatings.
Figure 2.2 illustrates the SEM images of the polished cross-section of the MPS-
HAP coating taken at progressively higher magnifications: (a) at 91 K; (b) 96 K;
(c) 910 K.
Fig. 2.2 SEM images of the polished cross-section of the MPS-HAP coating taken at
progressively higher magnifications: a at 91 K; b 96 K; c 910 K, reprinted with kind
permission from Mukhopadhyay [13]
2.2.2 Transitional Metal Nitride Coatings
Using hard coatings for protection of structure constituents against abrasion is of a

great interest. Due to their high hardness, nitride coatings, such as titanium nitride,
titanium carbo-nitride, titanium boro-nitride, and titanium aluminide nitride, are
very suitable for cutting tools and drilling machines. In addition transitional metal
nitrides are among important materials in decorative coating industry since they
create beautiful colors within the range of visible wavelength. Hard coatings of
titanium nitride, produced by PVD and CVD methods are used for a long time on
industrial scale. For practical apply these hard coatings must be efficiently stuck
with context. In spite of those mentioned above, PVD is a linear method and
coating’s cohesion to matrix is less than CVD method. This is caused by diffusion
of coating material during CVD thermal process. The most important drawback of
CVD method is corrosive nature of applied gasses, such as SiCl4, and TiCl4 which
may jeopardize health of operators.
In addition, it is possible for matrix to be deformed due to imposing in high
temperature of the environment. For these applications, drills, and gears it is required
to a low deposition temperature to prevent deformation of coated constituents and
loss of their mechanical properties. These objectives are difficult to obtain in thermal
CVD. On the other hand, a lower deposition temperature (480–560°C) is needed to
develop titanium nitride coatings. However, this technology is not very handy and
only a limited number of commercial and industrial equipment are produced through
this method. Hence, there has been an effort to produce nano-crystalline coatings
with better cohesion, using PVD method with ions contributions.
Atomic bombardment of developed layer can delay grain growth and cause
development of nano-crystalline layers. Through IBAD there it is a strongly
expectation for development of metallic nitride coatings with a noticeable
improvement in abrasion, corrosion, electrical strength, and optical properties with
a change in deposition parameters, such as atomic flux, ionic energy, matrix
temperature, and etc. IBAD is addressed for a process through that a thin layer is
developed simultaneously using PVD method, using an independent ionic beam.
Though IBAD method it is possible to control ionic flux and energy. IBAD method
is mostly used because of a need for independent control of layer composition and
better cohesion between matrix and coating. Through changing deposition
parameters, such as atom flux, ion energy, matrix temperature, and etc. it is pre-
dicted to be a particular improvement in coatings’ characteristics.
Production of hard coatings with transitional metal nitrides, through IBAD
method is an extensive study area. These nitrides include titanium nitride,
chromium nitride, vanadium nitride, zirconium nitride, and aluminum nitride.
Also, their obtained coatings have different mechanical and chemical proper-
ties. For example, titanium nitride has a structure similar to that of NaCl, but
titanium nitride have more hardness, higher chemical stability, and efficient
cohesion to matrix, which makes it most famous coating for cutting tools.
Titanium nitride is oxidized at temperatures higher than 500°C. This causes
development of pure titanium oxide, attached to titanium nitride, which leads to
reduce of abrasive resistance of titanium nitride coatings. Due to development
of a passive and compacted oxide layer, chromium nitride indicates a higher
resistance against oxidization in comparison with chromium oxide, which limits
next oxidization. Aluminum nitride is among substances which can be applied
at higher temperatures, where nitrogen and aluminum atoms are bonded with
strong covalent bonds. Once, this coating is subjected to high temperatures,
aluminum move to surface and compose aluminum oxide layer, which is an
extremely efficient barrier to prevent later oxidization reactions. IBAD method
is more applied in practical investigations. At thin layers, low rate of energy
(less than 100 eV) for ionic fluid is applied at lower temperatures to control
fine structures of the layers.
When matrix temperature is lower than 15% of coatings material’s melting
point, the layer includes co-axis fine grains, ranged 20–50 nm. This is caused by
low mobility of deposited atoms at lower temperatures of the matrix. Next zone is
fine transitional zone of the fine structure between columnar zones, where tem-
perature varies between 3 and 15% of matrix melting point. Atoms can migrate at
higher temperatures of matrix due to surface diffusion. In next zone one can
observe columnar structure since deposited atoms have enough surface mobility to
diffusion and increase of grain size. In final zone grain growth is controlled by
volumetric diffusion and obtained when matrix temperature is higher than 50% of
melting temperature [14–18].
2.2.3 Super Rough and Super Hard Nanocrystalline Coatings
At industrial applications there is an increasing demand for coatings having higher

resistance against oxidation, higher hardness, and longer life than those of single
layer coatings. To supply industrial needs for development of improved coatings,
there has been many efforts to design and produce super consolidated coatings.
Some researchers proposed notion of designing solids with strong coatings, using
two alternative layers with high and low elastic constants. Each layer’s thickness
must be in nano range and there must be no dislocation source between layers. If
dislocations could be created in the zone of materials with lower modulus, they
must be overcome to the noticeable stress diffused from the phase with higher
modulus, before creep phenomenon (along the layers). Thus they must prohibit the
creep along the layers. Such multilayer coatings are called super-lattice and their
two layers can be metallic, carbide, and nitride. A multilayer includes different
piled materials on atomic scale. During multilayer coatings designing both related
structural and constitutional factors must be considered. These factors are: Grain
size, layers individual thickness, combination module, the number materials
interfaces (assuming the last layer is resistant against abrasion) [19–21].
Physical and mechanical properties of some hard materials can be combined in
multilayer coatings, leading to optimization of materials properties. Abrasion is one
of most important factors for destruction of engineering equipment. For instance,
cutting tools are subjected to great loads, high temperatures, and inefficient lubri-
cation; hence during mechanisms such as scratching, cohesion, thermal softening,
and chemical abrasion there will be an overall abrasion on them. Then, to improve
their characteristics it is recommended to use some multi-constituents coatings such
as titanium nitride, aluminum/titanium nitride and aluminum/chromium/nickel
nitride. Succeeding progresses leads to bring on development of multi-layer coat-
ings such as titanium-aluminum nitride, chromium nitride and aluminum-titanium
nitride and vanadium nitride. It seems that these multi-layers are of a higher
potential for improving cutting tools lifetime. According performed studies, mul-
tilayer coating of aluminum-titanium nitride/chromium nitride have highest abra-
sive resistance and hardness, in comparison to other coatings. Besides, multilayer
film of titanium nitride/aluminum nitride also enjoys both high mechanical and
anti-oxidation properties. When it comes to compare multilayer coatings with
single layer one, there reveals to be some advantages and disadvantages including:
1. A multilayer film may have a better hardness and ductility, comparing with all
layers one by one.
2. A multilayer film with limited thickness has equal or higher mechanical sta-
bility with each of single layers.
3. A multilayer with desirable constituents from different single layer films can be
adapted with practical needs.
4. There is an increase in cohesion between multilayer film and matrix.
5. Remained stress in multilayer film decreases.
6. Multilayer films have a more compact structure.
There are different methods for producing these multilayers but the most
common way is through evaporation, due to its highest efficiency among the other
methods for controlled preparation of high quality structures on atomic scale. On
the other hand, electrochemical methods are also very efficient, for their low costs
and possibility for mass production. As well as abrasive properties, which are
initial reasons for using multilayer coatings, reaching to suitable magnetic prop-
erties it is suggested to use such nano-multilayers. For multilayer coating—where
growth conditions are decent—it is possible for magnetic stabilization at one
direction (vertical to layer plain). Particularly, some multilayer films based on Co,
such as Co/Pd, Co/Pt, and Co/Au, indicate a high magnetic anisotropy at vertical
directions. Tri-layers of Co/Cu/Co have same situations [22–34].
It has been proved that this anisotropy of the properties is due to Co layer
thickness. When its thickness decreases (up to 0.4 nm) its magnetic properties
have an increase and magnetic direction of multilayer film changes from parallel to
coating layer to vertical on Co layer thickness. Current advances in coating
technology, using PVD and CVD plasma methods, lead to deposition of multilayer
coatings with more preferable mechanical and chemical properties. As an example
for these multilayer structures, one can name Al/Cu and Al/Ag. Once dual layer’s
constant reaches to 5 nm, hardness of vanadium nitride/titanium nitride and nio-
bium nitride/titanium nitride coatings reaches to 50 GPa. Super-lattice coatings
enjoy higher hardness than that of single-layer coatings such as titanium nitride,
vanadium nitride, and niobium nitride.
Increasing hardness in super-lattice coating was investigated, based on exam-
ination of dislocations mixed movements within and into the layers. The model
implies a maximum peak, where there is a difference in shear modulus between
two materials and their sharp interface. Here, once super-lattice constant is more
than 5 nm its hardness declines to 14 Gpa. Super-lattice’s physical properties have
made them suitable to be used in Micro Electromechanical Systems (MEMS), as a
small tool for protection against abrasion. Layers in super-lattice should be
amorphous; as amorphous can connect the lattice more conveniently. Hard single-
layer nano-composite coatings were designed, using plasma CVD process. This is
occurred at high frequency under direct current. Through this process a hard
transitional metal nitride and a covalent nitride (e.g. silicon nitride or bore nitride)
are simultaneously deposited to obtain immiscible phases with interfaces and high
cohesion energy. In the other words, the coating includes transitional metal nitride,
where nano-crystalline with 4–6 nm size is located in an amorphous matrix with
thickness of less than 1 nm. Such a coating is called nano-composite layer
[35–47].
As an interesting example of size dependency, plasma electrolysis has been
used for fabrication hard nanocrystalline layers. The usage of nanocrystalline
plasma electrolytic saturation by applying pulsed current in an organic electrolyte
based on Glycerol has been studied. Response Surface Methodology was applied
to optimize the operating conditions for small nanocrystallite sizes of coatings.
The levels studied were peak of applied cathodic voltage range between 500 and
700 volts, peak of applied anodic voltage between 200 and 400 volts and the ratio
Fig. 2.3 SEM nanostructure for treated samples by cathodic plasma electrolysis with average
size of a 32.6 nm and b 95.1 nm [48]
of duty cycle of cathodic direction to duty cycle of anodic direction of 0.25–0.35.

The usage of high applied cathodic voltages and low anodic voltages and also low
ratio of duty cycle of cathodic direction to duty cycle of anodic direction is more
suitable for achieving lower sizes of complex nanocrystallites. The samples with
high height to width ratio of distribution curves of nanocrystallites have simul-
taneously, smaller average sizes and lower length to diameter ratio of nanocrys-
tallites [48].
Response surface methodology proved to be fairly accurate in predictive
modeling and optimization of conditions for minimizing the average sizes of
nanocrystallites obtained in pulsed bipolar nanocrystalline plasma electrolytic
carbo-boriding, and that the average sizes of nanocrystallites to be reasonably
approximated by quadratic non-linearity. In this process, the samples with high
height to width ratio of distribution curves of nanocrystallites have smaller average
sizes of nanocrystallites and lower length to diameter ratio of nanocrystallites.
Figure 2.3 illustrates SEM images of treated samples with different effective
factors. These samples have different average size of nanocrystallites. Narrower
distributions for lower average size of nanocrystallites were observed for these
samples. Figure 2.4 illustrates the distribution curves of these samples [48].
2.2.4 Nanocomposite Coatings
The first investigations on composite coatings were performed in 1962. In 1970 for
the first time Ni-SiC composite coating was used to improve engines abrasive
resistance. This composite is yet applied for some panels in automobile industry.
Composite coatings are obtained through simultaneous deposition of tiny neutral
particles in a metallic matrix. Due to its competence for producing films with
excellent mechanical properties such as abrasive resistance, wear strength, hard-
ness, and lubrication, this method is matter of great interest. Simultaneous depo-
sition of non-metallic and metallic phases for development of composite layers has
Fig. 2.4 Distribution curves of nanocrystallites for mentioned treated samples in a Fig. 2.3a and
b Fig. 2.3b [48]
a significant improvement in most of mechanical and physical properties of the

coating. Such properties depend on neutral particles morphology in composite
coating. Furthermore, metallic matrix of nano-composite coatings exhibit unique
optical and magnetic properties and are promising for production of materials for
fine tools.
Applied ceramic particles mostly include aluminum oxide, carbide, chromium
oxide, titanium oxide, molybdenum oxide, tungsten carbide, and etc. Besides,
polymeric particles such as polyethylene and polytetrafluoroethylene are used to
decrease friction ratio and achieve a nonstick composite surface. According to
performed studies, fine-grained Ni-SiC composite has a smoother surface and there
is stronger bond between SiC and Ni. Once SiC particles are bigger than 0.1 lm,
usually there develops an oxide layer on SiC particles which have a weak bond
with nickel matrix, which leads to development of cavities and cracks in grains
boundary. On the other hand, interface of a very fine SiC and mixed Ni is free of
any defect. In the same volumetric fraction very fine particles are more abundant,
which prevent grains growth at higher temperatures. However, investigations show
a decrease in particles size leads to decrease of simultaneous deposition of the
particles.
It was showed that concentration of SiC (with dimension of 0.1 lm), obtained
from spinning wheel test, in a nickel sulphamate solution is less than 0.7 weight
percentage, which is very close to thresholds scale obtained from EDS analysis. In
contrary, concentration for carbide, where grain size is 0.2 and 2.8 lm, is 2 and 6
volumetric percentage, respectively. In general, concentration changes of poly-
ethylene particles surrounded in the matrix on an electrode of a spinning plain is
obtained basically from throw analysis. According this model, the required amount
for simultaneous deposition of 5 lm particles is 10 time less than that of 20 lm
particles. Although it is long time since hard metallic coatings application through
plating deposition has a drastic advancement, but mechanisms of simultaneous
deposition have not completely been solved, yet [49–61].
Guglielmi was the first who proposed successful two-staged absorption
mechanism. Through this mechanism he suggests that the results depend on vol-
umetric fraction of co-deposited particles with Langmuir absorption isotherm. The
first step of this free absorption mechanism is where particles from metallic ion
coating on the cathode have a considerable amount of free physical absorption. In
this step there is a layer of absorbed ions and solvent molecules; and also there is a
reaction between electrodes and particles. The first step is a strong absorption
which seems to be with contributed to electrical field, as a strong electrochemical
reaction causes strong absorption of the powder on the electrolyte. Absorbed
particles progressively are surrounded by metallic layer. This mechanical model
can be expressed as equation below:

C Mi 1
¼ expðA BÞg þ C ð2:1Þ
a nFqm V0 k
where: M: deposited metal’s atomic weight, io: exchanged current density, n:

deposited metal capacity, F: Faraday constant, qm: density of deposited metal, g:
extra voltage of electrode reaction, and k: Langmuir isotherm constant, which is
determined by intensity of the reaction between particles and cathode. B and V0
parameters are dependent on particles deposition and both play the same role with
A and i0, which are dependent on metallic deposition. Guglielmi model’s
parameters changes with deposition system changes, such as SiC and titanium
oxide particles with nickel in sulphate bath or alpha aluminum oxide particles with
copper in CuSiO4 plating bath. The mechanism shows a simple effective method to
analyze direct effect of basic parameters on composite plating [62–68].
Recently, electrodeposition of tertiary Al2O3/Y2O3/CNT nanocomposite by

using pulsed current has been studied. Coating process has been performed on
nickel sulphate bath and nanostructure of obtained compound layer was examined
with high precision figure analysis of SEM images. The effects of process vari-
ables, i.e. Y2O3 concentration, treatment time, current density and temperature of
electrolyte have been experimentally studied. Statistical methods were used to
achieve the minimum of corrosion rate and average size of nanoparticles. Finally
the contribution percentage of different effective factors was revealed and con-
firmation run show the validity of obtained results. Also it has been revealed that
by changing the size of nanoparticles, corrosion properties of coatings will change
significantly in same trend. AFM and TEM analysis have confirmed smooth sur-
face and average size of nanoparticles in the optimal coating.
The Taguchi method for the design of experiment has been used for optimizing
tertiary nanocomposite electrodeposited coating process parameters for the cor-
rosion protection of treated samples. The contribution of Y2O3 concentration is
more than the sum of the contributions of all the other three factors. It is evident
that, among the selected factors, Y2O3 concentration has the major influence on the
corrosion rate of performed coatings. It can be seen that the current density is
second important factor that affects on corrosion rate of the treated substrates.
Furthermore, it can be assumed that treatment time and temperature of electrolyte
have almost the same effect on corrosion rates of coatings because of the minor
difference in the contribution percentages among these two factors. By ranking
their relative contributions, the sequence of the four factors affecting the corrosion
rate is Y2O3 concentration, current density, treatment time and temperature of
electrolyte. In the case of average size of nanoparticles ranking of effective factors
by their relative contributions is as same as for corrosion rate which show strong
relation among these two measured properties of coatings. AFM and TEM analysis
have confirmed smooth surface and average size of nanoparticles in the optimal
coating. Figures 2.5 and 2.6 illustrate the SEM and AFM images of optimal
coating, respectively [69].
2.2.4.1 Nitride Nano-Composite Coatings
These coatings have typical structure of nc-MnN/a-Si3N4, where c and n are,

respectively, crystalline and amorphous phases and Mn stands for transitional
metals such as Ti, W, V, and Zr. In nano-composite coatings, transitional metal-
nitride phase is hard enough to bear exerted load while, on the other hand,
amorphous nitride provides flexibility of the structure. Based on computer simu-
lations plastic deformation in nano-crystalline materials, where particle size is less
than 10 nm, can be corresponded with particle boundary. Here, grains boundaries
slip—which is controlled by diffusion of grain boundary—may be responsible
for plastic deformation in nano-crystalline materials. Slip is caused by
atomic movements and stress induced from 3D free migration; in the other
words, once nano-crystalline materials are extremely tiny indicate soft behaviors.
Fig. 2.5 SEM nanostructure

of optimal nanocomposite
coating [69]
Fig. 2.6 AFM surface

profile of optimal
nanocomposite coating [69]
Hence, an increase of hardness is required locking in grains slip boundaries. Indeed,

this is the reason for increase of hardness in nc-MnN/a-Si3N4 system, for nano-
composite coatings of nc-TiN/a-Si3N4 and nc-W2N/a-Si3N4, where particles’ size
decreases up to 4 nm. It was declared that these developed nano-composite coatings
by CVD method, will reach to diamond hardness (70–80 MPa), where grain size is
about 2 nm. Achieving a high hardness, nitride phase concentration must be around
17–23 molar percentage. The reason for hardness increase is progress of submerged
nitride’s nano-structure. nc-MnN/a-Si3N4 system shows noticeable thermal stability
until 1,000°C. CVD plasma process provides high chemical activity for gas and
controlled surface mobility, as well as ionic bombardment.
Other methods such as PVD can be used for preparation of other nano-crystalline/
amorphous coatings, such as titanium carbide in a carbon matrix or tungsten carbide
in carbon matrix, which are of a unique combination of hardness and ductility.

Carbon serves as a hard, ductile, and lubricating matrix; while nano-particles act as
crystals which enhance hardness and other mechanical properties. As nc-MnN/a-
Si3N4 with high elasticity typically shows brittle behavior, some researchers designed
nano-grain coatings (where grain size is 10–50 nm) with high ductility in an amor-
phous matrix. This state leads to development of dislocations; however they are too
small for expansion of cracks. Segregation of larger grains leads to adjustment of
non-apparent strains and development of nano-cracks between crystals, which finally
results in plasticity behavior. According to this state, titanium carbide coatings in a
carbon matrix include: hardness of 30 GPa, fraction coefficient: 0.15–0.2, and duc-
tility: 4 times greater than nano-crystalline titanium carbide. According to above,
super-lattice or multilayer coating is materials which can be applied in MEMS
method. All in all, silicon and other electronic materials are used for production of
mechanical miniature panels (micro-machines), such as membranes, cantilever,
gears, engines, and valves, using standard process of concentrated circuit industry
instead of surface machining.
Surface machining is a process for creating surface structures from tiny
deposited layers. Surface fine-structures’ thickness varies from 0.1 to several
micrometer to final size of 10–500 micrometer. Currently, some researchers pro-
duced super-nano-crystalline coatings of diamond with CVD method, by short
waves using unique chemical such as C–Ar or methane-Ar. Hence carbon couples
are obtained from methane through following reactions.
2CH4 ! C2 H2 þ 3H2 ð2:2Þ
C2 H2 ! C2 þ H2 ð2:3Þ
There is a very small amount of hydrogen in atmosphere. Through traditional

CVD method, developed diamond film constitutes: methane (1%) and hydrogen
(99%), and an extra hydrogen contained gaseous mixture. This extra mixture
solves diamond phase and develops columnar morphology with larger grain
size and higher surface roughness. Final rough surface of diamond micro-
structure can cause extra scratches along slip plain. It was applied the term of
super-nano-diamond coatings to make a distinction among these materials,
micro-structures of diamond with grain size of 1–10 micrometer, and nano-
crystalline diamond (50–100 nm). AFM studies for thin films of super-nano and
micro diamond showed that super-nano diamond coating has s smoother sur-
face. These coatings’ hardness is about 88GPa and their modulus is close to
that of mono-crystalline diamond (70GPa). Besides, their fracture strength is
too much more than that of silicon, silicon carbide, pseudo-diamond carbon,
and mono-crystalline diamond. This film’s fracture coefficient is comparable
with that of natural diamond and its abrasion against hard materials is a
minimum amount, due to smooth appearance of the surface. Thus, in these
layers with improved mechanical and tribological properties, are ideal materials
for MEMS applications [30, 70–79].
2.2.4.2 Nanocomposite Coatings of Ni/Al2O3
Nano-composites coatings of Ni/Al2O3 are used to enhance abrasive resistance of

metal’s surface in micro-tools. Although micro-composite coating of Ni/Al2O3 has
had a significant advancement, but there are some difficulties during their prepa-
ration. Volumetric amount of alumina particles in Ni/Al2O3 composite coating is
not controllable in quantitative sense and particles in composite coating are per-
sistent. Some researchers recorded that alumina particles can easily stick to each
other in electrolyte. This causes weak mechanical properties in the coatings.
Alumina weight in composite coating can be increased between 3.5 and 14.6%,
using inverse pulse electrical deposition, which results in improvement of
mechanical properties. In spite of that distribution of tiny alumina particles is yet a
problem during coating preparation. Putting smaller neutral particles in sediment
layer is more difficult, due to problem of neutral particles distribution. Volumetric
amount of nano-particles within the composite coating under work circumstances
is very few. Distributed particles in an electrolyte solution are persistently moving.
Once one particle reach to another one, their energy content defines weather
they are separated or connected. Particles connection occurs when their absorption
energy is higher than detractive energy. The pure energy in a continuous structure
rests upon nature and condition of the system. Information about structure of
interface zone is an important factor to perceive stability of solid particles dis-
persion in an electrolyte. For creating decent dispersion for alumina particles in a
nickel sulfamate bath chemical and physical methods, which change particles size
in interface zone, are necessary. Chemical effect occurs once particles involve
absorbed surfactants or macro molecules for development of electrostatic inter-
ference in internal particles. Under particular circumstances this interference
results in increase of absorbed layer rejection and situational entropy release at
internal particles. On the other hand, chemical effect occurs once particles absorb a
destructive energy such as ultrasonic. Creation of ultrasonic waves in liquid
environment results in an extraordinary pressure (100 atm), which induces huge
stress and destruction of cohesive energy between internal particles.
Through previous investigations, the average size of continuous alumina in
deionized water, and nickel sulfamate bath were 183 and 1,109 nm, respectively. It
seems that effect of solution’s ionic stability on particles accumulation in nickel
bath is not negligible. Average dimensions of continuous alumina using physical
dispersion by ultrasonic energy decreases up to 280 nm, while this reduction is
448 nm when it comes to use chemical dispersion released from surface factors in
nickel bath. Although chemical and physical dispersion are considered at elec-
trochemical preparation of nano-composite coating, these methods, to some extent,
impede dispersion of neutral alumina particles in nickel sulfamate bath since
electrolyte ionic concentration is an important factor in effective distribution of
aluminum particles. Alumina particles distribution in a dilute nickel sulfamate
bath, along using ultrasonic dispersion, is an effective method to prevent continuity
of alumina particles [80–93].
2.2.4.3 Al Based Composite Nano-Coatings
Al based composites with aluminum borate whiskers—which are created using

high pressure casting—indicate a comparable strength and modulus with those of
aluminum composites with SiC or silicon nitride whiskers. However, they have a
lower thermal expansion and higher abrasive resistance. Besides, another priority
of these whiskers is their very low costs in comparison with those of SiC—1/20 of
SiC whiskers. Hence, aluminum borate whisker is of great qualifications for
expansion of aluminum based composite applications. Also, based on existed
theoretical and empirical studies, it was revealed that aluminum borate whisker is
unstable in Al alloys, and the reaction occurs in their interface. To control reaction
in interface, nitriding process of these whiskers, based on thermodynamic calcu-
lations, was suggested. To reach a continuous and homogenous phase nitrided
nano-coating must be used. Phase analysis implies presence of BN and alumina on
nitrided surface. Nitrided nano-coating with thickness of 40–60 nm isolates the
whisker from surrounding matrix and aluminum/coating interface will be free
reaction productions [60, 94–104].
2.2.4.4 Al/TiO2 Nanocomposite Coatings
Titanium oxide is of abundant usage in gas sensors and photo-catalysts. For

example, it is used in gas sensors to detect explosion released gases such as natural
gas and hydrogen. Due to their crystalline structure, surface area, their cavity types
(in terms of opening and closure), and their size distribution, photo-catalysts are
used for segregation of air pollutants and organic contaminator in waters. It has
been currently shown that TiO2 nano-coatings are of a greater sensation compared
with that of micro-structure ones. The easiest and simplest way to achieve a
nano-coating with thermal spray method is using raw materials with nano-size.
However, directly adding such nano-powders during spray process is difficult.
Moreover, plasma or gas flame leads to melting and removing its initial structure.
Therefore, it was achieved that better characteristics through simultaneous spray of
the other substance which prevents development of Ti-O2 powder in the furnace.
Thus particles of metallic Al, which are of a lower temperature and higher reac-
tivity in comparison with TiO2, are added to Al/TiO2 composite powders to
enhance spraying efficiency. Al particles have significant role to create homoge-
nous sediment. They lead to reach to unique characteristics of nano-structures,
maintaining nanometric structure during spraying process [105–115].
2.2.4.5 Al/Al2O3 Nanocomposite Coating
Useful effect of alumina nano-particles was recorded in 1990’s. It is found that

development of nano-size dual metallic phases in alumina can noticeably enhance
its thermal and mechanical characteristics. Metallic phase exhibits higher thermal
conductivity and resistance against thermal shock in comparison with alumina

ceramic. Also, metallic phase can increase ceramic’s ductility as metallic particles
deform plastically. In performed operations on metallic/alumina nano-composites,
metals such as Cr, Ni, Fe, W, titanium carbide were used, which leads to 2–3 times
increase of ductility. Second phase has been added through mechanical combining
of alumina and metallic powders, and their under-pressure sintering of graphite
crucibles.
The main problem of mechanical combination method is to find out how to
reach to second phase’s fine dispersion and favorite thermal expansion difference
between alumina and metal. Thus, a chemical coating method was used for
preparation of ceramic/metallic nano-composites, which has variant advantages
compared with mechanical combination method. The obtained powder in this
method is more homogenous and of a higher cohesion between metal and ceramic.
Preparing nano-composite coating of Al2O3/Al wet chemical coating method was
applied. Aluminum nano-particles are solved in appropriate solution, then Al2O3 is
added, and finally considered composite is deposited in the solution. Through
occurred reactions, there develops a thick Al(OH)3 layer on aluminum particles’
surface which, after calcification, is converted to alpha alumina nano-particles
(with grain sizes of 10–20 nm) and distributed Al particles. The advantage of
Al2O3/Al composite is development of a thin transition layer between Al and
Al2O3, which is able to improve their bond [110, 116–127].
2.2.4.6 Nanostructured Coatings of Tungsten Carbide/Ni-Co
Although tri-valence chromium ions, and particularly hexa-valence ones, are very
poisonous, chromium plated coatings are widely used to enhance surface abrasive
resistance. Another problem of plated chromium coatings is their decrease in
thermal mobility with increase of temperature, so hardness and abrasive resistance
of plated layers reduces. Hereabout there have been many studies in surface
engineering to find a suitable substitute for this coating, leading to promising
results. First choice is tungsten carbide or tungsten-carbide/cobalt. As it previously
mentioned nano-crystalline materials show unusual chemical, physical, and
mechanical properties, in comparison with amorphous ones. This is caused due to
nano-crystalline materials’ noticeable decrease in grain size and volumetric ratio
of grain’s boundary, and triple connections. Here, a decrease in tungsten carbide
grain size up to 70 nm in tungsten-carbide/Co composite leads to a two-time
increase in abrasive resistant.
Nano-crystalline nickel with grain sizes of 10–20 nm, created with electrical
deposition method, has abrasive resistance of 100–170 times and friction ratio of
40–45% higher than that of multi-crystalline nickel, where grain size is
10–100 lm. it was found that nano-composite coating of diamond in nickel matrix
under effect of distributed nano-diamond strength indicates less internal stress and
higher fine-hardness. Mentioned nano-composite shows excellent abrasive
characteristics at room and even higher temperatures. Anti-abrasive properties of

this composite coating are 4 times more than that of pure nickel coating [128–130].
2.3 Electrochemistry Role in Production of Nano-Coatings
Electrochemistry is an advanced technology in production of nano-particles.

Before studying use of different electrochemical methods for nano-coatings pro-
duction, first it should be defined that how colloidal chemical state leads to cre-
ation of nano-particles. This leads to better understanding of electrochemistry
concept and its effect on nano-coatings. In colloid science, nano-particles mostly
obtained from surfactant contained saturated solutions. The first rule of organic
ligands is inactivation of surface and development in suspending state. This
preparation technique of nano-particles is called engaged sedimentation.
Similar methods for development of nano-particles on conductive matrix have
dramatically advanced in electrochemistry. It has been proved that adding surface
intermediates can lead to deposition of nano-particles during plating. Additives
prevent particles growth and maintain particles’ size to be approximately constant.
A more common method is creating changes in plating parameters, e.g. voltage or
current. However, there is another two-step method including a high extra voltage
in a short time for germination of metallic particles on surface and then slow
growth of particles in a lower extra voltage. Low extra voltage results in minimum
change (about 7%) in particle size. this stops diffusion of mixed layers and
decrease in growth rate. particles shape produced by engaged electro-deposition
depends on applied matrix and extra voltage. Metals such as Au, Ag, Ni, and
polymeric nano-particles with spherical geometry on graphite matrixes, are created
by this method. Palladium nano-wires with 55 nm diameter and length of several
hundred meters were created through this method, which are used in a polymeric
matrix as hydrogen sensor. It is worthy to say this wires strength decrease when
they are subjected to hydrogen [80, 131–140].
2.3.1 Electro-Deposition Using Porous Templates
Electro-deposition is one of the effective methods in nano-composite production.

For its low costs and high production potential, it is of a great interest. The only
way to produce nano-coatings through this method is changing parameters such as
current, voltage, bath composition, pH, and etc. It is also found that in most cases
created coatings properties with electro-chemical method is preferable, compared
with the other methods; because most compacted coating without any pre-stress is
produced through this method. Material development using porous templates to
control size and shape is a common method to create nano-particles. Despite, there
are many problems of using templates in sedimentation methods, due to
2.3 Electrochemistry Role in Production of Nano-Coatings 47
heterogeneity and pores block; however grain growth in electro-deposition can

only occur suing a template.
Template electrodes are constituted from materials such as etched Mica and
porous alumina membrane. Electro-deposition is applied using a template for
preparation of nano-wire made of different materials. Through an advance ini-
tiative in production, using templates, nano-wires are created by periodic move-
ments of wording electrode in a solution including Au ions and a solution
including Ag ions. Difference in Au and Ag cross sections creates wires with nano-
barcodes. Electro-deposition method with template, for preparation of materials
with high surface area includes used nano-pores. Spherical poly-styrene nano-
particles are created on an Au matrix of a colloidal cell. In electro-deposition a
metal develops on an electrode, a metal-polystyrene develops, and then polysty-
rene particles are solved and a metallic layer with nano-pores will create.
Currently, so many researchers have had focus on common plating methods
with direct current as deposition methods for creation of nano-crystalline mate-
rials. In most cases, electro-deposition is a product with no porosity on it and there
are no integration processes, compared with other methods for producing nano-
crystalline materials. Through this method one can either create coating on surface
or make a definite shape (such as foil, sheet, or regular shapes). Using this method,
some special metals (e.g. Ni, Co, Pd), dual alloys (such as Ni–P, Co-W, Ni-Zn, and
Ni-Mo), and triple alloys (like Ni–Fe–Cr) can be produced. Basically, electro-
deposition results in production of nano-structural material whenever process
parameters (such as bath composition, pH, temperature, extra voltage, and etc.) are
selected in a way that electro-crystallization induced by germination is in a high
rate and grain growth has a low rate.
Electro-crystallization occurs under effect of two competitive reactions: pro-
duction of new crystals and growth of existed crystals, under effect of different
factors. Two main steps determining the rate are: charge transition step on elec-
trode surface and surface diffusion of extra ions on crystal surface. Grain growth
occurs at low extra voltages and high surface diffusion rate. On the other hand,
high extra voltages and low surface diffusion lead to development of new grains
[141–153].
2.3.2 Nano-Coatings Properties
Determined properties associated with crystalline nano-coatings reveals that these

properties can be categorized in two groups:
1. Coating properties which are strongly depended on grain size including:
abrasive resistance, strength, malleability, hardness, friction coefficient, elec-
trical resistance, solid solubility, hydrogen solubility, permeability, local wear
resistance, stress corrosion cracking, and thermal stability.
2. Properties which are weakly influenced by grain size, including: bulk density,
thermal expansion, Young modulus, and coercivity.
2.4 Mechanical Properties
As it is expected plastic deformation behavior of nano-crystalline materials is

strongly depended on grain size. Most performed tests are related to determination
of fine-hardness at room temperature on samples with thickness of 0.1–0.5 lm;
where first they are plated on Ti matrix and then Ti is used to determine fine-
hardness.
The results of hardness measurement for plated Ni–P whiskers at room tem-
perature were reported. Same results were obtained for Pd and Cu produced from
neutral gas evaporation method. An increase in grain size is accompanied with
considerable decrease of hardness in range of lower than 20 nm. These observed
reductions of hardness are not corresponded with Hall–Petch behavior. Recently,
performed investigations on tensional strength of Ni nano-crystal at room tem-
perature have shown a behavior similar to that of determined with hardness. It is
found that grain boundary diffusion in creep phenomenon is not an efficient factor
to determine mechanical behavior of Pd and nano-crystalline Cu at room tem-
perature. Start point for hardness decrease, i.e. deviation from Hall–Petch
behavior, occurs once triple lines occupy a high ratio of sample volume. This
phenomenon is generally in accordance with softening effect of triple lines.
Through electrochemical grinding of wires to sizes lower than grains average size,
triple connections can be displaced in fine structures. At all cases this transition,
increase of strength, and decrease of malleability is shown from co-axis state to
columnar one.
Modified theory of dislocation locking with fewer numbers of dislocations can
be used to explain deviational behavior from Hall–Petch equation. It was shown
that there is a considerable decrease in Hall–Petch gradient—obtained in critical
circumstances—due to presence of a spread dislocation cycle. Some researchers
state that dislocation mechanism is not used for nano-crystalline material with
grain size lower than a critical limit, for example 10 nm, for FCC metals.
A combined model, based on above geometric assumptions for matrix, volumetric
ratio of intra-crystalline and crystalline constituents, were proposed to determine
nano-crystalline materials strength. It has been proved that the model can be
applied for interpretation of different approaches including deviation from Hall–
Petch equation and negative gradient of Hall–Petch curve. This analysis includes
quadric nodes where triple lines meet each other, as well as grain binderies and
triple connections. Strength distribution for grain boundaries (rgb), triple links
(rtl), and triple nodes (rqn), as:
rqn [ rtl [ rgb
Researchers also, reached to an analytical explanation to examine creep rate of
nano-crystalline materials for a diffusion mechanism involving triple lines. Gen-
eral rate of the creep is sum of creep rate due to network diffusion, grain boundary
diffusion, and triple line diffusion. It has been proved that, due to triple line
diffusion, creep speed has stronger association with grain size compared with grain
2.4 Mechanical Properties 49
boundary diffusion. For instance, distribution of triple line diffusion in creep speed
at stable stage seems to be inverse power of four, which is one order more than that
of grain boundary diffusion and two orders more than that of grain-size-depended
network diffusion in matrix. Besides, in comparison with dislocation mechanism,
where applied stress power is more than 3, secondary creep rate, yet, is linearly
related with tensional stress. Conclusion was that at higher stresses, grain
boundary slip is main deformation mechanism at room temperature for pure
electro-deposited nano-crystalline nickel. There was recorded a negative gradient
of Hall–Petch, where grain size was less than 10 nm. One can claim that deviation
from Hall–Petch equation might be for dynamic creep process induced from dif-
fusion mechanisms [154–164].
Thanks to advancements in applications of electro-deposited nano-crystalline
materials, recently a comprehensive investigation was carried out on their
mechanical properties. Also yield strength and tensional strength increase with
grain size decrease, well as considerable increase in hardness. It is interesting to
know that work coefficient of hardness decrease to around zero where grain size
reduces up to 10 nm. For typical materials, material malleability with reduction in
grain size up to 50% of length to fracture in tension decreases to 15 and 1%, where
grain size is 10 and 1 nm, respectively. It is found that in most of cases there is
more malleability in buckling. For grain sizes of 10 nm, a slow return in mal-
leability was recorded. Compared with multi-crystalline Ni, abrasion rate of
electrodeposited nano-crystalline Ni is intensely decreased and its friction ratio is
fairly low. In contrary with recent calculation about nano-crystalline materials,
carried out with methods with homogenizing stage, electrodeposited nano-
crystalline Ni shows no significant decrease in Young modulus. This approves the
previous obtained results which mention a drop in Young modulus in nano-
processes is due to high value of remained porosity.
Numerous investigations have been performed on the formation of nanocom-
posite layers during recent years, such as papers about Ni–P-TiO2 as lubricious
layer, Ni-SiC and Ni-Co-SiC as wear and corrosion-resistant coatings, Ni-TiO2 as
photocatalytic layer, and Ni-SiO2 as corrosion-resistant layer. The most important
features of a well-performed layer are constant concentration along the nano-
composite layer and uniform distribution of nanoparticulates in matrix. Some
modifications in electrodeposition such as using pulsed current and ultrasonic bath
were usually employed for better dispersion of nanoparticulates in obtained
nanocomposite layer. Some papers reported usage of ultrasonic bath during
nanocomposite electrodeposition process. Results about the effect of the ultrasonic
condition outside of the cell during electrodeposition demonstrated that the
ultrasonic condition increases uniform distribution of Al2O3 nanoparticulates but
decreases their concentration in the metallic matrix. Also, some reports were
published about the effect of pulsed current on electrochemical coating process. It
has been revealed that usage of pulsed current will lead to fabrication of harder
nanocomposite layers. Pulse generator has been utilized for fabricating nano-
composite layer in order to achieve more concentration of carbon nanotubes and to
increase the uniform distribution of nanoparticulates in deposited layer [137].
There is no wide study on specific nickel-tungsten/carbon nanotube (Ni-W/

CNT) nanocomposite layer formation by electrodeposition. Ni-W/CNT nano-
composite layer was performed by pulsed current and study the concentration of
nanoparticulates and process effective parameters on the electrochemical and
mechanical properties of coated samples. Distribution of nanoparticulates in
nanocomposite layers has also been investigated. The effect of duty cycle on
distribution of carbon nanotubes in nanocomposite layers shows strong attendance
but does not change the W content in the metallic matrix. Microhardness increased
for different nanocomposite layers with different amounts of carbon nanotubes.
Microhardness of nanocomposite layers did not change significantly by changing
the duty cycle.
Figure 2.7 illustrates the nanostructures of nanocomposite layers formed by
different (low, medium, and high) duty cycles of pulsed current. Comparison of
nanostructures of obtained nanocomposite layers shows that increasing duty cycle
significantly alters the distribution and content percentage of carbon nanotubes in
nanocomposite layers. It has been revealed that carbon nanotube content will
increase from 4.3 to 13.1 wt% by increasing duty cycle from 20 to 80%,
respectively, and agglomeration of nanoparticulates will decrease in higher duty
cycles. The first mentioned result was predictable since in higher duty cycles the
Fig. 2.7 Nanostructures of Ni-W/CNT nanocomposite layers formed by different duty cycles of
pulsed current: a 20% (AFM); b 50% (AFM); c 50% (TEM); d 80% (AFM) [137]
2.4 Mechanical Properties 51
electrochemical reaction for deposition of the metallic matrix has longer times for
its occurrence; hence, deposition of nanoparticulates in layer has longer times to
occur (in each cycle of pulsed current). By considering ideal distributed nano-
particulates in electrolyte, it can be concluded that increasing duty cycle will lead
to longer ‘‘on times’’ (of applied pulsed current in each cycle) and lower applied
potential (for obtaining constant average current density), which means lower
power for embedment of nanoparticulates into nanocomposite layer, so agglom-
eration is less than that in lower duty cycles that act in the opposite manner.
Figure 2.8 shows that the W content in the metallic matrix did not change
significantly by increasing duty cycle of pulsed current. Changing trend of the W
content is the same as carbon nanotube content. W content increased from 10.8 to
12.1 wt%. It can be assumed that the interaction of nanoparticulates and pulsed
current has an influence on the W content in the metallic matrix. It can easily be
concluded that effect of carbon nanotubes is much more than duty cycle, and
decreasing carbon nanotube content will also lead to a decrease in the W content of
the metallic matrix [137].
Microhardness of Ni-W and nanocomposite layers with respect to different
concentrations of carbon nanotubes as well as different applied duty cycles is
reported in Table 2.1, which increases from 522 HV for Ni-W alloy to 779 HV for
nanocomposite layer with 13.1 wt% of carbon nanotubes. Also, the W content in
nanocomposite layer will not change by changing the duty cycle of pulsed current,
so increasing microhardness of the obtained different nanocomposite layers with
the applied different duty cycles should be concerned by the presence of carbon
nanotubes. As mentioned before, there is less carbon nanotube in nanocomposite
layers, which are formed by lower duty cycles, but the microhardness of nano-
composite layers will not change significantly by changing the applied duty cycles
(Table 2.1). Thus, increasing duty cycle will lead to mutual effect of higher
contents of carbon nanotubes in the metallic matrix with simultaneous less normal
distribution, which in total will lead to approximately constant microhardness of
the obtained layer. Figure 2.9 illustrates the distribution of carbon nanotubes in a
500 nm 9 500 nm area of analyzed SEM nanostructures. Changing trend of dis-
tribution in this figure confirms our conclusions.
Fig. 2.8 Influence of duty

cycle of pulsed current on
CNT nanoparticulate contents
in obtained nanocomposite
layers and W contents in the
metallic matrix of
nanocomposite layers [137]
Table 2.1 Microhardness of Sample Duty cycle/% HV

Ni-W/CNT nanocomposite
electrodeposited layers [137] Ni-W – 522
Ni-W/CNT 20 725
35 739
50 754
65 767
80 779
2.5 Corrosion Properties
In general, corrosion resistance of nano-crystalline materials in aqueous solutions

is of great importance in an extensive area for future applications. There performed
few studies in this area. Both improved and disadvantageous results for devel-
opment of nano-crystalline in corrosion process have been recorded for corrosion
behavior of nano-crystalline produced by amorphous materials crystallization.
Obtained results are highly influenced by weak characteristics of crystallized
amorphous materials. In the other words, during last few years, there have been
considerable advancements in perception of fine structures effect on corrosion
properties for materials produced by electrodeposition process. In previous studies,
polarization at both constant and changing potentials, with deaerated 2 N sulfuric
acid (pH = 0) were performed on bulk pure Ni nano-crystals with grain sizes of
50, 32, and 500 nm and compared with pure multi-crystalline Ni with grain size of
100 lm.
Nano-crystalline specimens show the same active-inactive-trance-passive
behavior; and differences are between passive current density and open circuit
potential. Nano-crystalline specimens indicate more intense current in passive
zone, implying higher corrosion rate. This current density is mostly because of
more grain boundaries and triple connections in nano-crystalline samples, creating
electrochemically active spots. This density difference in current density decreases
for higher potentials (1,100 mV versus Calomel reference electrode). At this
potential difference, final dissolve rate overcome to structurally control dissolve
rate, existed at low potentials. Another obvious difference in polarization result, in
varying potential of nano-crystalline and multi-crystalline samples, is open circuit
potential. It seems that positive transition of open circuit potential for nano-
crystalline samples is due to catalyst properties of hydrogen releasing reaction.
Both samples show extensive corrosion; however this corrosion is more homog-
enous nano-crystalline Ni, while sample with grain size of 100 lm reveals more
developed local corrosion across grain boundary and triple connections. XRD
analysis of polarized samples for passive zone suggests that created passive layers
on nano-samples are less developed. This porous layer allows nano-crystalline
sample for a more homogenous destruction; while, on the other hand, for coarse
Ni, destruction of passive layer first happens at grains boundary and triple
connections rather than crystal surface, leading to preferred invasion in these
zones. There has been obtained similar approaches for corrosion behavior of
2.5 Corrosion Properties 53
Fig. 2.9 Distributions of CNT nanoparticulates in the metallic matrix of nanocomposite layers
for different applied duty cycles of pulsed current: a 20%; b 50%; c 80% [137]
nano-crystalline stainless steel (304) with grain size of 25 nm, in HCl, obtained
through spraying process. A decrease of sensitivity against local corrosion is due to
fine-grained micro-structure, conducts in an even distribution of Cl ions.
Recently, corrosive behavior of Ni nano-crystals, in 30 weight percentage KOH
solution and a solution with normal pH of 3 weight percentage of NaCl, has been
studied which produced results similar to those of sulfuric acid. Compared with
Ni multi-crystal, overall corrosion has an increase; however, nano-crystalline
materials are more protected against this local destruction which leads to cata-
strophic fracture. Using salt spraying test, it was found that under electrochemical
conditions fie-structure of Ni has a few effect on final corrosive performance. Both
micro-crystalline and nano-crystalline coatings reveal similar corrosive protection
on steel samples.
Another corrosion study was performed on nano-crystalline Ni according to
existed conditions on steam generator alloy, as a part of electro-sleeve develop-
ment program. Tests of sensitivity against intra-granular invasion and stress-
accompanied sensitivity against corrosion were performed on polytonal acids and
MgCl2, while alternative emerging test was carried out in NaCl. The results show
that electrodeposited nano-crystalline Ni with grain size of 100 nm is resistant
against intra-granular phenomena such as grain boundary invasion and corrosion
with grain boundary stresses. This material is resistant against local pitting attacks
and shows just a negligible sensitivity against crevice corrosion. Second group of
tests are concentrated on particular environments, where steam generator materials
are imposed. These environments include alkaline, acidic, and a compound of
oxidizing and reducing particles ones. Tests have shown excellent strength of
nano-crystals in base and reducing acidic environments. Resistance against cor-
rosion is limited in acidic and oxidizing environments [165–174].
2.6 Hydrogen Transition and Sensitivity
Hydrogen transition behavior in thin sheets of nano-crystalline Ni, with average

size of 17 nm at temperature of 293°K, is determined using electrochemical dual
storage. Based on determined permeability, permitted flux values, and surface
fraction (i.e. given volume), these changes are due to hydrogen transition across
distinct triple connections, grains boundary, and network paths. Permeability of
triple connection is about 3 and 70 times quicker than grain boundary and network
diffusion, respectively. This shows effect of triple connections defects. Moreover,
diffusion from triple connection zones in nano-crystalline Ni implies importance of
triple connection defect on bulk properties of nano-crystals. Nano-crystalline
Ni with average size of 20 nm shows more electro-catalytic behavior, in com-
parison with cooled, fine grained, and completely annealed Ni.
Another study on hydrogen transition behavior of Ni, using electrolytic
charging method, shows that an essential increase in permeability of hydrogen and
its capacity is obtained whenever Ni is in nano-crystalline form. Collecting
2.6 Hydrogen Transition and Sensitivity 55
hydrogen in dual electrodes of Ni with same thickness has this following order:
nano-crystal, fine grain, mono-crystalline structures. Besides, apparent concen-
tration of hydrogen in a 20 nm sample is around 60 times more than that of mono-
crystalline structure, based on allowed exchanges. Hydrogen permeability and
capacity is due to its more amounts of intra-crystalline spaces, offering these
following features:
1. High density from short circle diffusional paths
2. More free volumes, resulting in more segregation of hydrogen
2.7 Magnetic Characteristics and Ionic Conductivity
Many experiments suggest that magnetic characteristics depend on material size.

Although understanding magnetic structure of nano-structure materials is far away
from its complete state, there is a clear imagination from saturated magnetism; as
recent contradictory results about chemical and physical structure of nano-crys-
talline materials is justifiable. According first studies, nano-crystalline materials
show a great deal of decrease in saturated magnetism with decrease in grain size.
Approximately 40% of decrease in saturation magnetism was obtained in com-
parison with bulk alpha Fe for nano-crystalline Fe with grain size of 6 nm,
developed by simultaneous deposition of nano-particles obtained from consoli-
dation of pure gas. This behavior is due to differences in magnetism fine-structure
of nano-crystal and common multi-crystalline Fe.
In a same way, strong effects of particle size on saturation magnetism were
obtained during study of super tiny unconsolidated particles produced through gas
evaporation. For super tiny particles (10–50 nm) of Ni, Co, and Fe, an intense
decrease was observed in saturated magnetism with grain size reduction, which
was accompanied with nonmagnetic oxidized layers on particle. Another study on
these super tiny particles has shown magnification is negatively associated with
decrease of particles size. Decrease in saturation magnetism is accompanied with
surface effects—which are more important than grain size. Also, decrease of
saturation magnetism rate in Ni powder, due to evaporation of produced gas
resulted from structural disorder in interface, was recorded.
Measured magnetic momentum of interface atoms is about half of that of atoms
in coarse grain material. Further, it was found that super tiny Ni particles satu-
ration magnetism considerably reduces with grain size decrease. It was recorded
that accidental magnification of nano-crystalline gallium (Ga) samples produced
by gas consolidation and dimensional compaction is about 75% of its multi-
crystal. It must be added all mentioned samples are created using gas consolidation
method resulting in production of materials with high internal porosity, which
creates a big deal of surface area for oxide development after posing to free air. On
the other hand, it was recorded that saturation magnetism is not significantly
associated with grain size. Ni grains size has been declined from 10 to 100 nm;
then for Ni samples with tiniest grain size observed magnetism is just 10% less
than that of multi-crystalline Ni. These results were observed for bulk nano-
crystalline Ni created with electro-deposition method and its creation mechanism
was said to be unavoidable development of porous oxide.
Obtained results are coordinated with recent calculations, implying effect of
structural disorder. At these studies, grain boundary size is a source for different
disorder states. Measurements show that magnetic momentum is not really sen-
sitive to magnitude of structure disorder from grain boundaries. Once material
structure is amorphous, average momentum is only 15% of decrease; hence, for
nano-crystalline Ni with grain sizes of 10 nm, where grain boundary atoms occupy
30% space, final effect of structural disorder on medium momentum would be
negligible. Other recent records prove these results. For instance, for nano-crystal
created by rolling, there is no significant difference in saturation magnetism for
material with grain sizes of 1 nm and 50 lm. similar results have recorded for
Ni nano-crystals. Also, for nano-crystalline Ni created from gas consolidation
method, before posing it to free air saturation magnetism is independent from grain
size, but as soon as its pose to free air saturation magnetism declines to 80% of its
original value.
Recently Ishihara et al. [175] fabricated thin films of La1.61GeO5-d as a new
oxide ionic conductor, on dense polycrystalline Al2O3 substrates by a pulsed laser
deposition (PLD) method and studied the effect of the film thickness on the oxide
ionic conductivity on the nanoscale. The effective deposition parameters were
optimized to obtain La1.61GeO5-d thin films with stoichiometric composition.
Annealing was found necessary to get crystalline La1.61GeO5-d thin films. It was
also found that the annealed La1.61GeO5-d film exhibited extraordinarily high
oxide ionic conductivity. Due to the nano-size effects, the oxide ion conductivity
of La1.61GeO5-d thin films increased with the decreasing thickness as compared
to that in bulk La1.61GeO5-d. In particular, the improvement in conductivity of
the film at low temperature was significant.The electrical conductivity of
the La1.61GeO5-d film with a thickness of 373 nm is as high as 0.05 S.cm-1
(log (r/S cm-1) = -1.3) at 573°K.
The oxide ion conductor is an important functional material applied in different
fields such as fuel cells, oxygen sensors, oxygen pumps, water electrolysis, and
oxygen separating ceramic membrane. Among these application areas, the elec-
trolyte of fuel cell is attracting much interest. Several numbers of new oxide ion
conductors such as strontium and magnesium doped lanthanum gallate (LSGM)
and La10Si6O27 apatite oxide and were reported recently. Among the new oxide
ion conductors fabricated recently, La-deficient La2GeO5, is highly interesting,
because of its high oxide ion conductivity over a wide range of oxygen partial
pressure and unique structure. In La2GeO5 based oxides, La deficiency leads to the
formation of oxygen vacancies and oxide ion conductivity in La1.61GeO5-d is the
highest in La2GeO5 based oxides. The transport number of the oxide ion is nearly
unity in the O2 partial pressure range 1–10-21 atm and the conductivity is com-
parable to that of well-known fast oxide ion conductors, e.g., La0.9Sr0.1-
Ga0.8Mg0.2O3-d and Gd-doped CeO2. Recently, nano-size effects on ionic
2.7 Magnetic Characteristics and Ionic Conductivity 57
conductivity have been attracting much interest because of improved ion con-
ductivity. Some researchers reported that the fluoride ionic conductivity in CaF2
and BaF2 hetero-layered films, prepared by molecular-beam epitaxy, increases
proportionally with increasing interface density, namely, decreasing thickness,
when the interface spacing is larger than 50 nm, which is in agreement with the
semi-infinite space-charge calculation. In contrast, due to the positive charge at
grain boundary, negative nano-size effects were reported for the oxide ion con-
ductivity in CeO2 based oxides. On the other hand, it is reported that the oxide ion
conductivity in the laminated films consisting of ZrO2 and Gd doped CeO2 (GDC)
thin film increases with decreasing number of lamination. The effects of nano grain
size on the ionic conductivity on La2GeO5 based oxide film and it was found that
the conductivity was improved by decreasing film thickness of La2GeO5. How-
ever, in the conventional study, nano-size effects are not studied systematically and
so, the nano-size effects are still not clear.
New oxide ion conductor of La1.61GeO5-d film of various thicknesses was
fabricated as thin films of varying thickness on dense polycrystalline Al2O3
substrates by using pulsed laser deposition. The obtained La1.61GeO5-d film by
Ishihara et al. [175] exhibited almost the pure oxide ionic conductivity and
the oxide ion conductivity increased with the decrease of the film thickness.
In particular, increase of conductivity at low temperature was more significant.
Considering the stable valence number of La and variable valence of Ge (3+ and 4+),
the amount of oxygen vacancies can be determined by the composition of the film.
Since the composition of the prepared La1.61GeO5-d films is almost the same, it is
generally considered that the increased conductivity may not be explained by the
change in the amount of oxygen vacancy but by the improved mobility of oxide ion
by the local stress caused by the mismatch in lattice parameter between the film and
the substrate. Figure 2.10 illustrates arrhenius plots of La1.61GeO5-d thin films and
Fig. 2.10 Arrhenius plots of

La1.61GeO5-d thin films and
that of bulk La1.61GeO5-d
sample, reprinted with kind
permission from Tatsumi
Ishihara [175]
Fig. 2.11 PO2 dependence of

the electrical conductivity in
La1.61GeO5-d thin film with
various thicknesses at 873°K,
reprinted with kind
permission from Tatsumi
Ishihara [175]
that of bulk La1.61GeO5-d sample. PO2 dependence of the electrical conductivity in

La1.61GeO5-d thin film with various thicknesses at 873°K can be seen in Fig. 2.11.
2.8 Thermal Stability
Thermal stability of nano-crystals is of a great importance in high temperature

applications. For electro-deposited nano-crystals thermal stability is examined
through TEM and an indirect method, involving determination of thermal stability
using harness measurements as a function of annealing time. For synthetic growth
of grains there are some preventing factors for grain boundary movements leading
to their thermal stability. There is a slowing dual force in nano-crystals due to
triple connections. It can be easily shown that grain growth for fined multi-crystal
materials is controlled by inherent movement of triple connections. For thermal
stability of nano-structures, extra distributions of triple connections lead to pre-
ferred dissolve in these spots. Such a dissolve was observed in nano-crystals in
triple connections using TEM method. Ni stability with grain sizes of 10 and
20 nm was investigated, using TEM. Degradation temperature for these materials
is 353°K. This lack of stability is due to unusual germination after annealing.
2.9 Nanocoatings Applications
Nano-crystalline structures made of electro-deposition have some commercial

applications, due to these following reasons:
1. Electro-shaping and electroplating are recognized industries with extensive
usage.
2.9 Nanocoatings Applications 59
2. Their low cost: Nano-crystals can be created using a simple modification in

bath electrical parameters applied for electroplating and electro-shaping
current.
3. High potential of producing materials, alloys, and composites with metallic
matrix in different forms at one stage (i.e. coatings, complicated shapes, and
etc.).
4. Capability of producing nano-structures with high density and no porosity.
2.9.1 Structural Applications
As it is expected from Hall–Petch assumptions, there are different practical

applications for nano-crystals based on existed criteria for development of resistant
coatings. Preferential mechanical properties of electro-deposited nano-structures
are among their most important industrial applications. Electroplating process is
applied for in situ maintenance of nuclear steam generator tubes. This process is
successfully applied in aqueous reactors in US and Canada and registered as a
standard method for repairing pressure tube. Through this application, Ni with
grain size of 100 nm, is created on interior walls of steam generator tubes to
perform a complete structural maintenance in places where primary homogeneity
of tube structure is mitigated. High strength and convenient malleability of these
100 nm grains result in application of a thin plate (0.5–1 mm) which minimizes
fluid current and heat transition in steam generator. Recent geometrical models and
empirical achievements have shown that nano-structural materials can have a high
resistance against creep and inter-granular cracking. Different applications of
nano-structural materials, where their inter-granular properties of resistance
against cracking are used, include: positive plates of Acid-Pb batteries and load
shaped lines (made of Cu, Pb, and Ni) for industrial applications.
2.9.2 Functional Applications
One of the most successful applications of nano-structural materials is in soft

magnetic materials for engines, transformators, and etc. Predicted decrease in
anisotropy of magnetic crystal during grain size decrease, compared to its pre-
defined thickness, has been investigated. Electro-deposited nano-crystals would
have a low coordination without causing any damage to saturation magnetism.
Hence, application of these ferromagnetic materials with high efficiency in
engines, transformators, anti-attack applications, has been enhanced due to recent
advancements in electroplating technology. Through this technology it is possible
to economically mass production of plates, thin sheets, and wires. Another
important application of electroplated nano-crystalline materials is for production
of thin copper-made sheets for print circuit sheets.
Etching rate increases when grain size declines and grain sizes of 50–100 nm
provide optimum etching with maintaining convenient electrical conductivity. At
it previously mentioned, high density of intra-crystalline defects is present in bulk
state and cutting free surface of nano-structure materials offers a good chance for
hydrogen and catalyst storage applications. There are many different applications
for usage of these materials in both electrodeposited and electro-shaping methods
for battery systems and alkaline fuel cell electrodes.
2.9.3 Classification of Applications
Improved hardness, wear and corrosion resistances, as well as decrease of satu-

ration magnetism, acceptable thermal range, elastic properties, and electrical
resistance make nano-crystal coatings an ideal candidate for protecting and
associated coatings (such as in contact of hard and soft surface, coatings with less
abrasive resistance, electronic conductivity, and alternative coatings for Cr and Cd
in aerospace applications). Once such thin coatings are used, sediment fine-
structural changes with coating thickness increase of a great importance.
Most previous studies on electrodeposited metals, not necessarily on their nano-
crystalline form, have shown that increase of coating thickness causes to increase
of grain size. For electrodeposited nano-crystalline Ni, it is found that first the
sediment was amorphous with transition to nano-crystalline state and then there is
an increase in grain size. In contrary, electrodeposited nano-crystals of Ni suggest
that in most cases nano-crystals are exactly settled on interface with matrix and
grain size is basically dependent from coating thickness. For distinct electro-
chemical conditions there is a thin transition layer made of coarser grains. Finally
it has been proven that at initial layer with thickness of 200 nm grain sizes is
independent from thickness [155, 176–185]. Table 2.2 introduces some applica-
tions of nano-coatings.
2.10 Key Points for Development
2.10.1 Environment and Stability
In most cases surface engineering leads to economically use of materials and,

consequently, profitability in many applications. For instance, increasing service
lifetime there will be a decrease in wastes and energy consumption, which caused
to retrieve improvement. Many advanced surface engineering processes have
negligible environmental effects. One of developing activities in this filed is
recoating of high-cost panels. Environmental rules, limiting each one of these
panels wear, have a big share in progress of these industries.
Table 2.2 Applications of some size affected nano-coatings
2.10
Industrial applications of Coatings resistant against scratch, wear, corrosion, and environmental Coatings resistant against scratch, abrasion, corrosion,
nano-coatings factors and environmental factors
Using alumina as a scratch, abrasion resistant coating
Manufacturing light resistant panels for airplane structure
Nano-metric corrosion protector coating
Using nano-particles for coating in transportation
industry
Using nano-metric coating of ceramics in navy force
Using nano-metric coating for strength increase
Using nano-metric coating for clothes
Key Points for Development
Manufacturing nano-metric coating of WC/Co–Ni

through electrodepositing method
Various types of optical coatings including antireflection, mist Using light-resistant layers of UV
resistant coating and protective coatings Surface improvement for making mist and steam
resistant layers
Making panels with nano-metric coating
Self-cleaner glasses
Coatings with medical, biologic, and environmental applications Nano-metric coating of inorganic particles for medical
applications
Using nano-particles in masks
Using nano-metric coating of hydroxyl-apatite for
making prosthesis
Using nano-composite coating for food packing
Anti-pollution materials in shipping industry
Nano-composite coating for dealing with viruses
Using Ag nano-particles as an anti-bacterial coating
Using TiO2 nanoparticles to decrease environmental
pollutions
(continued)
61
Table 2.2 Continued
62
Coatings with electrical and electronic applications Making transparent conductor coatings using carbon nano-tubes
Using nano-metric coating in solar cells
Nano-metric coating of Ni particles with oxides
Using nano-metric polarizer layers in production of LCD monitors
Manufacturing transparent electrically conductor nano-metric coating
Increasing storage capacity by magnetic nano-layers
Development of nano-metric coating for lubrication of surfaces
2 Size Dependency in Nanostructures
2.10 Key Points for Development 63
2.10.2 Weight and Volume Reduction
From this viewpoint, applied panels—especially ones used in vehicle—are con-

sidered. Al, Ti, and Mg alloys are required for improvement of surface corrosive
and abrasive resistance. In these cases a mixture of two or several processes are
needed in surface engineering. Also, polymers’ surface engineering has a great
potential for development in structural applications.
2.10.3 Smart Layers and Structures
Application of enhanced structures is of suitable accountability for increasing

environmental conditions. This can conduct in more development in technolog-
ical application of sensors which are able to create a revolution in applications
such as intelligent anti-oxide layers in steam turbines, self-watching structures,
and packing food products. At all of these cases surface engineering plays a key
role.
2.10.4 Processes’ Understanding
Surface engineering processes and relationship between processes’ features

should be better understood. This adequate perception leads to improvement of
process control quality and trustable quality and more insurance of the buyer.
Modeling has a key role at these processes and generating convincing data is
preferable. Some of important technologies of surface engineering must be
improved through development of processes to increase rate of marked layer or
change step by step processes to a continuous ones.
2.10.5 Training
Engineers must mainly be aware of surface engineering potential and its exact role
on designing; also mechanical engineering courses should involve these points.
For instance, surface engineering must be created as a major in manufacturing
engineering. Lack of harmony and compatibility between industrial needs and
academic works will create some problems. This has been examined in various
cases. Surface engineering programs will finally cause to a development in uni-
versity and industry, which should be better emphasized.
2.11 Surface Engineering Share in Key Industry Sections
Building planes and vehicles comprehensively depend on surface-engineered

panels. About 80% of these industries make use of coating. England has first
position in field of steam turbines coating and annually obtains 1 billion pound
bonus. Advanced coating of panels has considerably increased during last decades.
In 1997, 23% of quick machining components for steel and 67% of monolithic
carbide panels are coated by physical and chemical evaporation. Coating with
Physical Vaporization Detector (PVD) method involves 5 billion pounds annual
revenue.
PVD coating in production of multi-layers for high efficiency cutting tools has
made dry machining possible, which needs a cooler coating with no decrease in
profitability. Surface engineering of dual compounds and light alloy panels are
used in special vehicles and advance applications such as coast equipment,
medicine, and sports. Continuous manufacturing and performance of packaging
industry is widely associated with surface engineering. Thanks to surface engi-
neering, 44 billion drink cans are annually produced in Europe. Coating role for
improvement of productions and their packaging is vital; especially in preventing
air and moisture diffusion on potato chips and prepared food, or as a protector
against crashing or cracking for thin glasses. Multilayer sputtering magnetron of
a coating with low diffusion on construction glasses decreases thermal waste to
60% during winters, which amounts to a significant annual figure of fuel/m2 of
glass. It is expected that 50% of buildings use these glasses till 2005. Plasma
improvement of polyethylene surface with high molecular weight causes its
durability against slight shakes, which is applied in medicine. For tissue recovery
with advanced bio-sensors, all attached plastic biomedical panels to substrates
use engineered surfaces to create efficient and compatible performance with
human body. All electronic panels and advance sensors, optical coatings, and etc.
also are benefited from surface engineering technology during building process
[186–188].
2.12 Estimation of Corrosion and Erosion Costs
During last 10 years, due to educations for improvement of awareness from cor-
rosion related issues, there was a 515 million pounds saving in England. Studies
show similar values of total gross products for India, China, and United States. For
United States decay costs exceeds 100 billion dollars annually. This is 1,300
million pounds for England, which is 3.5% of State gross product, where 3.0
million pounds is saved. This amount is 48–50 billion dollars in United States,
which compose 4% of per capita gross production. As it previously remarked, this
amounts to 10% of national gross production in developing countries.
2.13 Surface Engineering in Automobile Industry 65
2.13 Surface Engineering in Automobile Industry
There are nearly 27 million cars and 3.3 commercial vehicles in England roads.
Car sale in Europe was about 12 million in 1997, where England share was about
1.7 million. It is estimated that car manufacturing will be 17% of England’s
surface engineering. Surface engineering has a significant role in this industry;
since 6% of engine building costs and power transfer is for coating technology.
Total produced color for this industry exceeds 300 million pounds. Protective steel
and body panels, as infrastructures, need to be repaired; so, many of them are
galvanized and prepared for painting with another suitable coating. While metals
mostly are coated by organic painting, plastics should be initially metalized. Here,
application of wet processes competes with advancements in PVD and CVD
methods. Market is not the only effective factor on technology progress, but there
are some environmental and legislation concerns which are considered as a
powerful encouragement in this field. Painting just involves about 2 kg of vehicles
weight, while painting process emits about 5 kg Volatile Organic Compounds
(VOC) to the atmosphere. Efforts for reduction of this effect led to development of
powder technology advancement. Most of coatings changes involve using the
CrVI, where some substitute are being made for that. Automobile industry is
directed to reaching products with higher compatibility with environment; as in
their producing method application of CrVI is avoided. Mentioned cases are only a
small part of coating applications.
2.14 Surface Engineering in Power Generation Industry
Here, power generation is addressed to high efficiency engines for aerospace

industry, marine gas turbines, and electric generating turbines. Gas turbines are
considered as a part of combinational cyclic developed machinery. Gas turbines
have some advantages compared with equipment of power generating from fossil
fuels, such as higher efficiency, lower constructing costs and using different fuels.
This equipment work at higher temperatures and combustion and hot gas pass
occurs within them. Here, creep, oxidization, and corrosion are regarded among
important factors. Achieving ideal conditions, coating is of a great importance.
Coating system is widely applied in gas turbines to protect gas pass route and
increase system lifetime. The following objectives are supposed to be achieved
during 5 coming years:
1. A 50°C increase in work temperature
2. 10,000 h increase of panels lifetime
3. One hundred percent Increase in system visitation time
4. A wide increase of applied fuels, natural gas, heavy fuels originated from coal,
biomass, and etc.
Achieving these objectives, coating systems should be developed. There are so

many researches in this field. Regarding various findings all studies are directed on
intelligent corrosion resistant coatings. These coatings can be appropriate answer
for corrosive environments, in order to avoiding panels’ oxidization. This state is
achievable through plasma spray technology, CVD, development in platinum
aluminate, and new insulating materials (layering and staining where both have
low electrical conductivity). As well as above-mentioned applications, use of
composite surfaces as a substrate for main layer of ceramics—which of a good
thermal compatibility with the layer as well as stability against corrosion—is also
progressing. Nowadays, there are comprehensive investigations at this area.
References
1. Arranz, M.A., Colino, J.M.: Nanoscale ripple formation in Co/Si(100) thin films with Ar+
beam etching. J. Phys. Conf. Ser. 200, 1–4 (2010)
2. Aubry, A., Lei, D.Y., Maier, S.A., Pendry, J.B.: Broadband plasmonic device concentrating
the energy at the nanoscale: the crescent-shaped cylinder. Phys. Rev. B Conden. Matter
Mater. Phys. 82 (2010)
3. De Arruda Rodrigues, C., De Tacconi, N.R., Chanmanee, W., Rajeshwar, K.: Cathodic
electrosynthesis of niobium oxide one-dimensional nanostructures with tailored dimensions.
Electrochem. Solid State Lett. 13, B69–B72 (2010)
4. Krzeminski, M., Molinari, M., Troyon, M., Coqueret, X.: Characterization by atomic force
microscopy of the nanoheterogeneities produced by the radiation-induced cross-linking
polymerization of aromatic diacrylates. Macromolecules 43, 8121–8127 (2010)
5. Liang, H.W., Liu, S., Yu, S.H.: Controlled synthesis of one-dimensional inorganic
nanostructures using pre-existing one-dimensional nanostructures as templates. Adv. Mater.
22, 3925–3937 (2010)
6. Liang, S., Fang, X., Xia, T.L., Qing, Y., Guo, Z.X.: Self-assembled magnetic nanohead-FeSi
nanowire epitaxial heterojunctions by chemical vapor deposition. J. Phys. Chem. C 114,
16187–16190 (2010)
7. Rinaldi, A., Correa-Duarte, M.A., Salgueirino-Maceira, V., Licoccia, S., Traversa, E.,
Dāvila-Ibāãez, A.B., Peralta, P., Sieradzki, K.: Elastic properties of hard cobalt boride
composite nanoparticles. Acta Materialia 58, 6474–6486 (2010)
8. Xiao, X., Sachdev, A.K., Haddad, D., Li, Y., Sheldon, B.W., Soni, S.K.: Stress-induced Sn
nanowires from Si–Sn nanocomposite coatings. Appl. Phys. Lett. 97 (2010)
9. Enz, T., Sieger, H., Fasel, C., Hahn, H.: Nanocomposite formation through thermal
decomposition of mixed samarium and magnesium citrate-derived gels formed by spray
pyrolysis. J. Am. Ceram. Soc. 91, 3066–3073 (2008)
10. Bobzin, K., Ernst, F., Zwick, J., Schlaefer, T., Cook, D., Nassenstein, K., Schwenk, A.,
Schreiber, F., Wenz, T., Flores, G., Hahn, M.: Coating bores of light metal engine blocks
with a nanocomposite material using the plasma transferred wire arc thermal spray process.
11. Gregory, O.J., Wnuk, S., Downey, M.A., Wnuk, V.: Improved thermal spray
instrumentation using intermediate nanocomposite coatings. In: Proceedings of the
International Instrumentation Symposium, pp. 223–233. (2004)
12. Gregory, Q.J., Wnuk, S., Downey, M.A., Wnuk, V.: Improved thermal spray
instrumentation using intermediate nanocomposite coatings. In: Technical Papers of ISA,
pp. 223–233. (2004)
References 67
13. Dey, A., Mukhopadhyay, A.K., Gangadharan, S., Sinha, M.K., Basu, D., Bandyopadhyay,
N.R.: Nanoindentation study of microplasma sprayed hydroxyapatite coating. Ceram. Int.
35, 2295–2304 (2009)
14. Grigore, E., Ruset, C., Li, X., Dong, H.: The influence of carbon content on the
characteristics of V–C–N coatings deposited by combined magnetron sputtering and ion
implantation (CMSII). Surf. Coat. Technol. 204, 2006–2009 (2010)
15. Fox-Rabinovich, G.S., Yamamoto, K., Kovalev, A.I., Veldhuis, S.C., Ning, L., Shuster,
L.S., Elfizy, A.: Wear behavior of adaptive nano-multilayered TiAlCrN/NbN coatings under
dry high performance machining conditions. Surf. Coat. Technol. 202, 2015–2022 (2008)
16. Ii, J., Kim, I., Dost, S.: Texture evolution in TiN, TaN and W2N thin films, In: Materials
Science Forum, pp. 1591–1596. (2002)
17. Solodukhin, I.A., Khodasevich, V.V., Uglov, V.V., Brizuela, M., Oate, J.I.: The use of
preliminary ion implantation and heating on the substrate for modifying TiN coating
properties and TiN/substrate interface. Surf. Coat. Technol. 142–144, 1144–1147 (2001)
18. Ji, H.B., Xia, L.F., Ma, X.X., Sun, Y., Sun, M.R.: Comparison of surface properties of Ti–
6Al–4V coated with titanium nitride, TiN+TiC+Ti(C,N)/DLC, TiN/DLC and TiC/DLC
films by plasma-based ion implantation. Acta Metallurgica Sinica (English Letters) 13, 967–
973 (2000)
19. Olszyna, A.R., Biesiada, K., Smolik, J.: Super-hard carbon layers produced on the Al2O3/
Al2O3+x%SiC (whiskers) ceramic cutting edges. Plasma Process. Polym. 4, S278–S281
(2007)
20. Guo, Y., Ma, S., Xu, K.: Effects of carbon content and annealing temperature on the
microstructure and hardness of super hard Ti–Si–C–N nanocomposite coatings prepared by
pulsed d.c. PCVD. Surf. Coat. Technol. 201, 5240–5243 (2007)
21. Reiße, G., Weißmantel, S., Rost, D.: Preparation of super-hard coatings by pulsed laser
deposition. Appl. Phys. A Mater. Sci. Process. 79, 1275–1278 (2004)
22. Zhou, J., Walleser, J.K., Meacham, B.E., Branagan, D.J.: Novel in situ transformable
coating for elevated-temperature applications. J. Therm. Spray Tech. 19, 950–957 (2010)
23. Tsotsos, C., Baker, M.A., Polychronopoulou, K., Gibson, P.N., Giannakopoulos, K.,
Polycarpou, A.A., Böbel, K., Rebholz, C.: Structure and mechanical properties of low
temperature magnetron sputtered nanocrystalline (nc–)Ti(N,C)/amorphous diamond like
carbon (a–C:H) coatings. Thin Solid Films 519, 24–30 (2010)
24. Abad, M.D., Muñoz-Márquez, M.A., El Mrabet, S., Justo, A., Sánchez-López, J.C.: Tailored
synthesis of nanostructured WC/a–C coatings by dual magnetron sputtering. Surf. Coatings
Technol. 204, 3490–3500 (2010)
25. Garcia-Torres, J., Gómez, E., Vallés, E.: Modification of magnetic and structural properties
of Co and Co–Ag electrodeposits by sulphur incorporation. Mater. Chem. Phys. 122, 463–
469 (2010)
26. Fabrizi, A., Cabibbo, M., Cecchini, R., Spigarelli, S., Paternoster, C., Haidopoulo, M.,
Kiryukhantsev-Korneev, P.V.: Thermal stability of nanostructured coatings. In: Materials
Science Forum, pp. 1–22. (2010)
27. Wang, Y., Li, Z., Du, J., Wang, B.: Mechanical properties of the plasma-enhanced
magnetron sputtering Si–C–N coatings. Appl. Surf. Sci. 257, 1–5 (2010)
28. McCrea, J.L.: Industrial implementation of nanostructured cobalt as an alternative to hard
chrome. Surf. Eng. 26, 149–152 (2010)
29. Zhao, J., Peng, X., Wang, F.: Fabrication of a nitrided coating on a novel Ni–Cr
nanocomposite with increased surface hardness. Mater. Res. Bull. 45, 420–424 (2010)
30. Abu Samra, H., Staedler, T., Aronov, I., Xia, J., Jia, C., Wenclawiak, B., Jiang, X.:
Deposition and characterisation of nanocrystalline Mo2N/BN composite coatings by ECR
plasma assisted CVD. Surf. Coat. Technol. 204, 1919–1924 (2010)
31. Weston, D.P., Harris, S.J., Capel, H., Ahmed, N., Shipway, P.H., Yellup, J.M.:
Nanostructured Co–W coatings produced by electrodeposition to replace hard Cr on
aerospace components. Trans. Inst. Met. Finish. 88, 47–56 (2010)
32. Maury, F., Douard, A., Delclos, S., Samelor, D., Tendero, C.: Multilayer chromium based
coatings grown by atmospheric pressure direct liquid injection CVD. Surf. Coatings
Technol. 204, 983–987 (2009)
33. Kumar, A., Kaur, D.: Nanoindentation and corrosion studies of TiN/NiTi thin films for
biomedical applications. Surf. Coatings Technol. 204, 1132–1136 (2009)
34. Ziebert, C., Albers, U., Stüber, M., Ulrich, S.: Constitution and mechanical properties of
nanocrystalline reactive magnetron sputtered V–Al–C–N hard coatings as a function of the
carbon content. Plasma Process. Polym. 6, S560–S565 (2009)
35. Mofidi, S.H.H., Aliofkhazraei, M., Rouhaghdam, A.S., Ghobadi, E., Mohsenian, E.:
Improvement of surface characteristics by electroplating hard chromium coating post
treated by nanocrystalline plasma electrolytic carbonitriding. Plasma Process. Polym. 6,
S297–S301 (2009)
36. Tsyntsaru, N., Dikusar, A., Cesiulis, H., Celis, J.P., Bobanova, Z., Sidel’Nikova, S.,
Belevskii, S., Yapontseva, Y., Bersirova, O., Kublanovskii, V.: Tribological and corrosive
characteristics of electrochemical coatings based on cobalt and iron superalloys. Powder
Metall. Met. Ceram. 48, 419–428 (2009)
37. Fox-Rabinovich, G.S., Kovalev, A.I., Aguirre, M.H., Beake, B.D., Yamamoto, K., Veldhuis,
S.C., Endrino, J.L., Wainstein, D.L., Rashkovskiy, A.Y.: Design and performance of AlTiN
and TiAlCrN PVD coatings for machining of hard to cut materials. Surf. Coat. Technol.
204, 489–496 (2009)
38. Krause, M., Bedel, L., Taupeau, A., Kreissig, U., Munnik, F., Abrasonis, G., Kolitsch, A.,
Radnoczi, G., Czigāny, Z., Vanhulsel, A.: Structural and mechanical characterization of
BCxNy thin films deposited by pulsed reactive magnetron sputtering. Thin Solid Films 518,
77–83 (2009)
39. Zeng, Z., Zhou, Y., Zhang, B., Sun, Y., Zhang, J.: Designed fabrication of hard Cr{single
bond}Cr2O3{single bond}Cr7C3 nanocomposite coatings for anti-wear application. Acta
Mater. 57, 5342–5347 (2009)
40. Stueber, M., Holleck, H., Leiste, H., Seemann, K., Ulrich, S., Ziebert, C.: Concepts for the
design of advanced nanoscale PVD multilayer protective thin films. J. Alloys Compd. 483,
321–333 (2009)
41. Boonyongmaneerat, Y., Saengkiettiyut, K., Saenapitak, S., Sangsuk, S.: Effects of WC
addition on structure and hardness of electrodeposited Ni–W. Surf. Coat. Technol. 203,
3590–3594 (2009)
42. Gupta, G., Mondal, K., Balasubramaniam, R.: In situ nanocrystalline Fe–Si coating by
mechanical alloying. J. Alloys Compd. 482, 118–122 (2009)
43. Bobanova, Z.I., Dikusar, A.I., Cesiulis, H., Celis, J.P., Tsyntsaru, N.I., Prosycevas, I.:
Micromechanical and tribological properties of nanocrystalline coatings of iron–tungsten
alloys electrodeposited from citrate-ammonia solutions. Russ. J. Electrochem. 45, 895–901
(2009)
44. Vojtĕch, D.: Properties of hard Ni–P–Al2O3 and Ni–P–SiC coatings on al-aased casting
alloys. Mater. Manufact. Process. 24, 754–757 (2009)
45. Jung, A., Natter, H., Hempelmann, R., Lach, E.: Nanocrystalline alumina dispersed in
nanocrystalline nickel: enhanced mechanical properties. J. Mater. Sci. 44, 2725–2735
(2009)
46. Mishra, S.K.: Nano and nanocomposite superhard coatings of silicon carbonitride and
titanium diboride by magnetron sputtering. Int. J. Appl. Ceramic Technol. 6, 345–354
(2009)
47. Krella, A., Czyzniewski, A.: Cavitation resistance of Cr–N coatings deposited on austenitic
stainless steel at various temperatures. Wear 266, 800–809 (2009)
48. Aliofkhazraei, M., Sabour Rouhaghdam, A., Heydarzadeh, A., Elmkhah, H.: Nanostructured
layer formed on CP–Ti by plasma electrolysis (effect of voltage and duty cycle of cathodic/
anodic direction). Mater. Chem. Phys. 113, 607–612 (2009)
49. Ranjith, B., Paruthimal Kalaignan, G.: Ni–Co–TiO2 nanocomposite coating prepared by
pulse and pulse reversal methods using acetate bath. Appl. Surf. Sci. 257, 42–47 (2010)
References 69
50. Guo, Y., Wang, Q.: Facile approach in fabricating superhydrophobic coatings from silica-
based nanocomposite. Appl. Surf. Sci. 257, 33–36 (2010)
51. Antonello, A., Brusatin, G., Guglielmi, M., Martucci, A., Bello, V., Mattei, G., Mazzoldi,
P., Pellegrini, G.: Hybrid organic-inorganic ZnS–loaded nanocomposite films for stable
optical coatings. Thin Solid Films 518, 6781–6786 (2010)
52. Moskalewicz, T., Wendler, B., Czyrska-Filemonowicz, A.: Microstructural characterisation
of nanocomposite nc–MeC/a–C coatings on oxygen hardened Ti–6Al–4V alloy. Mater.
Charact. 61, 959–968 (2010)
53. Liu, X.W., Devaraju, M.K., Yin, S., Sato, T.: Calcium-doped ceria/titanate tabular
functional nanocomposite by layer-by-layer coating method. J. Solid State Chem. 183,
1545–1549 (2010)
54. Heidarian, M., Shishesaz, M.R., Kassiriha, S.M., Nematollahi, M.: Characterization of
structure and corrosion resistivity of polyurethane/organoclay nanocomposite coatings
prepared through an ultrasonication assisted process. Prog. Org. Coat. 68, 180–188 (2010)
55. Sharif, M., Faghihi-Sani, M.A., Golestani-Fard, F., Saberi, A., Soltani, A.K.: Coating of
graphite flakes with MgO/carbon nanocomposite via gas state reaction. J. Alloys Compd.
500, 74–77 (2010)
56. Mège-Revil, A., Steyer, P., Cardinal, S., Thollet, G., Esnouf, C., Jacquot, P., Stauder, B.:
Correlation between thermal fatigue and thermomechanical properties during the oxidation
of multilayered TiSiN nanocomposite coatings synthesized by a hybrid physical/chemical
vapour deposition process. Thin Solid Films 518, 5932–5937 (2010)
57. Vartiainen, J., Tuominen, M., Nättinen, K.: Bio-hybrid nanocomposite coatings from
sonicated chitosan and nanoclay. J. Appl. Polymer Sci. 116, 3638–3647 (2010)
58. Guo, Y., Jiang, D., Zhang, X., Zhang, Z., Wang, Q.: Room temperature synthesis of water-
repellent polystyrene nanocomposite coating. Appl. Surf. Sci. 256, 7088–7090 (2010)
59. Wo, P.C., Munroe, P.R., Zhou, Z.F., Li, K.Y., Xie, Z.H.: Effects of TiN sublayers on the
response of TiSiN nanocomposite coatings to nanoidentation and scratching contacts.
Mater. Sci. Eng. A 527, 4447–4457 (2010)
60. Abdul Samad, M., Sinha, S.K.: Nanocomposite UHMWPE-CNT polymer coatings for
boundary lubrication on aluminium substrates. Tribol. Lett. 38, 301–311 (2010)
61. Mulligan, C.P., Blanchet, T.A., Gall, D.: CrN–Ag nanocomposite coatings: high-
temperature tribological response. Wear 269, 125–131 (2010)
62. Bahadormanesh, B., Dolati, A.: The kinetics of Ni–Co/SiC composite coatings
electrodeposition. J. Alloys Compd. 504, 514–518 (2010)
63. Fan, Y., Chen, D.: Control-steps and influence factors of SiO2 electrodeposition process
with Zn coatings. In: Advanced Materials Research, pp. 1416–1419. (2010)
64. Rudnik, E.: Influence of Cs+ ions on codeposition of SiC particles with Ni–Co alloy. Trans.
Inst. Metal Finish. 87, 239–245 (2009)
65. Liu, H., Chen, W.: Electrodeposited Ni–Al composite coatings with high Al content by
sediment co-deposition. Surf. Coat. Technol. 191, 341–350 (2005)
66. Hu, F., Chan, K.C.: Electrocodeposition behavior of Ni–SiC composite under different
shaped waveforms. Appl. Surf. Sci. 233, 163–171 (2004)
67. Ramesh Bapu, G.N.K., Thiruchelvam, T.: Validity of adsorption mechanism for
electrodeposited zinc composites. Bull. Electrochem. 17, 405–408 (2001)
68. Chang, Y.C., Chang, Y.Y., Lin, C.I.: Process aspects of the electrolytic codeposition of
molybdenum disulfide with nickel. Electrochim. Acta 43, 315–324 (1998)
69. Mirzamohammadi, S., Kiarasi, R., Aliov, M.K., Sabur, A.R., Hassanzadeh-Tabrizi, A.:
Study of corrosion resistance and nanostructure for tertiary Al2O3/Y2O3/CNT pulsed
electrodeposited Ni based nanocomposite. Trans. Inst. Metal Finish. 88, 93–99 (2010)
70. Ulrich, S., Ye, J., Stüber, M., Ziebert, C.: Cubic boron nitride based metastable coatings and
nanocomposites. Thin Solid Films 518, 1443–1450 (2009)
71. Popov, C., Bliznakov, S., Kulisch, W.: Influence of the substrate nature on the properties of
nanocrystalline diamond films. Diam. Relat. Mater. 16, 740–743 (2007)
72. Perez-Mariano, J., Lau, K.H., Sanjurjo, A., Caro, J., Casellas, D., Colominas, C.: TiSiN
nanocomposite coatings by chemical vapor deposition in a fluidized bed reactor at
atmospheric pressure (AP/FBR-CVD). Surf. Coat. Technol. 201, 2217–2225 (2006)
73. Kulisch, W., Popov, C., Vorlicek, V., Gibson, P.N., Favaro, G.: Nanocrystalline diamond
growth on different substrates. Thin Solid Films 515, 1005–1010 (2006)
74. Li, Y.S., Kiyono, H., Shimada, S., Lu, X., Hirose, A.: Mechanical and field emission
properties of CGed Si(C,N) films synthesized by PECVD from HMDS precursor. Diam.
Relat. Mater. 15, 1727–1731 (2006)
75. Lattemann, M., Sell, K., Ye, J., Persson, P.A.O., Ulrich, S.: Stress reduction in
nanocomposite coatings consisting of hexagonal and cubic boron nitride. Surf. Coat.
Technol. 200, 6459–6464 (2006)
76. Li, Y.S., Shimada, S., Kiyono, H., Hirose, A.: Synthesis of Ti–Al–Si–N nanocomposite
films using liquid injection PECVD from alkoxide precursors. Acta Mater. 54, 2041–2048
(2006)
77. Winkelmann, A., Cairney, J.M., Hoffman, M.J., Martin, P.J., Bendavid, A.: Zr–Si–N films
fabricated using hybrid cathodic arc and chemical vapour deposition: structure vs.
properties. Surf. Coat. Technol. 200, 4213–4219 (2006)
78. Yoon, J.K., Kim, G.H., Han, J.H., Shon, I.J., Doh, J.M., Hong, K.T.: Low-temperature
cyclic oxidation behavior of MoSi2/Si3N4 nanocomposite coating formed on Mo substrate at
773 K. Surf. Coat. Technol. 200, 2537–2546 (2005)
79. Polini, R., Amar, M., Ahmed, W., Kumashiro, S., Sein, H., Colligon, J.S.: A study of
diamond synthesis by hot filament chemical vapour deposition on nanocomposite coatings.
Thin Solid Films 489, 116–121 (2005)
80. Aliofkhazraei, M., Rouhaghdam, A.S., Ghobadi, E., Mohsenian, E.: Electrodeposition and
mechanical and corrosion resistance properties of tertiary Ni-W/Al2O3/CNT nanocomposite
coatings. In: Advanced Materials Research, pp. 12–16. (2010)
81. Ciubotariu, A., Benea, L., Lakatos-Varsanyi, M., Dragan, V.: Electrochemical impedance
spectroscopy and corrosion behaviour of Al2O3–Ni nano composite coatings. Electrochim.
Acta 53, 4557–4563 (2008)
82. de Hazan, Y., Werner, D., Z’Graggen, M., Groteklaes, M., Graule, T.: Homogeneous Ni–P/
Al2O3 nanocomposite coatings from stable dispersions in electroless nickel baths. J. Colloid
Interf. Sci. 328, 103–109 (2008)
83. Feng, Q., Li, T., Teng, H., Zhang, X., Zhang, Y., Liu, C., Jin, J.: Investigation on the
corrosion and oxidation resistance of Ni–Al2O3 nano-composite coatings prepared by
sediment co-deposition. Surf. Coat. Technol. 202, 4137–4144 (2008)
84. Feng, Q., Li, T., Yue, H., Bai, F., Qi, K., Jin, J.: Sediment co-deposition of nanostructured
Ni-Al2O3 composite coatings. In: Key Engineering Materials, pp. 244–247. (2008)
85. Feng, Q., Li, T., Zhang, Z., Zhang, J., Liu, M., Jin, J.: Preparation of nanostructured Ni/
Al2O3 composite coatings in high magnetic field. Surf. Coat. Technol. 201, 6247–6252
(2007)
86. Liu, Y., Ren, L., Yu, S., Han, Z.: Influence of current density on nano-Al2O3/Ni+Co bionic
gradient composite coatings by electrodeposition. J. Univ. Sci. Technol. Beijing Min.
Metallurg. Mater. (Eng Ed) 15, 633–637 (2008)
87. Liu, Y., Yu, S.R., Ren, L.Q., Han, Z.W.: Nano-Al2O3/Ni + Co gradient composite coating
by electrodeposition. Jilin Daxue Xuebao (Gongxueban)/J. Jilin Univ. (Engineering and
Technology Edition) 39, 154–158 (2009)
88. Mirzamohammadi, S., Aliov, M.K., Sabur, A.R., Hassanzadeh-Tabrizi, A.: Study of wear
resistance and nanostructure of tertiary Al2O3/Y2O3/CNT pulsed electrodeposited ni-based
nanocomposite. Mater. Sci. 46, 76–86 (2010)
89. Wu, B., Xu, B.S., Zhang, B., Lü, Y.H.: Preparation and properties of Ni/nano-Al2O3
composite coatings by automatic brush plating. Surf. Coat. Technol. 201, 6933–6939 (2007)
90. Zhang, H., Zhou, Y., Hu, H.: Preparation and oxidation performance of an-Al2O3-modified
chromizing coating. Xiyou Jinshu Cailiao Yu Gongcheng/Rare Metal Mater. Eng. 38, 1655–
1658 (2009)
References 71
91. Zheng, H.Y., An, M.Z.: Electrodeposition of Zn–Ni–Al2O3 nanocomposite coatings under
ultrasound conditions. J. Alloys Compd. 459, 548–552 (2008)
92. Zheng, H.Y., An, M.Z., Lu, J.F.: Surface characterization of the Zn–Ni–Al2O3
nanocomposite coating fabricated under ultrasound condition. Appl. Surf. Sci. 254, 1644–
1650 (2008)
93. Zhou, Y.B., Chen, H.Y., Zhang, H.J., Wang, Y.D.: Oxidation of Al2O3-dispersion
chromizing coating by pack-cementation at 800°C. Trans. Nonferrous Metals Soc. China
(English Edition) 18, 598–602 (2008)
94. Wang, H., Zuo, D., Chen, G., Sun, G., Li, X., Cheng, X.: Hot corrosion behaviour of low Al
NiCoCrAlY cladded coatings reinforced by nano-particles on a Ni-base super alloy. Corros.
Sci. 52, 3561–3567 (2010)
95. Barshilia, H.C., Acharya, S., Ghosh, M., Suresh, T.N., Rajam, K.S., Konchady, M.S., Pai,
D.M., Sankar, J.: Performance evaluation of TiAlCrYN nanocomposite coatings deposited
using four-cathode reactive unbalanced pulsed direct current magnetron sputtering system.
Vacuum 85, 411–420 (2010)
96. Chatterjee, S., Shariff, S.M., Padmanabham, G., Majumdar, J.D., Choudhury, A.R.: Study
on the effect of laser post-treatment on the properties of nanostructured Al2O3–TiB2–TiN
based coatings developed by combined SHS and laser surface alloying. Surf. Coat. Technol.
205, 131–138 (2010)
97. Tang, F., Alam, T., Moody, M.P., Gault, B., Cairney, J.M.: Challenges associated with the
characterisation of nanocrystalline materials using atom probe tomography. In: Materials
Science Forum, pp. 2366–2369. (2010)
98. Wang, H., Zuo, D., Yan, J., Huang, M., Li, X.: Effects of nanometer Al2O3 particles on
oxidation behaviors of laser cladding low Al NiCoCrAlY coatings. Oxid. Met. 74, 49–60
(2010)
99. Masanta, M., Ganesh, P., Kaul, R., Roy Choudhury, A.: Microstructure and mechanical
properties of TiB2–TiC–Al2O3–SiC composite coatings developed by combined SHS, sol-
gel and laser technology. Surf. Coat. Technol. 204, 3471–3480 (2010)
100. Lu, H., Zhang, W., Zhang, R., Xu, H., Wang, H., Chen, D., Yang, D.: Preparation of Fe
coating Al2O3 nanometer composite powder and its mechanical properties after hot press
sintering. Preparation of Fe coating Al2O3 nanometer composite powder and its mechanical
properties after hot press sintering. In: Advanced Materials Research, pp. 16–19. (2010)
101. Gao, J., He, Y., Wang, D.: Fabrication and high temperature oxidation resistance of ZrO2/
Al2O3 micro-laminated coatings on stainless steel. Mater. Chem. Phys. 123, 731–736 (2010)
102. Olszōwka-Myalska, A., Myalski, J., Botor-Probierz, A.: Microstructural characteristics of
an AZ91 matrix-glassy carbon particle composite. Adv. Eng. Mater. 12, 609–616 (2010)
103. Wang, L., Wan, S., Wang, S.C., Wood, R.J.K., Xue, Q.J.: Gradient DLC-based
nanocomposite coatings as a solution to improve tribological performance of aluminum
alloy. Tribol. Lett. 38, 155–160 (2010)
104. Yin, B., Liu, G., Zhou, H., Chen, J., Yan, F.: Microstructures and properties of plasma
sprayed FeAl/CeO2/ZrO2 nano-composite coating. Appl. Surf. Sci. 256, 4176–4184 (2010)
105. Han, Y., Wu, G., Li, H., Wang, M., Chen, H.: Highly efficient ultraviolet photodetectors
based on TiO2 nanocrystal-polymer composites via wet processing. Nanotechnology 21
(2010)
106. Labille, J., Feng, J., Botta, C., Borschneck, D., Sammut, M., Cabie, M., Auffan, M., Rose, J.,
Bottero, J.Y.: Aging of TiO2 nanocomposites used in sunscreen. Dispersion and fate of the
degradation products in aqueous environment. Environ. Pollut. 158, 3482–3489 (2010)
107. Lu, Z., Ren, M., Yin, H., Wang, A., Ge, C., Zhang, Y., Yu, L., Jiang, T.: Preparation of
nanosized anatase TiO2-coated kaolin composites and their pigmentary properties. Powder
Technol. 196, 122–125 (2009)
108. Dinh, N.N., Chi, L.H., Long, N.T., Thuy, T.T.C., Trung, T.Q., Kim, H.K.: Preparation and
characterization of nanostructured composite films for organic light emitting diodes. J. Phys.
Conf. Ser. 187 (2009)
109. Dinh, N.N., Chi, L.H., Chung Thuy, T.T., Trung, T.Q., Truong, V.V.: Enhancement of
current-voltage characteristics of multilayer organic light emitting diodes by using
nanostructured composite films. J. Appl. Phys. 105 (2009)
110. Yang, S.M., Chang, Y.Y., Lin, D.Y., Wang, D.Y., Wu, W.: Thermal stability of TiAlN and
nanocomposite TiAlSiN thin films. J. Nanosci. Nanotechnol. 9, 1108–1112 (2009)
111. Dinh, N.N., Chi, L.H., Thuy, T.T.C., Thanh, D.V., Nguyen, T.P.: Study of nanostructured
polymeric composites and hybrid layers used for light-emitting diodes. J. Korean Phys. Soc.
53, 802–805 (2008)
112. Oliveira, J.C., Manaia, A., Cavaleiro, A.: Hard amorphous Ti–Al–N coatings deposited by
sputtering. Thin Solid Films 516, 5032–5038 (2008)
113. Abdel Aal, A.: Hard and corrosion resistant nanocomposite coating for Al alloy. Mater. Sci.
Eng. A 474, 181–187 (2008)
114. Zhai, C.S., Wang, J., Li, F., Tao, J.C., Yang, Y., Sun, B.D.: Thermal shock properties and
failure mechanism of plasma sprayed Al2O3/TiO2 nanocomposite coatings. Ceram. Int. 31,
817–824 (2005)
115. Parlinska-Wojtan, M., Karimi, A., Coddet, O., Cselle, T., Morstein, M.: Characterization of
thermally treated TiAlSiN coatings by TEM and nanoindentation. Surf. Coat. Technol. 188–
189, 344–350 (2004)
116. Zahmatkesh, B., Enayati, M.H.: A novel approach for development of surface
nanocomposite by friction stir processing. Mater. Sci. Eng. A 527, 6734–6740 (2010)
117. Pourhosseini, J., Zakeri, M., Rahimipour, M.R., Salahi, E., Pourhosseini, G.R.: Preparation
of FeAl–Al2O3 nanocomposite via mechanical alloying and subsequent annealing. Mater.
Sci. Technol. 26, 1132–1136 (2010)
118. Zhitomirsky, V.N., Kim, S.K., Burstein, L., Boxman, R.L.: X-ray photoelectron
spectroscopy of nano-multilayered Zr–O/Al–O coatings deposited by cathodic vacuum
arc plasma. Appl. Surf. Sci. 256, 6246–6253 (2010)
119. Lv, H., Zhao, W., An, Q., Nie, P., Wang, J., Chu, P.K.: Nanomechanical properties and
microstructure of ZrO2/Al2O3 plasma sprayed coatings. Mater. Sci. Eng. A 518, 185–189
(2009)
120. Chen, C.H., Li, H.Y., Chien, C.Y., Yen, F.S., Chen, H.Y., Lin, J.M.: Preparation and
characterization of a-Al2O3/Nylon 6 nanocomposite masterbatches. J. Appl. Polym. Sci.
112, 1063–1069 (2009)
121. Kulkarni, T., Wang, H.Z., Basu, S.N., Sarin, V.K.: Phase transformations in mullite-based
nanocomposites. Int. J. Refract Metal Hard Mater. 27, 465–471 (2009)
122. Stüber, M., Albers, U., Leiste, H., Seemann, K., Ziebert, C., Ulrich, S.: Magnetron
sputtering of hard Cr–Al–N–O thin films. Surf. Coat. Technol. 203, 661–665 (2008)
123. Wang, S.C., Tseng, C.H.: Effects of Al2O3 nanoparticle on the microstructure and magnetic
properties of Co/Al2O3 coatings prepared by composite plating. In: Advanced Materials
Research, pp. 131–139. (2008)
124. Chang, Y.Y., Chang, C.P., Wang, D.Y., Yang, S.M., Wu, W.: High temperature oxidation
resistance of CrAlSiN coatings synthesized by a cathodic arc deposition process. J. Alloys
Compd. 461, 336–341 (2008)
125. Du, X., Xu, Y.: Formation of Al2O3–BaTiO3 nanocomposite oxide films on etched
aluminum foil by sol-gel coating and anodizing. J. Sol Gel. Sci. Technol. 45, 57–61 (2008)
126. Balani, K., Bakshi, S.R., Chen, Y., Laha, T., Agarwal, A.: Role of powder treatment and
carbon nanotube dispersion in the fracture toughening of plasma-sprayed aluminum oxide-
carbon nanotube nanocomposite. J. Nanosci. Nanotechnol. 7, 3553–3562 (2007)
127. Hannula, S.P., Turunen, E., Keskinen, J., Varis, T., Fält, T., Gustafsson, T.E., Nowak, R.:
Development of nanostructured Al2O3–Ni HVOF coatings. In: Key Engineering Materials,
pp. 539–544. (2006)
128. Vida-Simiti, I., Jumate, N., Negrea, G., Sechel, N., Coman, C.: Structure of some composite
materials for excessive wear applications. Metalurgia Int. 14, 137–140 (2009)
129. Lin, W.S., Qian, S.Q., Xu, M.M.: Wear behavior of electro-brush plating Nano-WC/PTFE-
Ni composite coatings. Mocaxue Xuebao/Tribology 27, 442–446 (2007)
References 73
130. Chen, H., Xu, C., Qu, J., Hutchings, I.M., Shipway, P.H., Liu, J.: Sliding wear behaviour of
laser clad coatings based upon a nickel-based self-fluxing alloy co-deposited with conventional
and nanostructured tungsten carbide-cobalt hardmetals. Wear 259, 801–806 (2005)
131. Mangam, V., Bhattacharya, S., Das, K., Das, S.: Friction and wear behavior of Cu–CeO2
nanocomposite coatings synthesized by pulsed electrodeposition. Surf. Coat. Technol. 205,
801–805 (2010)
132. Zanella, C., Lekka, M., Bonora, P.L.: Effect of ultrasound vibration during electrodeposition
of Ni–SiC nanocomposite coatings. Surf. Eng. 26, 511–518 (2010)
133. Zhou, Z.F., Pan, Y., Lei, W.X.: Ni nanocomposite films formed by Ni nanowires embedded
in Ni matrix using electrodeposition. Trans. Nonferrous Metals Soc. China (English Edition)
20, 637–642 (2010)
134. Frade, T., Bouzon, V., Gomes, A., da Silva Pereira, M.I.: Pulsed-reverse current
electrodeposition of Zn and Zn–TiO2 nanocomposite films. Surf. Coat. Technol. 204,
3592–3598 (2010)
135. Xue, Y.J., Liu, H.B., Lan, M.M., Li, J.S., Li, H.: Effect of different electrodeposition
methods on oxidation resistance of Ni–CeO2 nanocomposite coating. Surf. Coat. Technol.
204, 3539–3545 (2010)
136. Wang, G., Zhang, K.: Superplastic Properties of Al2O3/Ni–Mn nanocomposite fabricated by
electrodeposition. J. Mater. Sci. Technol. 26, 625–628 (2010)
137. Aliofkhazraei, M., Ahangarani, S., Sabour Rouhaghdam, A.: Effect of the duty cycle of
pulsed current on nanocomposite layers formed by pulsed electrodeposition. Rare Metals
29, 209–213 (2010)
138. Tsai, Y.C., Hong, Y.H.: Electrodeposition of platinum and ruthenium nanoparticles in
multiwalled carbon nanotube-nafion nanocomposite for methanol electrooxidation.
J. Nanomater. 2009 (2009)
139. Ramalingam, S., Muralidharan, V.S., Subramania, A.: Electrodeposition and
characterization of Cu–TiO2 nanocomposite coatings. J. Solid State Electrochem. 13,
1777–1783 (2009)
140. Hosseini, M.G., Abdolmaleki, M., Sadjadi, S.A.S., Boroujen, M.R., Arshadi, M.R.,
Khoshvaght, H.: Electrodeposition of Ni-WndashB nanocomposite from tartrate electrolyte
as alternative to chromium plating. Surf. Eng. 25, 382–388 (2009)
141. Wang, P., Gao, L., Wang, L., Zhang, D., Yang, S., Song, X., Qiu, Z., Murakami, R.I.:
Magnetic properties of feni nanowire arrays assembled on porous AAO template by AC
electrodeposition. Int. J. Modern Phys. B 24, 2303–2307 (2010)
142. Hu, F., Chan, K.C., Yue, T.M., Surya, C.: Dynamic template assisted electrodeposition of
porous ZnO thin films using a triangular potential waveform. J. Phys. Chem. C 114, 5811–
5816 (2010)
143. Xia, X.H., Tu, J.P., Xiang, J.Y., Huang, X.H., Wang, X.L., Zhao, X.B.: Hierarchical porous
cobalt oxide array films prepared by electrodeposition through polystyrene sphere template
and their applications for lithium ion batteries. J. Power Sour. 195, 2014–2022 (2010)
144. Ma, B., Li, Y., Zhao, J., Li, X., Xin, W.: Novel structural functional films based on self-
assembly template and electrodeposition: synthesis and characterization of porous Ni/YSZ
films. Thin Solid Films 517, 5172–5175 (2009)
145. Ibrahim Khan, M., Xu, W., Xiaoye, J., Bozhilov, K.N., Ozkan, C.S.: Study of a single insb
nanowire fabricated via DC electrodeposition in porous templates. J. Nanosci. Nanotechnol.
9, 2639–2644 (2009)
146. Deng, M.J., Leong, T.I., Sun, I.W., Chen, P.Y., Chang, J.K., Tsai, W.T.: Fabrication of
porous tin by template-free electrodeposition of tin nanowires from an ionic liquid.
Electrochem. Solid-State Lett. 11, D85–D88 (2008)
147. Phok, S., Rajaputra, S., Singh, V.P.: Copper indium diselenide nanowire arrays by
electrodeposition in porous alumina templates. Nanotechnology 18 (2007)
148. Gelves, G.A., Murakami, Z.T.M., Krantz, M.J., Haber, J.A.: Multigram synthesis of copper
nanowires using ac electrodeposition into porous aluminium oxide templates. J. Mater.
Chem. 16, 3075–3083 (2006)
149. Yan, H., Yang, Y., Fu, Z., Yang, B., Xia, L., Fu, S., Li, F.: Fabrication of 2D and 3D ordered
porous ZnO films using 3D opal templates by electrodeposition. Electrochem. Commun. 7,
1117–1121 (2005)
150. Gerein, N.J., Haber, J.A.: Effect of ac electrodeposition conditions on the growth of high
aspect ratio copper nanowires in porous aluminum oxide templates. J. Phys. Chem. B 109,
17372–17385 (2005)
151. Yan, H., Yang, Y., Fu, Z., Yang, B., Wang, Z., Xia, L., Yu, S., Fu, S., Li, F.: Fabrication of
2D ordered porous ZnO films using 3D opal templates by electrodeposition. Chem. Lett. 34,
976–977 (2005)
152. Wu, M.T., Leu, I.C., Yen, J.H., Hon, M.H.: Novel electrodeposition behavior of Ni on
porous anodic alumina templates without a conductive interlayer. J. Phys. Chem. B 109,
9575–9580 (2005)
153. Kumar, S., Kumar, S., Chakarvarti, S.K.: SEM morphology and XRD characterization of Ni
microstructure arrays synthesized by dc electrodeposition in porous polycarbonate
templates. J. Mater. Sci. 39, 3249–3251 (2004)
154. Hou, K.H., Chang, Y.F., Chang, S.M., Chang, C.H.: The heat treatment effect on the
structure and mechanical properties of electrodeposited nano grain size Ni–W alloy
coatings. Thin Solid Films 518, 7535–7540 (2010)
155. Bhanvase, B.A., Sonawane, S.H.: New approach for simultaneous enhancement of
anticorrosive and mechanical properties of coatings: application of water repellent nano
CaCO3-PANI emulsion nanocomposite in alkyd resin. Chem. Eng. J. 156, 177–183 (2010)
156. Han, B., Lu, X.: Effect of nano-sized CeF3 on microstructure, mechanical, high temperature
friction and corrosion behavior of Ni–W composite coatings. Surf. Coat. Technol. 203,
3656–3660 (2009)
157. Ballarre, J., Jimenez-Pique, E., Anglada, M., Pellice, S.A., Cavalieri, A.L.: Mechanical
characterization of nano-reinforced silica based sol-gel hybrid coatings on AISI 316L
stainless steel using nanoindentation techniques. Surf. Coat. Technol. 203, 3325–3331
(2009)
158. Lekka, M., Koumoulis, D., Kouloumbi, N., Bonora, P.L.: Mechanical and anticorrosive
properties of copper matrix micro- and nano-composite coatings. Electrochim. Acta 54,
2540–2546 (2009)
159. Zanella, C., Lekka, M., Bonora, P.L.: Influence of the particle size on the mechanical and
electrochemical behaviour of micro- and nano-nickel matrix composite coatings. J. Appl.
Electrochem. 39, 31–38 (2009)
160. Dhoke, S.K., Bhandari, R., Khanna, A.S.: Effect of nano-ZnO addition on the silicone-
modified alkyd-based waterborne coatings on its mechanical and heat-resistance properties.
Prog. Org. Coat. 64, 39–46 (2009)
161. Fedorischeva, M.V., Sergeev, V.P., Popova, N.A., Kozlov, E.V.: Temperature effect on
microstructure and mechanical properties of the nano-structured Ni3Al coating. Mater. Sci.
Eng. A 483–484, 644–649 (2008)
162. Wilson, G.M., Saied, S.O., Field, S.K.: Mechanical and physical properties of C and C–Cr
sputter coatings measured at the nano-scale. Thin Solid Films 515, 7820–7828 (2007)
163. Park, S.Y., Kim, M.C., Park, C.G.: Mechanical properties and microstructure evolution of
the nano WC–Co coatings fabricated by detonation gun spraying with post heat treatment.
Mater. Sci. Eng. A 448–451, 894–897 (2007)
164. Jiang, L., Lam, Y.C., Tam, K.C., Li, D.T., Zhang, J.: The influence of fatty acid coating on
the rheological and mechanical properties of thermoplastic polyurethane (TPU)/nano-sized
precipitated calcium carbonate (NPCC) composites. Polymer Bull. 57, 575–586 (2006)
165. Pinto, E.M., Ramos, A.S., Vieira, M.T., Brett, C.M.A.: Brett, A corrosion study of
nanocrystalline copper thin films. Corros. Sci. 52, 3891–3895 (2010)
166. Saha, G.C., Khan, T.I.: The corrosion and wear performance of microcrystalline WC–
10Co–4Cr and near-nanocrystalline WC–17Co high velocity oxy-fuel sprayed coatings on
steel substrate. Metallurg. Mater. Trans. A Phys. Metallurgy Mater. Sci. 41, 3000–3009
(2010)
References 75
167. Liu, L., Li, Y., Wang, F.H.: Pitting corrosion behavior of a sputtered nanocrystalline thin
film of austenitic stainless steel in 3.5 mass% NaCl solution. Corros. Sci. Protect. Technol.
22, 283–288 (2010)
168. Luo, W., Xu, Y., Wang, Q., Shi, P., Yan, M.: Effect of grain size on corrosion of
nanocrystalline copper in NaOH solution. Corros. Sci. 52, 3509–3513 (2010)
169. Chandrasekar, M.S., Shanmugasigamani, M.S., Malathy, P.: Synergetic effects of pulse
constraints and additives in electrodeposition of nanocrystalline zinc: corrosion, structural
and textural characterization. Mater. Chem. Phys. 124, 516–528 (2010)
170. Xu, J., Zhou, C., Jiang, S.: Investigation on corrosion behavior of sputter-deposited
nanocrystalline (MoxCr1-x)5Si3 films by double cathode glow plasma. Intermetallics 18,
1669–1675 (2010)
171. Nie, F.L., Zheng, Y.F., Cheng, Y., Wei, S.C., Valiev, R.Z.: In vitro corrosion and
cytotoxicity on microcrystalline, nanocrystalline and amorphous NiTi alloy fabricated by
high pressure torsion. Mater. Lett. 64, 983–986 (2010)
172. Okouchi, H., Seki, Y., Sekigawa, T., Hira, H., Kawamura, Y.: Nanocrystalline LPSO Mg–
Zn–Y–Al alloys with high mechanical strength and corrosion resistance. In: Materials
Science Forum, pp. 1476–1481. (2010)
173. Lee, H.B., Wuu, D.S., Lee, C.Y., Lin, C.S.: Study of the corrosion behavior of
nanocrystalline Ni–P electrodeposited coating. Metallurg. Mater. Trans. A Phys.
Metallurg. Mater. Sci. 41, 450–459 (2010)
174. Sousa, C.C., Kiminami, C.S.: Corrosion of Fe-based nanocrystalline alloys with soft
magnetic properties. J. ASTM Int. 7, 1–12 (2010)
175. Ishihara, T., Yan, J., Matsumoto, H.: Extraordinary fast oxide ion conductivity in
La1.61GeO5-[delta] thin film consisting of nano-size grain. Solid State Ionics 177, 1733–
1736 (2006)
176. Ravi, S., Ganesh, K.V., Ramanathan, A., Annamalai, J., Jaiswal, P.K.: Development of nano
crystalline nickel coating for engineering applications. In: Key Engineering Materials,
pp. 487–492. (2010)
177. Koleva, D.A., Boshkov, N., Bachvarov, V., Zhan, H., de Wit, J.H.W., van Breugel, K.:
Application of PEO113-b-PS218 nano-aggregates for improved protective characteristics of
composite zinc coatings in chloride-containing environment. Surf. Coat. Technol. 204,
3760–3772 (2010)
178. Wang, R.M., Wang, B.Y., He, Y.F., Lv, W.H., Wang, J.F.: Preparation of composited nano-
TiO2 and its application on antimicrobial and self-cleaning coatings. Polym. Adv. Technol.
21, 331–336 (2010)
179. Seong, M.R., Kwon, J., Lee, G.Y., Kim, D.K., Kim, Y.S., Lee, C.S.: Optimization of surface
coating condition using vapor form of alkanethiol on Cu nano powders for the application of
oxidation prevention. Appl. Surf. Sci. 256, 2332–2336 (2010)
180. Wang, J.E.: Application of nano-titatium polymer coating to the coolers in oil refine factory.
Corros. Protect. 30, 933–935 (2009)
181. Izumi, T., Izumi, K., Kuroiwa, N., Senjuh, A., Fujimoto, A., Adachi, M., Yamamoto, T.:
Preparation of electrically conductive nano-powder of zinc oxide and application to
transparent film coating. J. Alloys Compd. 480, 123–125 (2009)
182. Tian, Z., Wang, X., Shu, L., Wang, T., Song, T.H., Gui, Z., Li, L.: Preparation of nano
BaTiO3-based ceramics for multilayer ceramic capacitor application by chemical coating
method. J. Am. Ceram. Soc. 92, 830–833 (2009)
183. Shibli, S.M.A., Jayalekshmi, A.C.: A novel nano hydroxyapatite-incorporated Ni–P coating
as an effective inter layer for biological applications. J. Mater. Sci. Mater. Med. 20, 711–718
(2009)
184. Lewis, F., Mantovani, D.: Methods to investigate the adhesion of soft nano-coatings on
metal substrates—application to polymer-coated stents. Macromol. Mater. Eng. 294, 11–19
(2009)
185. Zhang, X., Cheng, X., Yin, H., Yuan, J., Xu, C.: Preparation of needle shaped nano-copper
by microwave-assisted water system and study on its application of enhanced epoxy resin
coating electrical conductivity. Appl. Surf. Sci. 254, 5757–5759 (2008)
186. Jacquot, P., Andreux, C., Stauder, B.: Effect of industrial surface finishes on heat treatment
and surface engineering of steel. Int. Heat Treat. Surf. Eng. 4, 110–116 (2010)
187. Stevenson, P., Ata, S., Evans, G.M.: Erratum: the behavior of an oscillating particle attached
to a gas–liquid surface (Industrial and Engineering Chemistry Research 48 (8025)). Ind.
Eng. Chem. Res. 49, 3504 (2010)
188. Kaufmann, H.: Industrial applications of plasma and ion surface engineering. Surf. Coat.
Technol. 74–75, 23–28 (1995)
Chapter 3
Characterization of Nanostructured
Coatings
3.1 Introduction
Materials with nano-crystalline structure are away from equilibrium state. Nano-
metric (nano-crystalline) structure is the term which is applied for each material
provided that its microstructure comprises of extremely fine particles, measuring
from 1 to 100 nm generally. Comparing materials with ordinary structure, nano-
structured materials, due to having high density of interface levels and also high
volume of crystal imperfections like vacancy and dislocations, show unique and
unparallel properties. In inter-crystal areas, atomic density and the way of
arrangement of atoms differ from crystal areas and consequently, physical and
chemical properties of inter-crystal areas differ from crystal areas as well. The
main reason behind this behavioral change can be defined as a result of superficial
energy increase in nano-crystalline materials. The special high level of nano-
structured materials and following increase of superficial free energy cause that
sensitive properties to surface (like superficial reaction phenomena) is improved
coupled with accelerating the processes which superficial energy is operated as
progressive force.
The inter-crystalline areas place in higher balance than crystalline areas in
terms of energy level. Hence, existence of these inter-crystalline areas can provide
necessary energy for overcoming thermo-dynamical and kinetic dams in nucle-
ation of new phases and increase rate of reaction accomplishment and formation of
new phases on the surface. In fact, inter-crystalline areas are considered as
appropriate centers for nucleation of new phases. The results obtained from Moth–
Shotky electrochemical tests indicated that passive film formed on iron electrode
surface was a semiconductor in a way that electron donor density in passive film is
reduced with the reduction of size of electrode surface grains. In the same
direction, density of oxygen-free places, which is regarded as hub of adsorbing
corrosive ions and causing eradication of passive film like chloride ion, is reduced
with the reduction of electron donor density at passive film and with the aim of
safeguarding balance of electrical load [1–15].

78 3 Characterization of Nanostructured Coatings
This subject resulted in increase of sustainability of passive film formed on

nano-crystalline iron surface. Also, results obtained from electrochemical
impedance indicated increase of density of passive film formed on surfaces with
smaller granule size. Since gradient of potential in passive film has been tasked
with controlling kinetics of transfer of load components like ions and electron in
passive film, increase of passive film density with reduction of sub-layer granule
size can be related to spread of energy band in passive film.
Sodium nitrate and sodium benzoate were used in partly neutral aqueous
solutions respectively with the aim of studying the effect of reduction of size of
superficial grains on kinetics of adsorbing corrosive inhibitors from mineral and
organic inhibitors. For effective adsorption of inhibitors on metal surface, inter-
action forces between metal and inhibitor should be larger than interaction forces
between metal and water molecules. The amount of inter-crystalline areas,
including grain boundaries and triple junctions, is increased in tandem with fining
size of granules. Existence of high amounts of inter-crystalline energy-rich areas at
nano-crystalline materials causes to place them in higher level of superficial
energy in comparison to microcrystal materials with the same chemical compound,
and consequently, reactivity between their surfaces and the environment is
increased. The results, obtained from electrochemical tests, indicated increase of
overlapping percentage and/or increase of inhibition efficiency with the reduction
of size of crystalline iron granules.
Here, a definition of nanostructured materials has first been mentioned.
Nanostructured materials create a new approach for improvement of properties,
without imposing any change in chemical composition. The unique and single
properties of nano-crystallites, in comparison with coarse multi-crystalline mate-
rials, originate from vast grain boundary and consequently, high inner-fuzzy
energy in them. This issue causes that knowing resources and reasons behind
increase of superficial energy of nano-crystalline materials is of paramount
importance. For this reason, indexes, which are constructive and effective on
increase of free superficial energy, have been discussed thermodynamically.
The production methods of nanostructured materials have been explained briefly.
With regard to using electrochemical deposition method for creation of nanostruc-
tured coating, mechanisms of growth and nucleation in electrical crystallization
process has been explained thoroughly. Some of the properties resultant from
nanostructured coatings have been reviewed in comparison with coarse-granular
structure. Moreover, properties of coatings have also been reviewed [16–24].
3.2 Definition of Nanostructured Materials
The nanostructured materials are defined to a group of materials which their

structural dimensions are measured in nanometric (nm) scale. More inclination is
on dimensions smaller than 100 nm. Hereunder are considered as salient specifi-
cation of nano-crystalline metallic systems with regard to their efficacy: sizes of
3.2 Definition of Nanostructured Materials 79
granules, areas of metal with direction of specified crystal screens, atomic density
gradient and areas with different chemical composition.
The various types of nanostructured materials enjoy two joint and common
specifications: (1) Atomic areas (granules or phases) have been restricted in space
smaller than micron scale. (2) High volume fraction of atoms exists in interface
areas. Nanostructured materials can be observed in dimensionless, one dimen-
sional, two dimensional and three dimensional forms. Atom nucleate or atom
sprouts have been recognized as dimensionless nanostructures. Nanorods and
similar nanostructures such as nano-whiskers can be considered as one dimen-
sional nanostructures while separate or isolated layers or multi-layers, grown in
one or two directions, are known as two-dimensional nanostructures. In addition,
nano-crystalline or nano-phases are considered as three-dimensional (3D) nano-
structures and regarded as highly-used nanostructures in metal systems. The sig-
nificance of nanometer scale is originated from the fact that some of properties
undertake remarkable amounts at this dimension range. Since properties of a solid
material is first controlled by density and atom co-ordination number, nano feature
of sizes of granules in crystalline materials, despite chemical composition in nano-
crystalline and microcrystalline state, causes that properties like specific heat,
thermal capacity, thermal extension coefficient, magnetic properties and
mechanical properties in nano-crystalline state are considered completely different
from microcrystalline state [25–31].
Birringer [32] has reported formation of nanostructure iron with average granule
size of 10 nm by gas condensation method. The results, obtained from images of
electron microscope, indicate fair correspondence with the model. It should be
noted that the average atomic density in grain boundaries stands at approximately
7–85% of density of atoms inside granules. Its main reason is related to misfit of
orientation and direction of atoms in interfaces. If density of a solid is decreased
uniformly (for example, if solid is expanded uniformly), inter-atomic space will be
increased and consequently, gravity forces between atoms are weakened to such an
extent that if this expansion is reached up to final limit i.e., 30–40%, then it may
result in separation of atoms. The results obtained from micrograph image with
high decomposition of iron nanostructured metal shows that reduction of density at
grain boundaries is not in uniform manner; rather, a distribution of atoms places in
grain boundary and averagely, their density is less in comparison with the atoms
placed inside granule. This subject has been reported for palladium metal by other
researchers. The actual nature of boundaries of grain in a nano-crystalline structure
has not yet been recognized completely.
Some researchers believe that there is not any difference between grain
boundaries in a nano-structure structure with large granule (coarse) structure.
Some others believe that grain boundary in nano-crystalline structure is amor-
phous. Since fraction of atoms placed at grain boundary areas is comparable with
fraction of atoms placed inside granules in a nano-crystalline structure, structure of
grain boundary and contact areas of grain boundaries is instable and show ten-
dency to lower energy level. Therefore, there exists strong driving force for growth
of granule in nanostructured materials and these materials are instable

thermodynamically.
Dense, crack-free piezoelectric thick film integrated on silicon substrate has
been the subject of considerable attention in recent years for potential application
in micro-electro mechanical systems (MEMS). Wang et al. [33] were proposed a
new spin-coating route for this purpose in which films are made from homogenous
slurry of sol–gel precursor and nano-sized powders. Ceramic PZT powders are ball
milled into different particle sizes by a higher energy planetary ball mill machine
and uniformly dispersed into, with a selected dispersant, a PZT sol–gel solution
identical with the powders in composition. The well-prepared resulting slurry
looks like paint and was spin deposited onto a silicon wafer, fired, and annealed in
the same manner as conventional sol–gel process. Thick films on platinum coated
silicon can be fabricated with this route. The microstructure, crystallization pro-
cess and the ferroelectric properties of the film have been investigated. It is
revealed that the success of this route is due to the elimination of the agglomer-
ation among the nano-sized particles. The smaller the particle, the more uniform
the microstructure. The film derived from micron-sized particles has the porous
structure with average pore size of sub-micron. For the films derived from nano-
sized particles, the nanocrystalline structure is obtained at sintering temperature of
600–700C and fully developed submicron-sized grains have been demonstrated at
sintering temperature of 700–800C. This thick film has comparative ferroelectric
properties with respect to bulk PZT ceramic.
Dense, crack-free piezoelectric thick film integrated on silicon substrate has
been the subject of considerable attention in recent years for potential application
in MEMS. Combining surface of micro-machined silicon wafer with piezoelectric
and ferroelectric films has resulted in novel devices such as micro fluidic devices,
micro-pumps, acoustic transducers, cantilever or bimorph accelerometer, ultra-
sonic devices, ink-jet printer heads, micro-actuators for high-density hard-disk
drives, and several others. These novel devices require the piezoelectric coating
either to actuate a substrate or self-resonate at an ultrasonic frequency. Since
resonant frequency, generative force and displacement of the devices are deter-
mined mainly by their dimensions and material properties such as density and
Young’s modulus, these novel devices require the films of specific dimensions.
The thickness of the piezoelectric films are typically in the range of 0.5–5 lm for
MEMS applications, 2–10 lm for micro-actuators with relatively large generative
force, 30–50 lm for ultrasonic transducers at frequency larger than 50 MHz and
50–200 mm for millimeter-sized devices. In addition, the density of the piezo-
electric film also plays an important role in overall performance of the devices.
Therefore, fabrication of crack-free and also dense thick films are of great
significance.
Wang et al. [33] concluded that high-energy ball-milling is demonstrated to be
an effective approach to obtain a well-dispersed slurry of fine powders and a sol–gel
solution slurry made this way can be used in spin-coating or screen-printing to
make dense thick films with uniform microstructures. The use of nano-sized
powder is of great benefit to the uniformity of the microstructure. The success of
this process can be ascribed to the elimination of the agglomeration among the
nano-sized particles. The film derived from micron-sized particle has the porous
structure with average pore size of sub-micron level thus it has low permittivity,
while the film derived from nano-sized particles has relatively poor ferroelectric
performance due to the poor crystallinity of the nano-sized powders. Figure 3.1
illustrates a schematic flow chart of thick film deposition using nanocrystalline
composite technique. Leakage current–voltage and resistivity characteristics of a
10-mm-thick PZT thick film prepared by using nanocomposite route can be seen in
Fig. 3.2. As an example, Fig. 3.3 shows an as-sintered surface morphology of a
screen-printing PZT thick films on Au/Al2O3 substrate annealed at 800C for
30 min. A totally new homogeneous polycrystalline matrix has been formed at the
expense of originally added powder-phase and sol–gel derived phase.
Fig. 3.1 Flow chart of thick

film deposition using
nanocrystalline composite
technique, reprinted with kind
permission from Zhu [33]
Fig. 3.2 Leakage current–

voltage and resistivity
characteristics of a 10-mm-
thick PZT thick film prepared
by using nanocomposite
route, reprinted with kind
Fig. 3.3 As as-sintered

surface morphology of a
screen-printing PZT thick
film on Au/Al2O3 substrate
annealed at 800C for
30 min. The fully developed
grains are sub-micron in size,
reprinted with kind
TiO2 nanoparticle coatings possess good thermal and electrical properties and
they are resistant to oxidation, corrosion, erosion and wear in high temperature
environments. This property is very important factor in the applications such as
pipelines, castings and automotive industry. Shanaghi et al. [34] applied a uniform
TiO2 nanoparticle coating on mild steel, using sol–gel method. The coating was
deposited on mild steel substrate by dip coating technique. The morphology and
structure of the coating were analyzed using SEM, AFM and X-ray diffraction.
The anticorrosion performances of the coating have been evaluated by using
electrochemical techniques. The film uniformity was retained in high temperatures
and no crack and flaking off from the substrate was observed. The tafel polari-
zation measurements provide an explanation to the increased resistance of TiO2
nanoparticle coated mild steel against corrosion and icorr was decreased from
18.621 to 0.174 (lA/cm2). AFM images from performed coatings indicate their
homogeneity and roughness. Stainless steels due to Cr2O3 presence on their sur-
face (and their low difference with TiO2 thermal expansion coefficient) are more
suitable than mild steel for substrate of sol–gel method. Performing an interlayer
on the surface of sample caused decreasing the difference of thermal expansion
coefficients between substrate and coating. Final coating was studied with AFM
and its roughness was in nanometric scale. Figure 3.4 illustrates AFM result of
final coating. The TiO2 nanoparticle sizes were about 40–60 nm obtained from
XRD and AFM.
3.3 Thermodynamics of Nanostructured Materials
As mentioned in the beginning, materials with nanometer (nano-crystalline)

structure are away from equilibrium state. The factors, which affect on additional
free energy of these materials, have been recognized. High density of interface and
sever changes of chemical composition and stress gradient are the cases which can
be effective in abnormal thermodynamic changes of these materials. The origin of
these impacts has been recognized theoretically and experimental tests have pro-
ven these cases as well. The nano-crystalline structure can be considered as
compound form, comprised of small crystalline areas with long-range order and
with various crystallography orientations and inter-connected lattice of inter-grain
areas, lacking any full crystalline order. The degree of additional free energy of
these materials is related to the following cases:
• Interface free energy,
• Interface curvature and inter-level connections,
• Stresses extant at interface,
• Mixture of phases (including semi-sustainable phases),
Fig. 3.4 AFM nanograph of

TiO2 nanoparticle coating on
mild steel by sol–gel method
a morphology of surface
b cross section, c relationship
between roughness of TiO2
nanoparticle coating and its
thickness obtained by AFM
[34]
• Chemical composition changes,

• Stresses as a result of coherency,
• Stresses as a result of non-coordination in thermal expansion,
• Lattice imperfections.
The above mentioned cases may create changes in degree of free energy of
other objects which have not nanometer (nano-crystalline) structure. Of course, the
utmost effect of these parameters is related to nanostructured materials, because,
length of layers, which causes stress and appearance of changes in chemical
composition, is very short. Effect of each above-mentioned factors on nano-
structured materials, is different. The degree of additional free energy changes
strictly hinges on the aforementioned cases and neutralization of these cases to
each other and balancing them for reaching the lowest free energy level is inev-
itable. For example, a semi-sustainable phase may be produced in structure of
material for reducing interface energies and consequently, this issue will reduce
total free energy of object. For better studying, the nanostructured materials can be
classified into the following four groups:
1. Mono-phase multi-crystalline materials
2. Multi-crystalline materials (Two or multiphase)
3. Filamentary composites
4. Filamentary thin films
For mono-phase multi-crystalline materials, utmost free energy increase is
related to grain boundary and inter-granule boundary connections. These con-
nections have the utmost effect on interface energy. Double-phase multi-crystal-
line materials have usually been formed from the phases which do not show any
reaction with each other and/or do not penetrate into each other. When granules are
measured very small, they are called as nano-phase. When two phases are com-
prised of metallic property, the term ‘‘nano-crystalline alloys’’ will be applied. If
one phase is metallic and the other phase is non-metallic, it is called granular
metal. Sample of these materials are solids which particles of a metal have placed
inside non-metallic background (like oxides). At this state, matrix phase is not
reacted with metal and metallic particles are placed away from each other in
isolated form. With regard to double-phase materials, the degree of radius of
curvature of phases is considered as the most significant issue. This issue can cause
increase of free energy and also can be considered as a driving force for
enlargement of granules. The other significant issue is increase of stresses as a
result of interface and also disparity of thermal expansion coefficient of phases and
granules in tandem with each other.
The cases discussed up to now, may have nanometer size in each three
dimensions. But other materials like composites with nanometer filaments have
nanometer structure only in two dimensions. Also, multilayer materials, which are
created through controlled deposition process, have nanometer structure only in one
dimension. With regard to multilayer materials, free energy increase effects include
effects of coherency stresses, interface stresses and also chemical composition
3.3 Thermodynamics of Nanostructured Materials 85
changes. Although double-phase multi-crystalline materials in normal condition

have been formed from phases which do not show reaction with each other, they
can be studied along with multilayer materials. Also, for nanometric materials, high
rate of imperfections like vacancies and dislocations, can be observed inside their
crystalline structure [9, 35–47].
3.4 Interfaces Thermodynamics
With regard to phase balance in microscopic structure, energy interface does not
play a significant role and only Gibbs free energy of whole object is important.
With regard to materials with microscopic structure, thermodynamics of interface
can be ignored. Of course, some common cases are controlled and monitored
through interface energy. For example, it can be referred to the phenomenon of
growth of grain. For nanostructured materials, conducting thermodynamics studies
merely on whole object is not sufficient due to very high density of interface. And
following interface thermodynamics should be taken into consideration. Interface
thermodynamics has been studied comprehensively by Gibbs which is briefly
explained in following sections [39, 41, 46, 48–52].
Comparative study of reactivity of nano- and micro-sized alumina and nickel
oxide, obtained by the electrical explosion of metal wires in oxidizing atmosphere,
was carried out for the reactions NiO ? MoO3, NiO ? Al2O3, and Al2O3 ?
Bi2O3 by coupled anneals of ceramics, measurements of the conductivity of
individual oxides and raw oxide mixtures, X-ray diffraction and differential ther-
mal analysis by Neiman et al. [53]. The total conductivity of nano-structured
oxides was found lower than that of micro-structured ceramics. Mixing bismuth
oxide with nano-structured alumina leads to stabilization of the low temperature
polymorph a-Bi2O3 up to 780C. The diffusion permeability of NiMoO4 layer
grown at the surface of NiO ceramics, having submicron grains, was found 2 times
lower if compared to NiMoO4 grown at micro-sized NiO ceramics. NiO and Al2O3
nano-powders preserve the high reactivity even when heated up to 1,000C.
Despite much attention and intensive investigation of the different physical
properties in nano-sized systems, there is an obvious lack of information available
on their reactivity and transport properties. Concerning the reactivity of such
systems, one can see that the majority of research work has been dealing with
surface reactions in supported catalytic systems, ion exchange and intercalation
processes but not with solid state synthesis. The latter class of interactions is the
most interesting for the clarification of reactivity peculiarities of substances in the
nano-state, oxides in this case. During the synthesis reaction, surface force field of
nano-sized grains in contact with reaction partner may influence the reactivity and
transport properties of partner and reaction product. The subject of greatest interest
is displaying the phenomena associated with specific features of the non-equilib-
rium state of nano-sized oxide in solid state reactions, namely trivial size factor
versus true (mesoscopic) size effect. According to recent ideas, the manifestations
of ‘‘trivial’’ size effect (increasing vapor pressure, reducing melting temperature,

etc.) can be predicted on the basis of classical thermodynamics of surfaces (Gibbs
equation) or small particles (Thomson–Kelvin equation) and are associated with
gradual increasing of specific area and volume fraction occupied by grain
boundaries. Contrary, the essence of ‘‘true’’ size effect relates to the change of
local parameters of the single- or multi-component system: change of predominant
charge carrier type, surface phase transitions, stabilization of non-equilibrium
structures via so-called hetero-phase doping, etc.
The synthesis reactions can be studied using powder mixtures or diffusion
couples of initial reagents, separately compacted. This gives a valuable opportunity
to obtain their complementary characteristics and to detect different details of the
reaction mechanism. In particular, the study of diffusion zone development via the
coupled anneals using nano-materials has not been carried out before. Another
remarkable aspect is that the majority of commercially available nano-powders are
produced by techniques where water is used as a solvent or happens to be one of the
by-products, e.g., sol–gel, spray techniques and hydrothermal synthesis. This might
lead to a specific ‘‘water memory’’ effect on the main reactivity characteristics.
Therefore, Neiman et al. [53] used nano-powders of NiO and Al2O3 obtained by the
electrical explosion of metal wires in an oxidizing atmosphere. They concluded that
the results obtained show that manifestation of the ‘‘nano-factor’’ depends on
the nature of the oxide-partner, in particular, on its solid state dispersal ability,
surface mobility, temperature and type of experiment (coupled annealing of cera-
mic compacts or interaction in the powder mixtures). Some of the results can occur
due to ‘‘trivial’’ size factor, i.e., increase in interaction contact area in powder
mixtures NiOn ? MoO3, NiOm,n ? Al2Om,n 3 (if at least one of the initial oxides is
nano-scaled) and low conductivities of nano-structured NiO and Al2O3. However,
some data cannot be explained on a conventional basis. This assertion relates to the
stabilization of a-Bi2O3 low temperature polymorph in contact with Al2On3 due to
the action of strong surface force of the latter. Figure 3.5 illustrates bright-field
TEM images of used nano-structured Al2O3 and NiO prepared by the electrical
explosion of metal wires. Figure 3.6 shows DTA curves for equimolar NiO–MoO3
mixtures while temperature dependencies of the conductivity of equimolar
NiO–Al2O3 as-pressed mixtures (heating–cooling) can be seen in Fig. 3.7.
3.5 Interface Traction
Generally, the main discussion is on interface in solid objects (between two phases
and/or between two granules inside one metal). But, for facilitation of modeling,
interface between two fluids are first considered. Actual interfaces have usually
limited width but for ease of analysis, interface between two parts, being com-
pletely uniform in terms of structure and properties, has been considered in line
form (or one curve) with zero width and is called Gibbs separating surface. When
this model is adapted with actual conditions, it is observed that interface will cause
3.5 Interface Traction 87
Fig. 3.5 Bright-field TEM

images of nano-structured
Al2O3 (a) and NiO
(b) prepared via the electrical
explosion of metal wires,
reprinted with kind
permission from Neiman [53]
Fig. 3.6 DTA curves for

equimolar NiO–MoO3
mixtures, reprinted with kind
Fig. 3.7 Temperature

dependencies of the
conductivity of equimolar
NiO–Al2O3 as-pressed
mixtures (heating–cooling),
reprinted with kind
creation of some additional terms. Specially, term of free energy increase per
surface unit which is shown with r. Generally, these additional terms are
dependant on the selected area for positioning of separating surface. Finding
accurate and appropriate place of separating surface has been studied by a number
of researchers [54–59].
Although situations can be selected for interface provided that additional terms
to be independent of curvature of interface and amounts of additional terms can be
set for that situation. For a fluid, term r is defined as degree of work which seems
necessary for production of a surface unit of interface. Mechanically, interface is
studied as a stretched part and r is numerical amount of main tensile stress. For
fluids, r is an inter-surface force and is usually called surface stress and/or interface
stress. For two fluid phases in equilibrium with each other, effect of r on interface
will cause pressure on surface of phases which are not equal with each other
necessarily, i.e., pressure on phase r (Pa) may differ from pressure on phase b (Pb):

1 1
Pa Pb ¼ r þ
r1 r2
At this equation, r1 and r2 are main radiuses of interface curve which their centers
are located in phase r. In a specific state, if phase r in spherical form with equal
radius r is placed inside phase b, the above equation will be as follows:
2r
Pa P b ¼
r
This equation is called Gibbs approach which is used for studying effects of
interface on solid surface.
3.5 Interface Traction 89
3.6 Additional Free Energy on a Solid with Nanometric

Structure
Free energy of a phase in a multi-crystalline material has higher amount than

materials with mono-crystalline state. Such additional amount is related to the
existence of inner-structure imperfections. High amount of grain boundary con-
stitutes major part of these imperfections. The amount of grain boundary can be
measured with regard to a nanostructured material. The total area, which a grain
boundary is occupied, is in compatible with d-1 in which d is diameter of granule.
The contact area of grain boundary has separate structure that can affect on degree
of free energy. Total length of these contact areas is proportional to d-2. Contact
area of these connections with grain vertices affect on free energy. The population
of these areas is proportional to d-3. Hence, additional free energy of whole object
(Gexcess) for volume unit is as follows:
Gexcess ¼ ad1 þ bd2 þ cd3
At this equation, a, b, and c are constants proportional to geometrical factors.

Parameter a is proportional to the degree of free energy increase of grain boundary
per surface area, b is proportional to connections energy per length unit and c is
related to three-dimensional (3D) energy (vertex energy). For any other object,
which does not have very small grain size, these terms can be ignored in above
equation. The posed analysis is analysis of effect of grain boundary on basis of
Gibbs Approach. In the same direction, additional terms related to imperfections
have been considered zero in ideal state. Of course, research activities have
indicated that properties of grain boundary are varied in its length. At this state,
average of these properties has merely been considered. Method of manufacturing
material is regarded as one of the most important and effective factors on the way
of positioning and distributing grain boundary. Even if distribution of grain
boundary can be considered as constant, when size of width of imperfections has a
larger amount in a way that it can be compared with diameter of grain (d), Gibbs
approach will not produce any response. Consequently, use of models like
‘‘penetration at grains boundary’’ seems necessary. With regard to multilayer
materials, which have been comprised of two different phases, if interface of
phases have properties independent from repetition distance of phases (k), then
terms related to contact of grain boundary and vertices will be omitted and
additional free energy per surface unit related to interface, is explained with the
following simple equation [60–69].
Gexcess ¼ ak1
3.7 Interface Stresses
When a reversible work is carried out with the aim of increase of a solid surface,
two separate states can be occurred. At first state, new surface may be produced by
the process like fracture or plastic flow. Here, a is known as work done by free
energy of surface (or interface). At second state, surface can be stretched in elastic
form. The carried out work is equal to superficial stress (interface stress) which is
shown with fij. At first process, new atoms are brought to the surface. Hence,
properties of surface in surface level will not be changed. On the contrary of the
first state, at the second state, new atoms do not proceed to the surface and
consequently, properties of surface are changed. Superficial stress is related to
surface free energy and also surface elastic strain. The equation related to it has
been shown in below:
fij ¼ rdij þ
or
fij ¼ rdij þ
oeij
At this equation, d is Kronecker Delta. For isotopic surfaces, isotopic superficial

stress can be defined with the amount of f. Elastic stress and elastic stretch will not
exist for interface between fluids. Therefore, eij will be equal to zero and f indicates
surface free energy. More research activity is needed for interface between solid
and liquid with regard to f. For sustainable surfaces, r is a positive amount and f will
have the same sign as r. Many tests and calculations have been made with regard to
the amount and sign of interface stress on free surfaces of metals. It seems that for
free surface of a metal, interface stress will have similar amount with interface
energy and will cause compressive stresses in micro-metallic particles. For a sphere
with radius r and a solid phase a which is placed inside liquid b, pressure difference
between two phases depends on f and at this state r does not play an effective role.
Hence, the above equation can be corrected as follows:
2f
Pa Pb ¼
r
For state of interface between two solid objects, if properties of interface in all
areas are considered equal, at least three inter-superficial forces will exist. Inter-
face free energy r and two interface stresses, apart from each other, one of which
is known as f, can be considered as a base for elastic tension in solid surface. Also,
pressure in surface of two solids depends on elastic modulus in each two solid
surfaces. Consequently, equation of pressure difference will be as follows:
2f 3Ba 12lb Ba
Pa Pb ¼ þ e
r0 4lb þ 3Ba 4lb þ 3Ba
At this equation, r0 is radius of hole in b solid background, provided that this
surface is stress free. Li and Bi are equal to shear modulus and bulk modulus of a
and b phases and e is interface stress of a and b phases [70–77].
3.8 Chemical Equilibrium in Curved Interface 91
3.8 Chemical Equilibrium in Curved Interface
Curved interface plays a key role in solvability. A specific state is assumed that
spherical-shaped solid phase a has been constituted merely from a constituent
A and is placed in fluid phase b that can be formed from various and many
constituents. Spherical phase has feature of equilibrium with surrounding area and
pressure inside sphere at this state depends on its radius. According to the fol-
lowing equation,
A this issue will cause changes in chemical potential of constituent
A in phase a la .

A A 2f
la r la r¼1 ¼ VaA
r
At this equation, V A/a is molar volume of constituent A inside phase a. Transfer of

atoms A between two phases of a and b will change interface surface. Therefore,
free energy of system will be changed as well. Consequently, chemical potential of
constituent A at surrounding fluid area will also be changed according to the
following equation.

A A A 2r
lb lb ¼ Va
r r¼1 r
For equilibrium state in planar interface, pressures in two phases and also chemical
potential will be equaled with each other. According to the above equations, it is
observed that when interface is a curve, not only pressure but also chemical
potential will also be changed.

lAb lAa r¼1 ¼ 0
r¼1
2ðr f Þ
lAb lAa r ¼
r r
If the two phases are fluids, then, f will be equal to r and chemical potential will
remain unchanged even with regard to curved surfaces in equilibrium state.
Changes of l A/B with radius obeys molar fraction changes of constituent A which
is solved in phase b. The changes at this molar fraction x A/B is obtained according
to the following equation:
0 1
xA A

B b r C Va 2r
ln@ A¼
xAb RT r
r¼1
At this equation, R is gas constant. The effective solvability of constituent A in

phase b, is increased in the vicinity of minute particles of c. Changes in x A/B can be
considered as a driving force for Ostwald Ripening phenomenon, causing changes
in distribution of a phase particles. If the phase which surrounds a particles is solid,

chemical equilibrium analysis will be more complicated. At this state, phase b
applies a non-hydrostatic stress. Hence, chemical potential inside it cannot be
defined. However, inter-surface free energy r plays a key role once again. Above
equations can be used in many of systems through such method. In previous dis-
cussions, chemical equilibrium was considered in interfaces which atom will move
from one phase to another phase and/or from one grain to other grain. In multi-
partial systems, this issue can be important i.e., in equilibrium state, each constit-
uent can have its unique interface in such a way that some constituents are
preferentially adsorbed to the interface surface and other constituents are prefer-
entially repelled. This property will affect on interface free energy. This affair
depends on temperature as well. It can be concluded that for equilibrium between
phases and between chemical constituents, interface free energy r is considered and
for the state of stress within solid phases, interface stress f is considered.
3.9 Influential Interface
In previous sections, interface was studied as a sharp specified separating surface.

However, in materials with nanometer (nano-crystalline) structure, this possibility
exists that this affair may not happen. Influential interface model is very important
for comprehension of actual penetration in interface and effect of microstructure on
it. This subject was studied by Hilliard et al. At this research, influential changes of
each intensive and scalar quantity (like density and concentration of a specified
part) in interface between two environments with different properties are discussed.
For this reason, the desired property has been considered as mole fraction of
constituent A (CA) in a double-constituent solid solution. It is assumed that these
parameters are changed with distance change (X). Also, it has been shown that
local Holmholtz free energy for f system not only depends on local chemical
composition of object, but also depends on local density gradient and also higher
differentials (derivatives) which is explained in the following formula:
2 !
oc
f ðxÞ ¼ f0 ðcÞ þ k
ox
x
At this equation, f0(c) is free energy per volume unit for a homogenous system with
molar fraction of c and in this formula k is energy gradient coefficient. In interface
between two insolvable objects, width of interface is determined by competition
between chemical composition gradient reduction and also material volume
reduction in a non-equilibrium composition. It has been anticipated that interface
width will depend on temperature, aimed at increasing penetration at higher tem-
peratures and diverging toward infinity. Energy gradient coefficient can be obtained
by models related to solid solution. This amount is positive for the solution which
shows more tendency to phase isolation (in other words, showing tendency to
3.9 Influential Interface 93
interface). This amount is negative for the solution which shows tendency to
chemical composition. Energy gradient in a phase, which shows tendency to iso-
lation, causes that total free energy, be increased.
3.10 Phase Interface
Another approach that can be studied is as follows: interface can be considered as

an isolating phase along with homogenous properties which in some cases, it can
contribute to studying behavior of material. Details of this hypothesis were studied
by some researchers. Generally speaking, direct measurement of thermodynamic
properties (enthalpy, entropy and Gibbs free energy) of nanostructured materials is
followed with doubt. In continuation, the results obtained from measurement of
components of nanostructure metals, produced by condensation processes, have
been explained thoroughly [78–89].
3.11 Measurement of Thermal and Electrochemical Properties
Knowing specific heat will give allowance of calculation of temperature changes

of enthalpy and entropy with respect to system. The absolute amounts of the
mentioned parameters, irrespective of this fact that entropy of materials follows
3rd rule cannot be calculated. For this reason, more interests are focused on
amount of enthalpy change (DH), entropy change (DS) and inter-phases free
energy change (DG). These amounts are related in below form with difference in
specific heat of phases.
DGðT1 Þ ¼ DHðT1 Þ T1 DSðT1 Þ

0 1
ZT1 ZT1
B DCP ðTÞ C
¼ DHðT0 Þ þ DCP ðTÞdT T1 @DSðT0 Þ þ dTA
T
T0 T0
More interest is on the difference of these amounts for nano-crystalline and mono-
crystal state.
For example: DH = H(Nano crystal) - H (Single crystal).
Here, (DH) can be calculated by measurement of exchanged heat but due to
lack of equilibrium between nanostructure and mono-crystalline state, determi-
nation of (DS) is impossible. Since electrochemical measurements greatly
contribute in determination of absolute amounts, they are of paramount signifi-
cance. The potential difference (DE) between electrodes of two samples is directly
related to Gibbs free energy:
l1 l2 DG
DE ¼ E1 E2 ¼ ¼
nF nF
Where E1 and E2 are electrochemical potentials of two samples (measured with

respect to reference electrode), l1 and l2 show chemical potentials of atoms in
samples, n is amount of charge of metallic ions and F is Faraday constant.
3.12 Condensed and Compressed Metals
Many well-grounded reports have been presented with regard to measurement of

specific heat of nanostructured materials like copper, palladium and platinum
which are produced based on inert-gas condensed method. The results obtained
from studies indicate that specific heat of nanostructured materials is more than
multi-crystalline materials with ordinary grains and even is more than amorphous
metals. Such difference is more for palladium metal, which is apparently related to
low density of this material. When measurements of additional specific heat are
used in low temperatures, it is observed that additional specific heat with a fair
approximate is related to absolute temperature in linear form within studied
thermal range (DCP = hT).
Enthalpy stored for nano-crystalline copper metal stands at 0.026 JK-2 mol-1
and it is equal to 0.077 JK-2 mol-1 for palladium metal. Since share of electrical
and magnetic parameters in specific heat can be ignored, additional specific heat of
nanostructured materials (in comparison with ordinary structure) is related to
situation entropy and high shakes of grain boundary. Recent research activities
have shown that additional specific heat for palladium belongs to presence of light
elemental impurities. Calorimetric measurements on the materials, which have
been compressed as much as 85%, show releasing of heat during annealing pro-
cess. This process is made during two stages, firstly, along with releasing of
unsustainable grain boundary and secondly, as a result of growth of grains. It
should be noted that total enthalpy stored for a sample with 12–18 nm grain size is
equal to 6.2 kJ mol-1 according to additional enthalpy as a result of grain
boundaries before and after relaxation process which stand at *2 and *1 JM-2
respectively which is very similar to accepted value for coarse-grain enthalpy.
Also, entropy increase is created with grain boundary in such a way that it can be
said that additional free energy is mostly related to enthalpy. Generally, electro-
chemical potential between single and multi-crystalline samples as size as ordinary
grains have slight disparity with each other but this difference is high between
these materials and nanostructured materials.
Since multi-crystalline materials or samples with nanostructure procedure are
not in internal equilibrium state, measurement of their electrochemical potentials is
very difficult. All results, which are obtained from above equation for determi-
nation of potential difference (DE), are related to difference in average chemical
potential of atoms that have participated in electrochemical reaction. Amount of
average chemical potential (l) for multi-crystalline samples with ordinary grain
size and also mono-crystalline samples can be a good approximation of sample’s
3.12 Condensed and Compressed Metals 95
actual chemical potential. But, this subject doesn’t apply for nanostructured
samples. Atoms extant in grain boundary may be more active than atoms inside
grains. This subject may affect electrochemical measurements to some extent.
Measurement of electrical driving force of palladium metal through the application
of melted salt electrolyte by some researchers at the temperature range of
613–693 K showed that nano-crystalline materials are even sustainable at rela-
tively high temperatures as compared with structures with normal grain size.
Electrical driving force difference of palladium is lessened with time between
nano-crystalline state and normal-sized grain state. In accordance with enthalpy
measurements, change in nano-crystalline samples is occurred at two stages.
First, it is followed with relaxation of grain boundary and then with increase of
grain size. Gartner has estimated additional free energy of nanostructured pal-
ladium, which is equal to *1 kJ mol-1 for grain size near 20 nm and approx-
imately *6.7 kJ mol-1 for grain diameter of 11 nm according to the free energy
increase of grain boundary approximately 1 jm-2. These amounts are in good
accordance with measurement carried out for additional enthalpy. It can be
concluded that for small sized grains up to *10 nm, grain boundary in nano-
crystalline pure metals doesn’t have properties different from multi-crystalline
properties in ordinary grain size. The grain boundary areas in nanostructured
samples result in increase of free energy which primarily is dependant to
enthalpy [90–102].
3.13 Methods for Production of Nanostructured Materials
Nano-crystalline materials can be produced by various methods. Provision of

nano-crystalline bulk materials can be obtained both with bottom-up arrangement
of atoms or molecules in nanometer clusters and through top-down methods which
starts with bulk solid and nanostructure is obtained by decomposition of bulk
structure. The bottom-up arrangement methods for atoms include inert-gas con-
densation and compression. This method has been comprised of evaporation of
metals inside a chamber, containing a partial pressure (approximately some hun-
dred Pascal) of a neutral gas like helium which evaporated atoms strike with the
atoms inside chamber and lose their energy, condensing into separate small
crystals as loose powders. Tiny condensed powders on the part cooled by accu-
mulated liquid nitrogen are separated by Teflon ring and guided into the com-
pressing device.
Irrespective of this fact that this method provides materials for initial study of
nanostructure properties, its disadvantages can be referred to the limitation of size
and being a two-stage process which may not be created at the stage of full
condensation and material contact. Generally speaking, methods of manufacturing
based on preliminary phase classify at three categories of steam, liquid and solid.
In Table 3.1, some samples of sub-branches methods of each of these categories
and type of crystal materials (in dimensional term) have been specified. Selection
Table 3.1 Various types of methods for manufacturing nano-crystalline materials

Initial Method Product nanometer
phase dimensions
Steam Inert-gas-condensation 3-D
Glazing physical steam, evaporating and sputtering Mono-dimensional
Plasma processes 3-D
Condensing chemical steam Two- and three dimensional
Chemical reactions 3-D
Liquid Fast freezing 3-D
Electrolyte glaze Mono- and three dimensional
Chemical reactions 3-D
Solid Milling and alloying mechanically 3-D
Crystallization of glassy phases 3-D
Sparkling erosion 3-D
Sliding erosion 3-D
of process depends on the parameters like capability of control of microstructure

components like size of grains, chemical composition and chemistry of surface or
degree of interface pollution and also process expenses and costs. Some methods
are very expensive and complicated while some others are cheap but do not create
a clean surface. Inert gas-condensation processes, grinding and mechanical
alloying, electrochemical deposition, crystallization of glassy phases and spray
conversion processing has more application for manufacturing of nanostructured
materials [25, 42, 103–110].
At all two-stage processes for formation of nanostructured materials, nanometer
particles are produced at first stage or powdered particles with nanometric struc-
ture are produced in mechanical erosion process. These particles should be sta-
bilized for formation of bulk. The problem of stabilization has been remained as an
open-air space for progress and development and has not thus far been settled. The
problem is related to the below issue: these processes are in dire need of combi-
nation of appropriate temperature and pressure for establishing atomic connection
between particles, aimed at establishing theoretical density in the long run of all
inter-particle contacts. This affair should be occurred without enlarging nanometer
microstructure and/or without establishing any structural imperfections and also
unwanted phases. Electrochemical deposition process is placed at the category of
bottom-up methods for production of nanostructured materials and is a mono-stage
process which does not need to be stabilized.
Coarse and thick coatings as a result of electrochemical deposition may be
interpreted as a bulk. After 1980s, electrical deposition was studied as a method for
production of nano-crystalline materials and then was developed as industrial pro-
duction method of these materials. Electrochemical deposition method occurs by
nucleation of crystals on sub-layer surface and their consequent growth along with
nucleation of new crystals. With the aim of obtaining nanometer grain size, nucle-
ation process should witness preference to growth. Variables in electrochemical
3.13 Methods for Production of Nanostructured Materials 97
deposition process include composition of bath, pH of bath, temperature, overvolt-

age, bath additives and type of imposed cathodic current.
Mirzamohammadi et al. [111] studied electrodeposition of tertiary Alumina/
Yitria/carbon nanotube (Al2O3/Y2O3/CNT) nano-composite by using pulsed cur-
rent. Coating process has been performed in nickel sulphate bath and nanostructure
of the obtained compound layer was examined with high precision figure analysis
of SEM nano-images. The effects of process variables, i.e., Y2O3 concentration,
treatment time, current density and temperature of electrolyte have been experi-
mentally studied. Statistical methods were used to achieve the minimum wear rate
and average size of nanoparticles. Finally the contribution percentage of different
effective factors was revealed and confirmation run showed the validity of
obtained results. Also it has been revealed that by changing the size of nanopar-
ticles, wear properties of coatings will change significantly. AFM and TEM
analysis have confirmed smooth surface and average size of nanoparticles in the
optimal coating.
Nickel and nickel-based alloys are used widely for numerous applications,
which most of them require corrosion, wear and heat resistances, including dif-
ferent turbine plants, nuclear power systems, and chemical and oil industries.
Ceramic or metal matrix nanocomposite coatings usually have special properties
such as dispersion hardening, self-lubricity, high temperature inertness, good wear
and corrosion resistance, chemical and biological compatibility. This accounts for
the increased application of Ni-based nanocomposites in different industries. In
order to meet the requirement for developing novel metal-based nanocomposites,
many preparation techniques have been investigated. Considering a technique
conducted at a normal pressure and ambient temperature and with low cost and
high deposition rate, electrodeposition is considered to be one of the most
important techniques for producing nanocomposites and nanocrystals.
Mirzamohammadi et al. [111] used the Taguchi method for the design of
experiment for optimizing tertiary (Al2O3/Y2O3/CNT) nanocomposite electrode-
posited coating process parameters for wear protection of treated samples. The
contribution of Y2O3 concentration is more than the sum of the contributions of all
the other three factors. It is evident that, among the selected factors, Y2O3 con-
centration has the major influence on the wear rate of performed coatings. It can be
seen that the current density is the second important factor that affects the wear
rate of the treated substrates. Furthermore, it can be assumed that treatment time
and temperature of electrolyte have almost the same effect on wear rates of
coatings because of the minor difference in the contribution percentages between
these two factors. By ranking their relative contributions, the sequence of the four
factors affecting the wear rate is Y2O3 concentration, current density, treatment
time and temperature of electrolyte. In the case of average size of nanoparticles
ranking of effective factors by their relative contributions is the same as for wear
rate which shows strong relation between these two measured properties of
coatings. AFM and TEM analysis have confirmed smooth surface and average size
of nanoparticles in the optimal coating and can be seen in Figs. 3.8 and 3.9
respectively.
Fig. 3.8 AFM nanostructure

of optimal nanocomposite
electrodeposited coating
[111]
Fig. 3.9 TEM (BFI)

nanostructure of optimal
nanocomposite
electrodeposited coating
[111]
3.14 Nano-Technological Compatibility in Coating
As it previously mentioned, coating industry is determined to use nano-technology

and nano-layers was even applied before advancements in nano-technology. First
of all, a complete relevant definition of nano-coating needed be offered. It may be
acclaimed that the best definition for nano-coating is a type of coating using nano-
structured materials such as:
• Nano-particles
• Nano-tubes
• Nano-wires
• Other available nano-structures such as nano-layers
Looking at this definition, one can state thickness of nano-coating may be more
than nano scale, but nano-materials are used. Here, one may ask why industries are
this much interested in using nano-coating.
Due to occurrence of quantum phenomena at sizes lower than 100 nm, nano-
materials are of unique features. In most of cases combination of these materials
improve many required characteristics, as well as keeping original materials
properties. Hence, using nano-materials a novel revolution happened in technology
3.14 Nano-Technological Compatibility in Coating 99
of making new materials, particularly composite ones. Many research centers have
started widespread movements and even produced some important materials such
as nano-particles. Some of materials have extensive industrial uses or are used in
key industries such heavy or military industries; then are of strategic applications
such as scratch resistant nano-composites. Nano-metric coating is widely used and
in some cases they even have commercial uses and are produced in mass
quantities.
3.15 Improvement of Coating Quality Using Nanotechnology
Coating has variant applications, such as protecting coatings against corrosion,

scratch, stain, denting, bending, foliation, or making water proof and acid resistant
coatings. Coating is used in every aspect of life from coating on glass, wood,
plastic, paper, fibers, or similar foliations, to coating in heavy industries and
special applications (e.g., military applications). Also, coatings have a key role as
protector against climatic conditions such as rain, snow, solar ultraviolet beam, or
chemical pollutions. Regarding abundant applications of coating in variant tools,
researchers have always been trying to promote coating quality and lower its costs
in academy and industry. Todays, advancements in technology have significantly
increased coating quality. Recently, Coating through nano-materials has reached to
practical scale and some famous supplier companies of industrial panels and
automobiles use this coating in their products [112–116]. With respect to applied
study in this field, main applications of nano-particles are categorized into fol-
lowing cases:
• Coat resistant against scratch, abrasion, corrosion, and environmental agents
• Variety of optical coatings, including coatings resistant against reflection and
fog, or protecting ones
• Coatings with medical, biological, and environmental applications
• Coatings with electrical and electronic applications
3.16 Abrasion, Scratch, and Corrosion Resistant Coatings
3.16.1 Coatings Resistant Against Scratch, Abrasion, Corrosion,

and Environmental Agents
Coatings resistant against scratch, abrasion, corrosion, and environmental agents

are mostly used to coat many panels. It is one of fields where nano-technology is
capable of creating dramatic changes. However, this type of coating is a large
market for applications of nano-products, due to its widespread usages. Then
industrial researches and production of these coatings are economically valuable.

Throughout following lines some of important applications of this coating will be
studied. Needless to say, this type of coating will be used in so many similar cases
and the following applications are ones which large industries are investing for
them or about to produce or supply their products.
3.16.2 Nano-Metric Abrasion, Scratch, and Corrosion Resistant

Coatings
Nono-technology advancements had significant effects on methods and processes

of coating. Nano-scale materials, including materials with particle size of lower
than 100 nm, are studied and prepared for industrial scale applications. Metallic
coating of stainless steel using crystalline nano-powder has higher hardness
compared with traditional materials. Other materials such as tungsten carbide
powder is also used for similar—but in smaller scale—applications. High Velocity
Oxy Fuel (HVOF) is among methods applied for nano-composite coating, where a
combination of polymer and ceramic is used. Advantage of this method is its lack
of destruction in polymer. To apply these materials, polymer-ceramic joining
mechanisms have to be promoted.
Also, thin layers coating has been applied to improve surfaces and constructing
new panels, although the objective of making nano-layers is achieving to inter-
esting, practical and quantum features of these systems. Once these thin layers are
made in such scales, they will be of particular properties, such as absorption of
ultraviolet beam, antistatic, and electrical conductivity, in comparison with its
mass state. Painting and coating industries are among pioneer industries which use
these interesting properties. The industries found that thin layers obtained from
nano-particles are of better cohesion to applied surface, more flexibility, and a very
small difference in their final prices. Through this method one can achieve
smoother layers, compared with traditional methods. These layers are used for
self-cleaner surfaces and scratch resistant coating. Todays, many companies use
different properties of nano-particles to improve coating quality.
Advanced Nano Products Co. Ltd in Taejon, South Korea, is one of active
companies in this field. At products of this company metallic oxide particles are
used to prevent intrusion of infrared, ultraviolet, and thermal light. Glasses coated
through this method can be used in windows of buildings, cars, and offices. One of
noteworthy advantages of these particles is their transparency at visible wave-
lengths (400–700 nm) and, consequently, invisibility with naked eyes. While some
particles are added to improve scratch resistance properties they diffract the light
and cause its seeming opaque, due to their coarse grains. On the other hand, adding
nano-particles maintains products transparency due to lack of light diffracting, as
well as improving other given characteristics. Other important applied materials
for this objective include Al2O3, antimony tin oxide (ATO), and ZnO, which is use
3.16 Abrasion, Scratch, and Corrosion Resistant Coatings 101
as zinc oxide in sun block coatings. ATO is also used for making antistatic
coatings. There are some other cases for practical applications of nano-particle,
such as coating of fire retardant wood doors and scratch resistant coatings. Also,
Mercedes Benz applied nano-coating as scratch resistant and antibacterial coating
at interior part of SLK, CL, S, SL, and E automobile series. Another developing
aspect is surface nano-coating with TiO2, which is used as a corrosion resistant
coating with self-cleaning properties [117–128].
3.16.3 Using Alumina as a Scratch and Abrasion Resistant

Coating
Among important objective of coating one can name enhancement of surface

resistance against scratch and abrasion, so material development and completion
and abrasion and scratch resistant coatings methods is of great importance. In most
industrial and military applications scratch and abrasion resistant coatings are very
important. Initiating advancements in nano-technology is its uses in different sec-
tions for products quality promotion nano-coating is applied to construction and
improvement of abrasion and scratch resistant coatings. One of important materials
for this aim is alumina nano-powder, developed by Nanodur Company. To use this
material it should be mixed in different colors, where due to its small particle sizes
there will be no significant changes in color and apparent features of the block.
3.16.4 Designing Light Resistant Panels for Plane Body
Thanks to nano-technology, Research and Development section of Boeing Company

has accomplished designing new materials for plane body. Their aim for upcoming
future is development of new materials, lighter and stronger than previous ones, for
plane body. Their employ from nano-coating leads to creation of panels with no need
for repainting, as well as producing stronger, lighter, and of longer life ones. This
method is also used to produce long-lasting batteries for satellites.
3.16.5 Ceramics Reinforced by Carbon Nano-Tubes
These ceramics were fabricated by researchers of materials science in Ve davice.

They can conduct electrical current and can be served as conductor or insulator,
depending to direction of applied materials. These materials are very hard and of a
great resistance against chemicals, so they can be applied as a convenient coating
for turbine fans. They are made of alumina powder plus 5–10% carbon nano-tubes,
with a scanty amount of niobium. Compared with pure alumina, these fabricated
materials are of grater electrical conductivity. They convey the heat along array of
carbon nano-tubes, while in the vertical direction they act as thermal insulator layer.
It is predicted that these ceramics be applied for thermal coating in coming future.
3.17 Nano-Coating Resistant Against Corrosion
NANOMAG has invented a type of nano-composite materials resistant against

corrosion, as a substitute for hazardous coating with Cr components. This coating
can be applied for reinforcement of Mg alloys. These coated alloys are used in
transportation, aerospace, and aviation industries. Weight reduction is one of most
important objectives followed for making vehicles, results in decrease of fuel
consumption and release of pollutants. For this aim Mg alloys are used for a long
time. Different methods are used to coat these alloys. Among them one can name
anodic coating and using CrVI components. First method is expensive, while the
latter is environmentally dangerous due to poisonous nature of CrVI components.
Regarding this point, the objective for development of nano-composite coating is
making a low priced and environmentally compatible product. This coating needs
to be of a high resistance against corrosion. Making such a product various
research groups are cooperating. Also countries such as Austria and Israel are very
active in this field. Among their objectives, one can name using these alloys in
exterior body of vehicles. For this type of coating, it is supposed to use Plasma-
Enhanced Chemical Vapor Deposition (PECVD), sol–gel, and ceramic coating
methods. Making these alloys there has been accomplished a noticeable promotion
in transportation industry and environmental pollution decreases. It is noteworthy
that these alloys recycling costs is lower than the others.
3.18 Using Nano-Particles for Coating in Transportation

Industry
PPG is one of most important producers of coating, esp. those used in transpor-
tation industry. This company also produces flat glasses, especial coatings, and
main coatings of aviation industry. The company mentions nano-materials of
silicon oxide as a convenient coat for transportation industry. The coating is of a
great resistance against foliation, scratch, dentation, and pollution stains. A thin
layer with a very strong lateral bond causes to high hardness of the coating and
increases its resistance against scratch. However, it must be noted this hardness
leads to coatings’ brittleness against thermal changes, hence layers with weaker
lateral bonds is recommended. Then, silicon colloidal coatings are used. PPG uses
alumina-silicate nano-particles as an essential material for coating process. It has
refractive index of 10 in its nano form. Particles are spherical with no color, and
their surface has no hydroxyl groups; above all they do not be coagulated in their
3.18 Using Nano-Particles for Coating in Transportation Industry 103
proximity. Surfaces coated with this material have a high resistance against foli-
ation, crushing, or scratching. Through optimization of composition and applying
nano-materials it is also possible to reach other useful features. This company
researches suggest adding only 1 weight percent nano-particles to traditional
coatings leads to a significant improvement in coating properties.
3.19 Coating Applications in Defense and Aerospace Industries
Coating is widely used in defense and aerospace industries to improve products

quality, capability, and safety. Among these coatings one can name ones resistant
against corrosion, decay, and wear or enhancing of surface quality. Some of
coating applications are: versatile nano-metric coatings, which now are in devel-
oping phase. These coatings are resistant against abrasion and corrosion; they can
also detect cracks, chemical and physical damages, and etc. in plain body. Besides,
they are of a high cohesion to coated block. Some of these coatings are also
capable of changing damaged part color, which helps detect damaged zone.
Using conventional coatings in defense industry is difficult and also hazardous
for people who are dealing with that. It must be noted that most of applied coatings
in defense industry should be touched by hand. This can cause many damages to
used coatings and the operator. Reports show that annual expenses of Defense
Ministry of United States for dealing with corrosion and abrasion problems exceed
10 billion dollars, where 2 billion dollar of this figure is allocated to coating.
Currently, 20% of US armies’ vehicles are worn-out, due to damages in coating
and need for repainting. Considering above discussions, it is planned to apply
intelligent coatings for vehicles used in military industries. Scratch resistant
coatings detect, repair, and moderate damages. Other important suggested coatings
are those with color change compatibility in different operational conditions of
battle arena for camouflage. These coatings are supposed to be applied in tanks or
military vehicles body to decrease visionary and detection capabilities.
3.20 Using Ceramic Nano-Coatings in US Navy
Strength and stability of nano-coatings has encouraged US navy to invest in this

field and use nano-coatings in military gears. Once using nano-coatings, objectives
such as increase of panels’ life and decrease of repair and maintenance expenses
are considered. Achieving this aim, there have been financial aids to different
centers to find a convenient material, and finally alumina and Titania were chosen.
After a while, a product, Babi2613, was emerged. Using this substance is not
recommended for coating applications due to its high costs. Every pound (453.6 g)
of this substance costs about 30–50 dollars.
Compared with traditional coating methods, nano-ceramic coatings show a

noticeable improvement in their characteristics, as some of required properties,
such as strength, has increased up to 4–6 times. Nowadays, US navy use nano-
coating in its equipment. Researchers declare that nano-ceramic coating is cur-
rently used for different pieces such as fan axle, periscope axle, and more than 150
other applications, where corrosion resistant surface is needed. For example, air
outlets and inlets in submarines are coated with nano-materials, which bring about
400,000 dollars in each military gear and 20 million dollars annual saving. Power
transfer axles in submarines or mine sweepers have also leads to 10 million annual
saving. These coatings can also be used for commercial aims.
Also in 2003, Spire Corp has received 75,000 dollars financial support to
develop nano-coating for orthopedic objectives. This group is determined to
develop nano-coatings, which are harder and have more cohesive coating and
minimum corrosion and abrasion.
References
1. Agarwal, S., Jain, A., Jain, P., Vyas, D., Ganesan, V., Jain, I.P.: Synthesis of nano-
crystalline Zr–M (M=Ni, Co, Fe, Cu) bilayer films and their thermodynamics of hydrogen
uptake by resistance measurement. Int. J. Hydrogen Energy 35, 9893–9900 (2010)
2. Carnall, J.M.A., Waudby, C.A., Belenguer, A.M., Stuart, M.C.A., Peyralans, J.J.P., Otto, S.:
Mechanosensitive self-replication driven by self-organization. Science 327, 1502–1506
(2010)
3. Cheluvaraja, S., Ortoleva, P.: Thermal nanostructure: an order parameter multiscale
ensemble approach. J. Chem. Phys. 132 (2010)
4. Chen, Z.G., Wang, P.W., Wei, B., Mo, X.M., Cui, F.Z.: Electrospun collagen-chitosan
nanofiber: a biomimetic extracellular matrix for endothelial cell and smooth muscle cell.
Acta Biomater. 6, 372–382 (2010)
5. Dussan, K.J., Cardona, C.A., Giraldo, O.H., Gutiérrez, L.F., Pérez, V.H.: Analysis of a
reactive extraction process for biodiesel production using a lipase immobilized on magnetic
nanostructures. Bioresour. Technol. 101, 9542–9549 (2010)
6. Gu, D., Baumgart, H., Abdel-Fattah, T.M., Namkoong, G.: Synthesis of nested coaxial
multiple-walled nanotubes by atomic layer deposition. ACS Nano 4, 753–758 (2010)
7. Ivanova, O.S., Zamborini, F.P.: Size-dependent electrochemical oxidation of silver
nanoparticles. J. Am. Chem. Soc. 132, 70–72 (2010)
8. Oliveira, C.L.P., Juul, S., Jørgensen, H.L., Knudsen, B., Tordrup, D., Oteri, F., Falconi, M.,
Koch, J., Desideri, A., Pedersen, J.S., Andersen, F.F., Knudsen, B.R.: Structure of nanoscale
truncated octahedral DNA cages: variation of single-stranded linker regions and influence
on assembly yields. ACS Nano 4, 1367–1376 (2010)
9. Perepezko, J.H., Imhoff, S.D., Hebert, R.J.: Nanostructure development during
devitrification and deformation. J. Alloys Compds. 495, 360–364 (2010)
10. Rahmani, A., Mousavi, H.Z., Fazli, M.: Effect of nanostructure alumina on adsorption of
heavy metals. Desalination 253, 94–100 (2010)
11. Shi, J., Wang, X.: Strain versus dislocation model for understanding the heteroepitaxial
growth of nanowires. J. Phys. Chem. C 114, 2082–2088 (2010)
12. Shi, Y., Zhang, F., Hu, Y.S., Sun, X., Zhang, Y., Lee, H.I., Chen, L., Stucky, G.D.:
Low-temperature pseudomorphic transformation of ordered hierarchical macro-mesoporous
SiO2/C nanocomposite to SiC via magnesiothermic reduction. J. Am. Chem. Soc. 132,
5552–5553 (2010)
References 105
13. Xu, C.H., Zhu, Z.B., Li, G.L., Xu, W.R., Huang, H.X.: Growth of ZnO nanostructure on
Cu0.62Zn0.38 brass foils by thermal oxidation. Mater. Chem. Phys. 124, 252–256 (2010)
14. Xu, Q.F., Wang, J.N., Sanderson, K.D.: Organic–inorganic composite nanocoatings with
superhydrophobicity, good transparency, and thermal stability. ACS Nano 4, 2201–2209
(2010)
15. Zeng, J., Zhang, Q., Chen, J., Xia, Y.: A comparison study of the catalytic properties of
Au-based nanocages, nanoboxes, and nanoparticles. Nano Lett. 10, 30–35 (2010)
16. Tominaka, S., Hayashi, T., Nakamura, Y., Osaka, T.: Mesoporous PdCo sponge-like
nanostructure synthesized by electrodeposition and dealloying for oxygen reduction
reaction. J. Mater. Chem. 20, 7175–7182 (2010)
17. Li, X., Li, P., Luo, M., Chen, X., Chen, J.: Controllable solvo-hydrothermal
electrodeposition of lithium vanadate uniform carnation-like nanostructure and their
electrochemical performance. J. Solid State Electrochem. 14, 1325–1332 (2010)
18. Zong, Z., Zhang, M., Lu, H., Xu, D., Wang, S., Tian, H., Liu, C., Guo, H., Gao, H., Zou, G.:
Synthesis of PbTe/Pb quasi-one-dimensional nanostructure material arrays by
electrodeposition. Appl. Phys. Lett. 96 (2010)
19. Ou, K.L., Wu, J., Lai, W.F.T., Yang, C.B., Lo, W.C., Chiu, L.H., Bowley, J.: Effects of the
nanostructure and nanoporosity on bioactive nanohydroxyapatite/reconstituted collagen by
electrodeposition. J. Biomed. Mater. Res. A 92, 906–912 (2010)
20. Bijani, S., Martínez, L., Gabás, M., Dalchiele, E.A., Ramos-Barrado, J.R.: Low-
temperature electrodeposition of Cu2O thin films: modulation of micro-nanostructure by
modifying the applied potential and electrolytic bath pH. J. Phys. Chem. C 113,
19482–19487 (2009)
21. Shen, X., Chen, X., Liu, J.H., Huang, X.J.: Free standing Pt-Au bimetallic membranes with
a leaf-like nanostructure from agarose-mediated electrodeposition and oxygen gas sensing
in room temperature ionic liquids. J. Mater. Chem. 19, 7687–7693 (2009)
22. Jiang, J., Kucernak, A.: Electrodeposition of highly alloyed quaternary PtPdRuOs catalyst
with highly ordered nanostructure. Electrochem. Commun. 11, 1005–1008 (2009)
23. Sun, F., Guo, Y., Song, W., Zhao, J., Tang, L., Wang, Z.: Morphological control of Cu2O
micro-nanostructure film by electrodeposition. J. Cryst. Growth 304, 425–429 (2007)
24. Yeo, S.H., Teh, L.K., Wong, C.C.: Fabrication & characterization of macroporous CdSe
nanostructure via colloidal crystal templating with electrodeposition method. J. Porous.
Mater. 13, 281–285 (2006)
25. Bux, S.K., Fleurial, J.P., Kaner, R.B.: Nanostructured materials for thermoelectric
applications. Chem. Commun. 46, 8311–8324 (2010)
26. Vaqueiro, P., Powell, A.V.: Recent developments in nanostructured materials for high-
performance thermoelectrics. J. Mater. Chem. 20, 9577–9584 (2010)
27. Garza-Navarro, M.A., Torres-Castro, A., Garca-Gutiérrez, D.I., Ortiz-Rivera, L., Wang,
Y.C., González-González, V.A.: Synthesis of spinel-metal-oxide/biopolymer hybrid
nanostructured materials. J. Phys. Chem. C 114, 17574–17579 (2010)
28. Ren, W., Cheng, C., Ren, Z., Zhong, Y.: The effect of the precursor nanopowder size on the
thermoelectric properties of nanostructured BiSbTe bulk materials. Phys. B Condens.
Matter 405, 4931–4936 (2010)
29. Jeong, G., Kim, Y.U., Krachkovskiy, S.A., Lee, C.K.: A nanostructured SiAl0.2O anode
material for lithium batteries. Chem. Mater. 22, 5570–5579 (2010)
30. McGlone, T., Streb, C., Long, D.L., Cronin, L.: Assembly of pure silver–tungsten–oxide
frameworks from nanostructured solution processable clusters and their evolution into
materials with a metallic component. Adv. Mater. 22, 4275–4279 (2010)
31. Jadoon, A.N.K., Khan, M.Z.: Surfaces, coatings and nanostructured materials. Surf. Eng. 26,
497 (2010)
32. Birringer, R.: Nanocrystalline materials. Mater. Sci. Eng. A 117, 33–43 (1989)
33. Wang, Z., Zhu, W., Zhao, C., Tan, O.K.: Dense PZT thick films derived from sol-gel based
nanocomposite process. Mater. Sci. Eng. B 99, 56–62 (2003)
34. Shanaghi, A., Sabour, A.R., Shahrabi, T., Aliofkhazraee, M.: Corrosion protection of mild
steel by applying TiO2 nanoparticle coating via sol-gel method. Prot. Metals Phys. Chem.
Surf. 45, 305–311 (2009)
35. Lim, S.K., Hong, E.P., Song, Y.H., Choi, H.J., Chin, I.J.: Poly(ethylene terephthalate) and
polyhedral oligomeric silsesquioxane nanohybrids and their physical characteristics.
J. Mater. Sci. 45, 5984–5987 (2010)
36. Evers, W.H., Nijs, B.D., Filion, L., Castillo, S., Dijkstra, M., Vanmaekelbergh, D.: Entropy-
driven formation of binary semiconductor–nanocrystal superlattices. Nano Lett. 10,
4235–4241 (2010)
37. Langhammer, C., Larsson, E.M., Kasemo, B., Zoric, I.: Indirect nanoplasmonic sensing:
ultrasensitive experimental platform for nanomaterials science and optical nanocalorimetry.
Nano Lett. 10, 3529–3538 (2010)
38. Barghamadi, M.: Kinetics and thermodynamics of isothermal curing reaction of epoxy-4,
4’-diaminoazobenzene reinforced with nanosilica and nanoclay particles. Polym. Compos.
31, 1442–1448 (2010)
39. Yuan, Q., Chen, J., Yang, Y., Misra, R.D.K.: Nanoparticle interface driven microstructural
evolution and crystalline phases of polypropylene: the effect of nanoclay content on
structure and physical properties. Mater. Sci. Eng. A 527, 6002–6011 (2010)
40. Datta, S., Conlisk, A.T., Kanani, D.M., Zydney, A.L., Fissell, W.H., Roy, S.: Characterizing
the surface charge of synthetic nanomembranes by the streaming potential method.
J. Colloid Interf. Sci. 348, 85–95 (2010)
41. Gupta, A., Sharma, S., Joshi, M.R., Agarwal, P., Balani, K.: Grain growth behavior of Al2O3
nanomaterials: a review. In: Materials Science Forum, pp. 87–130. (2010)
42. Karimi, E.Z., Zebarjad, S.M., Khaki, J.V., Izadi, H.: Production of carbon nanotubes using
mechanical milling in the presence of an exothermic reaction. J. Alloys Compd. 505, 37–42
(2010)
43. Slota, J.E., He, X., Huck, W.T.S.: Controlling nanoscale morphology in polymer
photovoltaic devices. Nano Today 5, 231–242 (2010)
44. Zhou, Y., Yang, M., Sun, K., Tang, Z., Kotov, N.A.: Similar topological origin of chiral
centers in organic and nanoscale inorganic structures: Effect of stabilizer chirality on optical
isomerism and growth of cdte nanocrystals. J. Am. Chem. Soc. 132, 6006–6013 (2010)
45. Lamour, G., Eftekhari-Bafrooei, A., Borguet, E., Souès, S., Hamraoui, A.: Neuronal
adhesion and differentiation driven by nanoscale surface free-energy gradients. Biomaterials
31, 3762–3771 (2010)
46. Macedo, T.R., Petrucelli, G.C., Airoldi, C.: Sorption and thermodynamic of cation-basic
center interactions of inorganic–organic hybrids synthesized from RUB-18. Thermochimica
Acta 502, 30–34 (2010)
47. Hóbor, S., Kovács, Z., Révész, A.: Estimation of heat production during high pressure
torsion of Cu-based metallic glass. J. Alloys Compd. 495, 352–355 (2010)
48. Liggieri, L., Miller, R.: Relaxation of surfactants adsorption layers at liquid interfaces. Curr.
Opin. Colloid Interf. Sci. 15, 256–263 (2010)
49. Kukhar, V.G., Pertsev, N.A., Kholkin, A.L.: Thermodynamic theory of strain-mediated direct
magnetoelectric effect in multiferroic film-substrate hybrids. Nanotechnology 21 (2010)
50. Wang, C., Tian, W., Ding, Y., Ma, Y.Q., Wang, Z.L., Markovic, N.M., Stamenkovic, V.R.,
Daimon, H., Sun, S.: Rational synthesis of heterostructured nanoparticles with morphology
control. J. Am. Chem. Soc. 132, 6524–6529 (2010)
51. Castro, R.H.R., Torres, R.B., Pereira, G.J., Gouv_ea, D.: Interface energy measurement of
MgO and ZnO: understanding the thermodynamic stability of nanoparticles. Chem. Mater.
22, 2502–2509 (2010)
52. Sampayo, J.G., Malijevsk, A., Müller, E.A., De Miguel, E., Jackson, G.: Communications:
evidence for the role of fluctuations in the thermodynamics of nanoscale drops and the
implications in computations of the surface tension. J. Chem. Phys. 132 (2010)
53. Neiman, A., Tsipis, E., Beketov, I., Kotov, Y., Murzakaiev, A., Samatov, O.: Solid state
interactions in nano-sized oxides. Solid State Ionics 177, 403–410 (2006)
References 107
54. Fan, H.B., Yuen, M.M.F.: A multi-scale approach for investigation of interfacial
delamination in electronic packages. Microelectron. Reliab. 50, 893–899 (2010)
55. Luo, J., Wang, X.: On the anti-plane shear of an elliptic nano inhomogeneity. Eur. J. Mech.
A Solids 28, 926–934 (2009)
56. Avazmohammadi, R., Yang, F., Abbasion, S.: Effect of interface stresses on the elastic
deformation of an elastic half-plane containing an elastic inclusion. Int. J. Solids Struct. 46,
2897–2906 (2009)
57. Liu, X., Li, S., Sheng, N.: A cohesive finite element for quasi-continua. Comput. Mech. 42,
543–553 (2008)
58. Yvonnet, J., Quang, H.L., He, Q.C.: An XFEM/level set approach to modelling surface/
interface effects and to computing the size-dependent effective properties of
nanocomposites. Comput. Mech. 42, 119–131 (2008)
59. Tong, L., Sun, X., Tan, P.: Effect of long multi-walled carbon nanotubes on delamination
toughness of laminated composites. J. Compos. Mater. 42, 5–23 (2008)
60. Heinrich, B.W., Iacovita, C., Rastei, M.V., Limot, L., Ignatiev, P.A., Stepanyuk, V.S.,
Bucher, J.P.: A spin-selective approach for surface states at Co nanoislands. Eur. Phys. J. B
75, 49–56 (2010)
61. Sheibani, S., Heshmati-Manesh, S., Ataie, A.: Structural investigation on nano-crystalline
Cu–Cr supersaturated solid solution prepared by mechanical alloying. J. Alloys Compd.
495, 59–62 (2010)
62. Williams, W.B., Mullany, B.A., Parker, W.C., Moyer, P.J., Randles, M.H.: Using quantum
dots to tag subsurface damage in lapped and polished glass samples. Appl. Opt. 48,
5155–5163 (2009)
63. Hu, M.Z., Lai, P., Bhuiyan, M.S., Tsouris, C., Gu, B., Parans Paranthaman, M., Gabitto, J.,
Harrison, L.: Synthesis and characterization of anodized titanium–oxide nanotube arrays.
J. Mater. Sci. 44, 2820–2827 (2009)
64. Fichtner, M.: Properties of nanoscale metal hydrides. Nanotechnology 20 (2009)
65. Lele, S.P., Anand, L.: A large-deformation strain-gradient theory for isotropic viscoplastic
materials. Int. J. Plast. 25, 420–453 (2009)
66. Jean, Y.C., Hung, W.S., Lo, C.H., Chen, H., Liu, G., Chakka, L., Cheng, M.L., Nanda, D.,
Tung, K.L., Huang, S.H., Lee, K.R., Lai, J.Y., Sun, Y.M., Hu, C.C., Yu, C.C.: Applications
of positron annihilation spectroscopy to polymeric membranes. Desalination 234, 89–98
(2008)
67. Brazard, J., Ley, C., Lacombat, F., Plaza, P., Martin, M.M., Checcucci, G., Lenci, F.:
Primary photoprocesses involved in the sensory protein for the photophobie response of
Blepharisma japonicum. J. Phys. Chem. B 112, 15182–15194 (2008)
68. de la Vega, U.P., Rettberg, P., Reitz, G.: Simulation of the environmental climate conditions
on martian surface and its effect on Deinococcus radiodurans. Adv. Space Res. 40,
1672–1677 (2007)
69. Liu, Y., Cain, J.P., Wang, H., Laskin, A.: Kinetic study of heterogeneous reaction of
deliquesced NaCl particles with gaseous HNO3 using particle-on-substrate stagnation flow
reactor approach. J. Phys. Chem. A 111, 10026–10043 (2007)
70. Wang, Q., Yang, F., Yang, Q., Guan, H., Chen, J.: The magnetism properties and surface
microstructure of NBR/Fe3O4 composites. Int. J. Polym. Mater. 59, 902–910 (2010)
71. Valcke, E., Marien, A., Smets, S., Li, X., Mokni, N., Olivella, S., Sillen, X.: Osmosis-
induced swelling of Eurobitum bituminized radioactive waste in constant total stress
conditions. J. Nucl. Mater. 406, 304–316 (2010)
72. Choi, Y.H., Bulliard, X., Benayad, A., Leterrier, Y., Mnson, J.A.E., Lee, K.H., Choi, D.,
Park, J.J., Kim, J.: Design and fabrication of compositionally graded inorganic oxide thin
films: mechanical, optical and permeation characteristics. Acta Mater. 58, 6495–6503
(2010)
73. Goudarzi, T., Avazmohammadi, R., Naghdabadi, R.: Surface energy effects on the yield
strength of nanoporous materials containing nanoscale cylindrical voids. Mech. Mater. 42,
852–862 (2010)
74. Park, J.M., Jang, J.H., Wang, Z.J., Kwon, D.J., Devries, K.L.: Self-sensing of carbon fiber/
carbon nanofiber-epoxy composites with two different nanofiber aspect ratios investigated
by electrical resistance and wettability measurements. Compos. A Appl. Sci. Manuf. 41,
1702–1711 (2010)
75. Zhang, L., Luo, M., Sun, S., Ma, J., Li, C.: Effect of surface structure of Nano-CaCO3
particles on mechanical and rheological properties of PVC composites. J. Macromol. Sci.
B Phys. 49, 970–982 (2010)
76. Brownlow, S.R., Moravsky, A.P., Kalugin, N.G., Majumdar, B.S.: Probing deformation of
double-walled carbon nanotube (DWNT)/epoxy composites using FTIR and Raman
techniques. Compos. Sci. Technol. 70, 1460–1468 (2010)
77. Gavrilov, N.V., Mamaev, A.S., Plotnikov, S.A., Rubshtein, A.P., Trakhtenberg, I., Ugov,
V.A.: Comparison testing of diamond-like a-C:H coatings prepared in plasma cathode-based
gas discharge and ta–C coatings deposited by vacuum arc. Surf. Coat. Technol. 204,
4018–4024 (2010)
78. Schaefer, B., Nirschl, H.: Electrohydrodynamic transport in nanoporous packed beds.
Chem. Eng. Sci. 65, 6320–6326 (2010)
79. Kondo, M., Heisler, I.A., Meech, S.R.: Reactive dynamics in micelles: Auramine O in
solution and adsorbed on regular micelles. J. Phys. Chem. B 114, 12859–12865 (2010)
80. Yao, Y., Fu, Q., Wang, Z., Tan, D., Bao, X.: Growth and characterization of two-dimensional
FeO nanoislands supported on Pt(111). J. Phys. Chem. C 114, 17069–17079 (2010)
81. Lioutas, C.B., Frangis, N., Todorov, I., Chung, D.Y., Kanatzidis, M.G.: Understanding
nanostructures in thermoelectric materials: an electron microscopy study of AgPb18SbSe20
crystals. Chem. Mater. 22, 5630–5635 (2010)
82. Levitas, V.I., Javanbakht, M.: Surface tension and energy in multivariant martensitic
transformations: phase-field theory, simulations, and model of coherent interface. Phys.
Rev. Lett. 105 (2010)
83. Gniadek, M., Donten, M., Stojek, Z.: Electroless formation of conductive polymer–metal
nanostructured composites at boundary of two immiscible solvents. Morphology and
properties. Electrochim. Acta 55, 7737–7744 (2010)
84. Deepthi, B., Barshilia, H.C., Rajam, K.S., Konchady, M.S., Pai, D.M., Sankar, J., Kvit,
A.V.: Structure, morphology and chemical composition of sputter deposited nanostructured
Cr–WS2 solid lubricant coatings. Surf. Coat. Technol. 205, 565–574 (2010)
85. Zhou, M., Li, J., Yan, F., Fan, X., Cai, L.: A facile ‘‘air-molding’’ method for
nanofabrication. Langmuir 26, 14889–14893 (2010)
86. Choi, Y.J., Chen, T.Y., Chiu, C.K., Luo, T.J.M.: Fabricating nanocomposite catalysts
through interfacial fusion of metallic nanoparticles. Mater. Res. Soc. Symp. Proc. pp. 33–38
(2010)
87. Koh, J.H., Seo, J.A., Koh, J.K., Kim, J.H.: Self-assembled structures of hydrogen-bonded
poly(vinyl chloride-g-4-vinyl pyridine) graft copolymers. Nanotechnology 21 (2010)
88. Chiu, P.Y., Shah, K., Sinnott, S.B.: Nanoindentation of surfactant aggregates. J. Colloid
Interf. Sci. 349, 196–204 (2010)
89. Konysheva, E., Blackley, R., Irvine, J.T.S.: Conductivity behavior of composites in the
La0.6Sr 0.4CoO3±d-CeO2 system: function of connectivity and interfacial interactions.
Chem. Mater. 22, 4700–4711 (2010)
90. Scott, G.D., Palacios, J.J., Natelson, D.: Anomalous transport and possible phase transition
in palladium nanojunctions. ACS Nano 4, 2831–2837 (2010)
91. Tsivadze, A.Y., Ionova, G.V., Mikhalko, V.K.: Nanochemistry and supramolecular
chemistry of actinides and lanthanides: problems and prospects. Prot. Metals Phys.
Chem. Surf. 46, 149–169 (2010)
92. Yang, K., Zhu, L., Xing, B.: Sorption of phenanthrene by nanosized alumina coated with
sequentially extracted humic acids. Environ. Sci. Pollut. Res. 17, 410–419 (2010)
93. Ossler, F., Canton, S.E., Larsson, J.: X-ray scattering studies of the generation of carbon
nanoparticles in flames and their transition from gas phase to condensed phase. Carbon 47,
3498–3507 (2009)
References 109
94. Emmerich, H.: Phase-field modelling for metals and colloids and nucleation therein—an
overview. J. Phys. Condens. Matter 21 (2009)
95. Barton, G., Carugno, G., Dodonov, V., Man’Ko, M.: International workshop 60 years of the
Casimir effect. J. Phys. Conf. Ser. 161 (2009)
96. Ziolkowski, L.A., Druffel, E.R.M.: The feasibility of isolation and detection of fullerenes
and carbon nanotubes using the benzene polycarboxylic acid method. Mar. Pollut. Bull. 59,
213–218 (2009)
97. Tang, P., Hao, J.: Formation mechanism and morphology modulation of honeycomb hybrid
films made of polyoxometalates/surfactants at the air/water interface. J. Colloid Interf. Sci.
333, 1–5 (2009)
98. Crisan, O., Von Haeften, K., Ellis, A.M., Binns, C.: Novel gas-stabilized iron clusters:
synthesis, structure and magnetic behaviour. Nanotechnology 19 (2008)
99. Park, K.H., Lee, S.Q., Kim, E.K., Moon, S.E., Cho, Y.H., Gokarna, A., Jin, L.H., Kim, S.,
Cho, W., Lee, Y.I.: Bio-information scanning technology using an optical pick-up head.
Ultramicroscopy 108, 1319–1324 (2008)
100. Wehbe, N., Heile, A., Arlinghaus, H.F., Bertrand, P., Delcorte, A.: Effects of metal
nanoparticles on the secondary ion yields of a model alkane molecule upon atomic and
polyatomic projectiles in secondary ion mass spectrometry. Anal. Chem. 80, 6235–6244
(2008)
101. Carazzone, C., Raml, R., Pergantis, S.A.: Nanoelectrospray ion mobility spectrometry
online with inductively coupled plasma-mass spectrometry for sizing large proteins, DNA,
and nanoparticles. Anal. Chem. 80, 5812–5818 (2008)
102. Chang, H., Kao, M.J., Chang, Y.C., Huang, D.Y.: A new approach of synthesis of Al2O3
nanofluid. In: Materials science forum, pp. 155–161. (2008)
103. Ibaseta, N., Biscans, B.: Fractal dimension of fumed silica: comparison of light scattering
and electron microscope methods. Powder Technol. 203, 206–210 (2010)
104. Boccaccini, A.R., Erol, M., Stark, W.J., Mohn, D., Hong, Z., Mano, J.F.: Polymer/bioactive
glass nanocomposites for biomedical applications: a review. Compos. Sci. Technol. 70,
1764–1776 (2010)
105. Boccaccini, A.R., Keim, S., Ma, R., Li, Y., Zhitomirsky, I.: Electrophoretic deposition of
biomaterials. J. R. Soc. Interf. 7, S581–S613 (2010)
106. Tabachenko, A.N., Martsunova, L.A., Skosyrskii, A.B., Belov, N.N., Yugov, N.T.,
Afanas’Eva, S.A.: Design of nanostructured cermet materials high-speed impact
conditions. Theor. Found. Chem. Eng. 44, 723–728 (2010)
107. Duraiswamy, S., Khan, S.A.: Plasmonic nanoshell synthesis in microfluidic composite
foams. Nano Lett. 10, 3757–3763 (2010)
108. Xin, Y., Wang, Z., Qi, Y., Zhang, Z., Zhang, S.: Synthesis of rare earth (Pr, Nd, Sm, Eu and
Gd) hydroxide and oxide nanorods (nanobundles) by a widely applicable precipitation route.
J. Alloys Compd. 507, 105–111 (2010)
109. Zhou, W., Liu, H., Boughton, R.I., Du, G., Lin, J., Wang, J., Liu, D.: One-dimensional
single-crystalline Ti–O based nanostructures: properties, synthesis, modifications and
applications. J. Mater. Chem. 20, 5993–6008 (2010)
110. Yang, L.Y., Feng, G.P., Wang, T.X.: Green synthesis of ZnO2 nanoparticles from
hydrozincite and hydrogen peroxide at room temperature. Mater. Lett. 64, 1647–1649
(2010)
112. Wu, C., Xie, Y.: Promising vanadium oxide and hydroxide nanostructures: from energy
storage to energy saving. Energy Environ. Sci. 3, 1191–1206 (2010)
113. Sekhon, B.S.: Food nanotechnology—an overview. Nanotechnol. Sci. Appl. pp. 1–15
(2010)
114. Wögerer, C., Almansa, A., Rempp, H.: IPMMAN—improvement of industrial production
integrating macro-, micro- and nanotechnologies. In: VDI Berichte, pp. 125–128. (2006)
115. Cayton, R.H.: Nanoparticle composites for coating applications. Paint Coat. Ind. 20, 48–54
(2004)
116. Koepenick, M.: Nano invasion: dream or reality? [La nano invasion: Reve ou realite?]. 15,
16–19 (2004)
117. Lekka, M., Zanella, C., Klorikowska, A., Bonora, P.L.: Scaling-up of the electrodeposition
process of nano-composite coating for corrosion and wear protection. Electrochim. Acta 55,
7876–7883 (2010)
118. Tambe, S.P., Naik, R.S., Singh, S.K., Patri, M., Kumar, D.: Studies on effect of nanoclay on
the properties of thermally sprayable EVA and EVAI coatings. Prog. Org. Coat. 65,
484–489 (2009)
119. Ahmad, Z., Ahsan, M.: Corrosion studies on the plasma-sprayed nanostructured titanium
dioxide coatings. Anti Corros. Methods Mater. 56, 187–195 (2009)
120. Wielage, B., Lampke, T., Zacher, M., Dietrich, D.: Electroplated nickel composites with
micron- to nano-sized particles. Key Eng. Mater. 283–309 (2008)
121. Kim, G.E., Walker, J.: Successful application of nanostructured titanium dioxide coating for
high-pressure acid-leach application. J. Therm. Spray Technol. 16, 34–39 (2007)
122. Soucek, M.D., Zong, Z., Johnson, A.J.: Inorganic/organic nanocomposite coatings: the next
step in coating performance. J. Coat. Technol. Res. 3, 133–140 (2006)
123. Guilemany, J.M., Dosta, S., Nin, J., Miguel, J.R.: Study of the properties of WC–Co
nanostructured coatings sprayed by high-velocity oxyfuel. J. Therm. Spray Technol. 14,
405–413 (2005)
124. Lekka, M., Kouloumbi, N., Gajo, M., Bonora, P.L.: Corrosion and wear resistant
electrodeposited composite coatings. Electrochim. Acta 50, 4551–4556 (2005)
125. Yuan, J., Zhou, S., Gu, G., Wu, L.: Effect of the particle size of nanosilica on the
performance of epoxy/silica composite coatings. J. Mater. Sci. 40, 3927–3932 (2005)
126. Brooman, E.W.: Wear behavior of environmentally acceptable alternatives to chromium
coatings: nickel-based candidates. Met. Finish. 102, 75–82 (2004)
127. Fuerbeth, W., Nguyen, H.Q., Schuetze, M.: Development of new corrosion resistant
coatings based on chemical nanotechnology. J. Corros. Sci. Eng. 6 (2003)
128. Nguyen, H.Q., Fiirbeth, W., Schiitze, M.: Nano-enamel: a new way to produce glass-like
protective coatings for metals. Mater. Corros. 53, 772–782 (2002)
Chapter 4
Size Effect in Electrochemical Properties
4.1 Introduction
Electro-crystallization processes happen at solid and liquid electrochemical

interface. Since driving force of this process is controlled by density of current and
electrode potential, it has attracted the attention of many researchers to itself.
Metal cathode deposition process on surfaces of other property and/or the same
property by electrolyte, containing metallic ions, is regarded as major studied
electrical crystallite process. Scanning Tunneling Microscopy (STM) and Atomic
Force Microscopy (AFM) have brought about this possibility to study the phe-
nomenon of electrical crystallization in in situ with the range of atomic level.
Exertion of metallic coating with electrical plating is based on discharge of
electrical load of metallic ions extant at electrolyte on cathode surface (sub-layer
or desired component for coating). Existing metallic ions precipitate on surface as
metallic atom with receiving electron from interface of solid-electrolyte conductor.
The electrons required for reduction of metallic ions are provided through various
methods. These electrons are either provided by a foreign potential source and/or
are provided by reductant agents extant in solution (coating with electroless
method).
Source of providing metallic ions are the metallic salts added to solution or
these metallic ions are supplied as a result of anodic solution (known as sacrificial
anodes). Electrochemical deposition process includes a great number of interme-
diate stages, the most important of which is as follows:
• Transfer of hydrated metallic ion or metallic complex from mass of solution to
cathode.
• Isolation of hydrated layer from metallic ion in metal-solution interface.
• Transfer of load and formation of ad-atom on cathode surface.
• Formation of crystalline nucleuses as a result of penetration of adsorbed atoms
on cathode surface.
• Connection of crystalline nuclei and formation of metallic layer.

112 4 Size Effect in Electrochemical Properties of Nanostructured Coatings
Transfer of metallic ion from bulk solution to cathode surface is as a result of

penetration and convection phenomena. Discharge of electrical load of adsorbed
ions and converting them into adsorbed atoms are made in double layers which is
instantaneously occurred at solution-metal interface. Although metallic ions lose
most of their charges at this stage, the remaining charge amount causes that a part
of hydration sheath to be remained. At this stage, these ions after passing through
dual layer are adsorbed on cathode surface and form adsorbed atoms. With the aim
of creation of a coherent metallic film on cathode surface, two stages or processes
must be occurred. These stages include nucleation and growth which are known as
electrical crystallization stages. In fact, nucleation stage includes migration under
control of adsorbed atoms which differs from penetration process inside solution.
The growth stage happens when created nuclei are reached to a critical size [1–14].
Nickel-tungsten/carbon nanotube nanocomposite layers with high content and
uniform dispersion of carbon nanotubes were fabricated using pulsed electrode-
position technique [15]. Nanocomposite layers were analyzed by scanning electron
microscopy, atomic force microscopy, microhardness, and Tafel polarization tests.
Effect of duty cycle of pulsed current or concentration of carbon nanotubes in the
metallic matrix has been investigated on electrochemical and mechanical prop-
erties of obtained layers. It has been shown that both electrochemical and
mechanical properties of nanocomposite layers that formed by pulsed current were
improved significantly with respect to un-composed Ni–W layer. Results were not
only concerned by concentration of carbon nanotubes in the layer but also influ-
enced by the distribution of nanoparticulates in the metallic matrix.
Plots of Tafel polarization tests for Ni–W and nanocomposite layers formed by
different duty cycles (or different concentrations of carbon nanotubes in the
metallic matrix) are shown in Fig. 4.1. Changing trend of corrosion potentials
(Ecorr) and corrosion current densities (icorr), which were analyzed through Tafel
Fig. 4.1 Tafel plots of (open square) Ni–W and Ni–W/CNT nanocomposite layers formed by
different duty cycles of pulsed current ((open triangle) 20% of duty cycle (or 4.3 wt% of carbon
nanotubes content), (times) 50% of duty cycle (or 9.1 wt% of carbon nanotubes content), and
(open circle) 80% of duty cycle (or 13.1 wt% of carbon nanotubes content) [15]
4.1 Introduction 113
Fig. 4.2 Changing trends of

Ecorr and icorr with respect to
applied duty cycle (or
concentration of CNT
nanoparticulates in the
metallic matrix) [15]
plots, are illustrated in Fig. 4.2. Addition of nanoparticulates will shift corrosion
potentials of electroplated layers towards noble direction (positive values).
Increasing the concentration of carbon nanotubes will have an effect in an opposite
manner, but the changing amount is ignorable. Changing trend of corrosion current
densities shows that increasing the amount of carbon nanotubes has an optimum
level for decreasing them. It was found that 9.1 wt% of carbon nanotubes in the
metallic matrix will show minimum corrosion current density of nanocomposite
layer. Surfaces have approximately no porosity, so it can be concluded that dif-
ferences in electrochemical properties are just related to the content of carbon
nanotubes and their distribution and amount of agglomeration in the metallic
matrix. When carbon nanotubes distribute uniformly, they will protect nanocom-
posites and substrates from corrosive agents and decrease the corrosion current
densities. In an opposite manner, the agglomerated nanoparticulates will decrease
the electrochemical properties of the obtained layer.
4.2 Thermodynamic Equilibrium
In equilibrium state in an electrochemical cell, electrochemical potential of extant

components should be equal.
~s;1 ¼ l
l ~ c;1 ¼ l
~ ad;1
~s;1 : electrochemical potential of electrolyte containing Mez metallic ions, l

l ~c;1 :
electrochemical potential of metal electrode (anode), l ~ad;1 : electrochemical
potential of metallic ions of Mez adsorbed on cathode surface.
Electrochemical potential of each of components is as follows:
~ 0s þ KT lnas;1 þ Ze /s;1
~s;1 ¼ l
l
~ 0c þ Ze /c;1
~ c;1 ¼ l
l
~0ad þ KT lnaad;1 þ Ze /c;1

~ad;1 ¼ l
l
In above equations, l0ad ; l0c ; l0s are standard chemical potentials, and
xad;1 and ac;1 ; as;1 ¼ 1 is ion activities and /c;1 ; /s;1 are galvanic potential of
electrolyte solution and metallic electrode (anode) respectively.
In equilibrium state, regarding above equation, and considering l ~c;1 ¼ l~s;1 ,
Nernst Equation, which indicates equilibrium potential of metallic electrode
immersed in solution containing metallic ions of the same material with activity
as,?, is obtained.
KT
E1 ¼ E 0 þ ln as;1
Ze
~ad;1 ¼ l
Also, in l ~ s;1 state, the following equation will be obtained:

ðl0 l0c Þ Kt as;1
E1 ¼ s þ ln
Ze Ze aad;1
With equalizing above equations, activity of adatoms in equilibrium state will
be calculated as follows:
0
ðl l0ad Þ
aad;1 ¼ exp c
KT
With the aim of commencing crystalline growth or process of formation of
nucleation on neutral surface of cathode, metal ions (Mez) in electrolyte should be
reached to supersaturated state. That is to say that electrochemical potential of ions
extant at solution should be more than electrochemical potential of metal electrode
(anode) ð~ls [ l~ c;1 Þ.
In fact, electrochemical supersaturation is defined as follows:
D~ ~s l
l¼l ~c;1 [ 0
l is defined as driving force for transmission

As it is observed, the amount of D~
of electrochemical phase. Thanks to its significance, it seems necessary that
controllable and measurable physical values should be expressed. General formula
used for D~ l is as follows:
l ¼ Zeg
D~
Where g indicates cathodic over-voltage which is defined as follows:
g ¼ E1 E
KT as
g¼ ln
Ze as;1
Regarding the aforementioned equations, electrochemical super-saturation state
for precipitation on neutral surface of cathode seems possible through two
methods. At the first method, ionic activity of solution (as) is kept constant in a(1)
s,?
4.2 Thermodynamic Equilibrium 115
amount and system state is changed from equilibrium point (1) to equilibrium
point (P), located at super-saturation area. This affair is made by change of
electrode potential from equilibrium state E(1) ? to a more negative amount
E = E(2)? . At second method, electrode potential is kept constant in E(2)
? amount
and ionic activity of solution is increased from equilibrium state of situation (2) to
super-saturation situation (P).
The second method of making super-saturation state is made by pulse poten-
tiostatic method. Also, this method is used for local precipitation of metal
nucleations as size as nano. Formation of a n-atomic nucleation from new phase
requires overcoming thermodynamic obstacle of nucleation work DGðnÞ ~ which is
explained according to the following formula:
~
DGðnÞ ¼ nD~
l þ /ðnÞ
Here, /(n) explains total energy increase as a result of creation of new interface
(creation of nucleation on cathode surface) [16–29].
4.3 Classical Nucleation Theory
At this theory, it has anticipated that nucleuses should be large enough. At this
state, the number of atoms (n) can be considered as a dependant variable and the
amount of /(n) is explained by energies related to specific free surface, interface
and linear interface in system constituted from cathode electrode, electrolyte and
~
nucleuses. At this state, DGðnÞ is a differential function and under conditions of
~
final limit ½dDGðnÞ=dn ¼ 0 we will have:
n¼nc
~
dUðnÞ
l¼
D~
dn n¼nc
The above equation is a general expression of Gibbs–Thomson equation which

l and size of critical nucleuses nc in
explains relation between super-saturation D~
an unsustainable equilibrium state. Studying theoretical formulas for nucleation
~
shows that relation between DGðnÞ in comparison with nucleus size n will have an
~ c Þ; nc ; D~
utmost state in n = nc [30–39]. The amounts of DGðn l are related to each
other for formation of a 3-D nucleus on sub-layer of external layer as follows:
~ c;3D Þ ¼ 1= Uðn
DGðn ~ c;3D Þ ¼ 1= nc;3D D~
l
3 2
If nucleus is formed in 2-D form on the surface, we will have:
~ c;2D Þ ¼ 1= Uðn
DGðn ~ c;2D Þ ¼ nc;2D D~
l
2
4.4 Atomic Nucleation Theory
At this state, the formed nucleuses are of very small size and therefore, size of
nucleus is considered as a separate variable and macroscopic classic theory is not
applicable. Here, formation process of nucleuses is explained by considerations
related to atom and through the application of general formula for nucleation work.
Relation between size of nucleus (n) in contrast with DGðnÞ ~ is not as a smooth
curve and has the minimums and maximums which are dependent on structure and
energy state of nucleus. The highest amount in a super saturation state indicates
size of critical nucleus. Non-continuous change in size of nucleuses in small-scale
dimensions will affect relation between D~ l and size of nucleus (n). In this state, for
each critical nucleus size, there is a supersaturation range instead of a constant
value D~ l. This specific property of small nucleuses will severely affect process of
formation of phase during electro-crystallization process and should be considered
at the time of interpretation of experimental information for electrochemical
nucleation on external surface. At this state, size of critical nucleuses does not
exceed size of some atoms [40, 41].
Properties of Si3N4/Ni electroplated nanocomposite such as corrosion current
density after long time immersion, roughness of obtained layer and distribution of
nanometric particulates have been studied [42]. All of the other effective factors
for fabrication of nanocomposite coatings have been fixed for better studying the
effect of the average size of nanoparticulates. The effects of the different average
size of nanometric particulates (ASNP) from submicron scale (less than 1 lm) to
nanometric scale (less than 10 nm) have been studied. The nanostructures of
surfaces were examined by a scanning electron microscopy (SEM), transmission
electron microscopy (TEM) and atomic force microscopy (AFM). Corrosion rates
of the coatings were determined using the Tafel polarization test. It has been seen
that decreasing the ASNP will lead to lower corrosion current densities however in
some cases pitting phenomena has been observed. The roughness illustrated a
minimum level while the distribution of nanometric particulates will be more
uniform by decreasing the ASNP. The effects of pulsed current on electrodepos-
ition (frequency, duty cycle) and concentration of nanoparticulates on electrode-
position bath on trend of obtained curves have been discussed. Response Surface
Methodology was applied for optimizing the effective operating conditions of
coatings. The levels studied were frequency range between 1,000 and 9,000 Hz,
duty cycle between 10 and 90% and concentration of nanoparticulates among
10–90 g l-1.
Figure 4.3 illustrates changing trend of corrosion current densities (CCD) after
immersion in 3.5 wt% NaCl solution in room temperature. As it can be seen from
this figure, however CCD will increase a little after long time immersion in cor-
rosive solution but lowering the ASNP will lead to lower CCDs which at first
indicate that decreasing ASNP is useful for decreasing CCD. However observa-
tions with unequipped eye did not indicate presence of pitting phenomena but
AFM studies show that nanocomposites with very low ASNP will show some
4.4 Atomic Nucleation Theory 117
Fig. 4.3 Changing trend of corrosion current densities for different ASNPs after immersion in
3.5 wt% NaCl solution in room temperature [42]
Fig. 4.4 AFM nanostructure

of nanometric pits of the layer
with ASNP equal to 9 nm
[42]
nanometric pits. Figure 4.4 shows the observed pits for the nanocomposite layer
with ASNP equal to 9 nm [42].
4.5 Kinetics of Formation of Nucleuses

in Electro-Crystallization
~
Nucleation work DGðnÞ is regarded as criteria of thermodynamic obstacle that
must be overcome in order to transfer (nc) ions from inside electrolyte solution for
formation of new atomic nucleuses on electrode surface. The rate of this process,
which is a kinetic value, is defined by parameter J(t). If nucleation rate is assumed
constant, and/or the amount of J(t) is reached constant amount of J0, dependency
of nucleation rate to over-potential and density will be as follows:
~ c Þ
DGðn
J0 ¼ Z0 Wk1 exp
kT
where ðcm2 ÞZ0 is the number of density of active points on the surface, (s-1)W is
joining frequency of isolated atoms to critical nucleuses and k-1 is a dimension-
free value which has been considered for disparity between the number of constant
critical nucleuses and quasi-equilibrium ones. In microscopy classic nucleation
theory, k-1 is defined as follows:
~ 1
1 DGðnc Þ 2
k ¼
3pn2c kT
and is known as Zeldovich factor. When critical nucleus is very small and its size
remains constant during supersaturation distances, its value is equal to one for
supersaturation state or active sub-layer. At this specific state of electrochemical
phase formation especially on external sub-layer surface, dependency of constant
nucleation rate to over-potential and concentration should be explained in atomic
theoretical terms of formation of electrochemical phase. At this state, the amount
of W will be equal to:

U azeE
W ¼ kt exp exp
kT kT
where kt is factor of frequency, a is charge transfer constant and U is energy

obstacle for transfer of ion from electrolyte solution to the critical nucleuses in
electrode potential (E = 0).
The above equation for W is used when supersaturation term D~ l is changed by
change of concentration of metal ions in a constant electrode potential E. With
substitution of equations, for equation of J0 in k1 ! 1 state, we will have:
J0 ¼ Z0 XðEÞcnc þ1
In such a way that:
nc ~ cÞ
c U þ azeE þ Uðn
XðEÞ ¼ kt exp
c1 c1 kT
Here, c? is equilibrium concentration of metal ions in temperature T. c?, c is

a
coefficients of activity in the form of c ¼ Cs;11
; c ¼ aCs respectively. The above
equation shows that critical nucleus size can be determined through experimental
information of J0(c) which has been obtained in a constant potential.
4.5 Kinetics of Formation of Nucleuses in Electro-Crystallization 119
dlnJ0
nc ¼ 1
dlnc
If supersaturation is considered with change of electrode potential (E) in con-
stant concentration (C? = c?as,?), it is better to use cathode over-potential in
above equation. At this case, constant nucleation rate in k1 ! 1 will be as
follows:

ðn þ aÞzeg
J0 ¼ Z0 Xðc1 Þexp
kT
~ cÞ
U þ azeE0 þ Uðn
XðcÞ ¼ kt ðc1 c01 Þ1x exp
kT
As it is observed, the size of critical nucleus size (ne) can be determined
through test information of J0(l) obtained in C = C? according to the following
formula:
kT d ln J0
nc ¼ a
ze dg
The above equations have been extracted through assuming constant number of
active areas for nucleation on surface of electrode which is regarded as the sim-
plest electrochemical phase state. In practice, the number of active sites for
nucleation on surface can depend on amounts of time, potential and pH [43–54].
4.6 Electrode Surface Energy State
Active points are probably considered as the most significant obstacle in nucle-
ation kinetics. Regarding the unique properties of a specific electrochemical sys-
tem, active points are appeared or disappeared completely different on surface of
electrode. The main reason of the issue is related to different chemical and elec-
trochemical reactions like adsorption and separation of organic and non-organic
ions or molecules, direct oxidation or reduction of electrode surface which is
occurred previously or concurrent with process of formation of nucleation on
electrode surface. That is to say that assumption of a neutral electrode is con-
sidered as a completely optimistic approach. A theoretical model has been pro-
posed for formation of nucleus thanks to time-dependency of number of active
points on electrode surface. If active points on electrode surface is appeared or
disappeared concurrent with nucleus formation process, time dependency of
number of nucleuses (N(t)) can be expressed by following second-order differ-
ential equation.
d2 N dN
þA þ BðN N0 Þ ¼ 0
dt2 dt
Here A and B is dependent on following factors: frequency of nucleation, Kn ¼

c Þ
Wk1 expDGðn a+
kT and appearing frequencies (K ) of active areas on electrode
surface and disappearing frequencies of active areas (Ka-) from electrode surface.
N0 = Z0a ? Z01 is equal to total active areas in t = 0 time. Here, Z01, Z0a is existing
active places and number of places having activation potential at t = 0 time
respectively. With analytical solution of above equation, nucleation rate JðtÞ ¼
dNðtÞ
dðtÞand also the number of nucleuses N(t) can be expressed theoretically.
It is observed
that nucleation rate shows an initial non-zero amount
Jð0Þ ¼ dNdt t¼0 ¼ Kn Z 0
a , a final amount of J(?) = 0 and also a maximum amount
in t = tm. Also, it is observed that amount of N(t) is changed from zero to a
maximum limit of N0 = Z0a ? Z01 in which all active areas are developed and are
occupied by new phases of nucleation. At this complicated state of formation of
electrochemical phase, the constant state can be set up only under specific terms
and conditions and after a certain time period. In fact, the amount, which is
measured as constant nucleation rate, not only specifies experimental information
with regard to kinetics of nucleation, but also clarifies appearance of active areas
on electrode (provided that this process is determiner of start state rate of phase
change). These cases should be considered while interpreting experimental
information on kinetics of formation of nucleuses on sub-layer of the same
material or another material [55–66].
4.7 Nucleus Situation on Electrode Surface
Based on law of probability distribution, the distance between nth neighbor of a

nucleus, which has been randomly distributed inside a v-dimensional space, can be
expressed as follows:
v=2 v=2 v
v p N0;v mn1
p N0;v rv;n
dPv;n ¼ rv;n exp drv;n
ðn 1Þ! Cð1 þ v=2Þ Cð1 þ v=2Þ
In fact, in above equation, parameter dPv,n specifies probability of presence of
nth neighbor of a nucleus at the distance between rv,n and rv,n ? drv,n where No,v is
nucleus’s average density, T is gamma function while v is spatial dimensions in
such a way that if nucleus is formed on a surface, v = 2 and if nucleus is formed
inside a 3-D space, v = 3. The average distance between nucleuses can be
Z1
Cðn þ 1=vÞ Cðn þ v=2Þ 1=m
rv;n ¼ rv;n dPv;n
ðn 1Þ! pv=2 N0;v
0
4.7 Nucleus Situation on Electrode Surface 121
It is observed that probability of presence of small distances on results obtained

from practical test is less in comparison with theoretical calculations. This subject
vanishes for second and third neighbors of nucleus. That is to say areas with
meager nucleation rate are and areas which their nucleation rate are decreased,
surround sustainable nucleuses. This issue has been observed in other electro-
chemical systems.
Electrodeposition of tertiary Al2O3/Y2O3/CNT nanocomposite by using pulsed
current has been studied [67]. Coating process has been performed on nickel
sulphate bath and nanostructure of obtained compound layer was examined with
high precision figure analysis of SEM images. The effects of process variables, i.e.
Y2O3 concentration, treatment time, current density and temperature of electrolyte
have been experimentally studied. Statistical methods were used to achieve the
minimum of corrosion rate and average size of nanoparticles. Finally the contri-
bution percentage of different effective factors was revealed and confirmation run
show the validity of obtained results. Also it has been revealed that by changing
the size of nanoparticles, corrosion properties of coatings will change significantly
in same trend. AFM and TEM analysis have confirmed smooth surface and
average size of nanoparticles in the optimal coating [67].
Electrodeposition is a very important scientific based technology. Coating wide
range of available base materials with electrodeposited layers of different metals/
alloys with different enhanced properties extends their use to industrial applica-
tions. Corrosion and wear are the effective factors in the failure of industrial
components; hence, many attempts have been made to find different methods of
reducing corrosion and wear costs. Recently, several techniques have been applied
to produce protective electrodeposited coatings, such as different alloys electro-
deposition, metal/oxide electrodeposition and nanocomposite electrodeposition.
Different obtained results exhibited that nanocomposite electrodeposited coatings
usually exhibit superior mechanical, electrochemical and oxidation properties as
compared to pure metal coatings as well as microcomposite electrodeposited
coatings. Improvement of these properties depended mainly on the size and the
percentage of the particles electrodeposited and the distribution status of the
nanoparticles. Due to high wear and corrosion rate, Ni-based nanocomposites with
Al2O3 or Y2O3 nanoparticles or carbon nanotubes (CNT) have been investigated
for a good protection of under friction parts.
The Taguchi method for the design of experiment has been used for optimizing
tertiary nanocomposite electrodeposited coating process parameters for the cor-
rosion protection of treated samples. The contribution of Y2O3 concentration is
more than the sum of the contributions of all the other three factors. It is evident
that, among the selected factors, Y2O3 concentration has the major influence on the
corrosion rate of performed coatings. It can be seen that the current density is
second important factor that affects on corrosion rate of the treated substrates.
Furthermore, it can be assumed that treatment time and temperature of electrolyte
have almost the same effect on corrosion rates of coatings because of the minor
difference in the contribution percentages among these two factors. By ranking
their relative contributions, the sequence of the four factors affecting the corrosion
Fig. 4.5 Relation among average size of nanoparticles and corrosion rate of electrodeposited
tertiary nanocomposite layer [67]
rate is Y2O3 concentration, current density, treatment time and temperature of

electrolyte. In the case of average size of nanoparticles ranking of effective factors
by their relative contributions is as same as for corrosion rate which show strong
relation among these two measured properties of coatings. AFM and TEM images
have confirmed smooth surface and average size of nanoparticles in the optimal
coating. Figure 4.5 illustrates relation among average size of nanoparticles and
corrosion rate.
4.8 Growth of 3-D Nano-Nucleuses
In l constant over-potential, the current I1(t) of a separate semi-spherical nucleus,

which is grown under combined conditions of charge transfer and limit current, is
" #
1 þ nt
I1 ðtÞ ¼ p 1
ð1 þ 2ntÞ1=2
The amounts of n and p will be as follows:

4pðzFDc1 Þ2 azFg ð1 þ aÞzFg

p¼ exp exp
i0 RT RT
4.8 Growth of 3-D Nano-Nucleuses 123

VM i20 2azFg ð1 2aÞzFg

n¼ exp exp
ðzFÞ2 Dc1 RT RT
where D is diffusion constant of metal ions and i0 is density of exchanged current

at nucleus-solution interface. Growth of a separate nucleus is highly dependent on
concentration and distribution of over-potential in the vicinity of nucleus.
Over-potential and concentration in distance q from a nucleus can be expressed
as follows:

I1 ðtÞ
cðqÞ ¼ c1 1
2pqFDc1

RT I1 ðtÞ
gðqÞ ¼ g þ ln 1
zF 2pqFDc1
With substitution of these two equations inside above equation, the constant
nucleation rate of J0(q) at the distance of q from nucleus will be as follows:
nc þ1
I1 ðtÞ
J0 ðqÞ ¼ J0 1
2pqzFDc1
Non-dimensional distribution of constant nucleation rate (critical nucleus)
around a semi-spherical nucleus inside the area was observed which over-potential
and concentration have been decreased. If various semi-spherical nucleuses are
formed on electrode surface, the local areas around nucleuses, which nucleation
rate has been decreased in there, are developed and are overlapped each other
gradually.
That is to say that a general theoretical model, indicating overall nucleation
rate, should be considered with taking into account effects of interaction of
nucleuses on each other.
When growth of nucleuses is carried on under conditions of controlled diffu-
sion, Total Current, provided that N(t) nucleuses are formed progressively on
electrode surface at time interval (t, 0), will be equal to:
1=2
D 1 1=2 2
iN ðtÞ ¼ bzFc 1 exp 0 pð8pcVM Þ Dt
J
pt 2
If N(0) nucleuses are appeared instantaneously at time t = 0 on electrode

surface, the following equation will be obtained:
1=2 n h io
D
iN0 ðtÞ ¼ zFc 1 exp N0 pð8pcVM Þ1=2 Dt
pt
In the above mentioned equation, b is a numerical constant. Specific property of
electrochemical nucleation is presence of a critical over-potential (lcrit) that below
this amount, nucleation rate of Jo is practically zero and above this amount, it is
increased exponentially. Regarding this subject, dual-polarization pulse is known

as an appropriate technique for electrochemical precipitation of metal nano-par-
ticles with a distribution of limited size and also compressed metal thin films.
In initial short pulse of l1 lcrit, a great number of metal nucleuses is formed.
Subsequently, only formed nucleuses are allowed to grow in second pulse of
l2 lcrit.
4.9 Metal Ion Structure
Existing ions in solution are primarily encircled by other species such as mole-
cules, ions, especially water molecules. When these ions are encircled by water
molecules, geometrical structure of water molecules plays a key role in subsequent
processes. The 104.45 angle formed between two hydrogen–oxygen bonds,
existing in water molecule, is as a result of strong bipolar forces inside it. Elec-
trostatic gravity between metal cations with positive charge and water molecules
results in hydration of existing ions or in other words, covering metal ions by water
molecules. The hydration process metal ions are shown in which for comparison,
display of an anion is also shown. Generally speaking, taking two major points into
consideration is of paramount significance.
Firstly, salt of most metals even in solid state is in hydrated form and therefore,
in many cases, metal salts in solid state are written similarly with actual hydrated
conditions. But, these two states differ from each other completely. Secondly, the
number of water molecules in hydrated formula of a salt is not an accurate and
clear-cut number in such a way that metal ions are generally encircled by
numerous layers of water molecules. With regard to hydration of anions and
cations, we should consider that cations, in comparison with anions, are hydrated
more and are encircled by water molecules completely. The reason for this phe-
nomenon is smaller ionic radius of cation in comparison with anion.
The number of water molecules, which create the first hydrated layer around a
metal ion, can be varied between 1 and 10 water molecules. Consequently, inter-
action of metal cations with water molecules, encircling a hydrated cation, forms an
electrical field around the cation. As it is observed, regarding weaker electrostatic
forces of external layers, balance of water molecules, encircling a metal ion, is
connected weakly to ion in such a way that this cation loses external layers of water
molecules and a metal cation encircled by a layer of water molecules is remained.
4.10 Double-Layer Structure
Upon placing metal in aqueous solution, an electrical dual layer is created at

interface of these two phases. Electrochemical double-layer structure severely
affects kinetics of metal precipitation. Numerous models were presented for
4.10 Double-Layer Structure 125
showing electrochemical double-layer structure between 1950 and 1970, the most
important classic models are explained in below [68–81].
4.10.1 Helmholtz-Perrin Model
Based on Helmholtz-Perrin Model, double layer includes a row of charged species

in metal-solution interface. According to this model, electrons are placed at
cathode side while metal ions are placed at electrolyte side equally. The distance
between these two layers (row) is at the level of ionic radius. At Helmholtz-Perrin
model, double electrical layer, similar to a capacitor, includes two compressed
parallel layers with constant capacity and potential gradient in Helmholtz layer
(dH) is linear.

du
dlinear ¼ Const:
dx
Helmholtz-Perrin Model is a very simple structured model of reality. At this
model, spatial distribution of metal ions against electrode surface, has not been
considered as a result of dual effects of electrostatic gravity forces and accidental
movements (as a result of thermal movements).
This model is not appropriate for condensed electrolytes, but does not show
actual spatial distribution of metal ions on cathode surface in diluted electrolytes.
4.10.2 Gouy-Chapman Model
At this model, fluid flow, which is of paramount importance especially for diluted
electrolytes, has been considered. Based on this model, concentration of metal ions
with increase of distance from cathode surface is reduced exponentially and this
density is reached zero level in whole solution. Therefore, a little number of ions is
adsorbed by forces existing on cathode surface. Based on Gouy-Chapman Model,
two potential distribution areas can be considered in cathode-electrolyte interface.
At the first area, potential increases linearly with distance from cathode and after this
area, penetration area is observed in which, potential is changed exponentially.
Inner layer in Gouy-Chapman Model is known as Helmholtz layer. At this layer,
potential gradient is approximately in linear form and in outer layer (penetration
layer), potential gradient is changed exponentially and this layer is developed to
whole solution. The way of potential changes at penetration area is expressed as
follows:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

du 2RT X s
zi Fu
ddiff ¼ ci exp 1
dx e i¼1 RT
In the above equation, R is gas constant, Y is absolute temperature, e is dielectric

constant, ci is concentration of metal ion in whole solution, zi is charge of metal
ion, and F is Faraday constant. In diluted electrolytes, the thickness of penetration
layer is measured approx. 10-4 cm while this thickness is measured approx. 10-7
to 10-8 cm in condensed electrolytes [82–87].
4.10.3 Stern-Graham Model
Gouy-Chapman Model is not able to introduce actual specifications of double layer

in the layer near to cathode and especially creates an adsorbent layer on cathode
surface of water bipolar. In addition, various species existing in electrolyte, like
superficial active anions or aqueous molecules existing in electrolyte, can also be
adsorbed on cathode surface. This phenomenon is known as specific adsorption or
contact adsorption. Hydration of anions, due to larger radius of anion compared to
cation, is weaker than hydration of cations. Hence, anions can be adsorbed on
cathode surface strongly and also can near cathode surface through losing hydrated
layer of a hydrated cation.
With regard to cations, due to keeping hydrate, cations are adsorbed by Cou-
lomb forces on cathode surface. The amount of these Columbus forces is function
of a cathodic potential. As it is observed, internal Helmholtz layer includes a
screen of adsorbed anions. External Helmholtz layer is a plate which passes from
charge centers of adsorbed metal ions and indicates external region of Helmholtz
layer. After this layer, penetration layer is placed which is comprised of movable
metal ions [88–94]. The concentration of ions with positive charge at this layer
should be at such a level that total electrical charge would be zero. Potential
gradient versus distance from metal-solution interface is as follows:
Du ¼ ulinear þ uspec þ udiffuse
4.11 Determining Stages for Rate of Electrode Reactions
There are numerous separate stages during transfer of metal ion from inside of
whole solution to creation of metal lattice on cathode surface. Each of these stages
can be a rate controller. The first stage at this route is transfer or movement of the
desired ions from whole solution to the vicinity of cathode. Metallic ions, which
exist either in hydrated or complex forms, first move towards cathode in solution.
This stage is usually carried out by convection flows inside solution. Migration
of ions under effect of potential gradient between anode and cathode can play a
key role in ionic transfer, but comparatively play a partial and meager role in
material transfer resulted from convection inside the solution. Transferred ions
reach external part of penetration layer and pass from penetration layer as a result
of existing concentration gradient. At this stage, solution convection does not play
4.11 Determining Stages for Rate of Electrode Reactions 127
a key role in transfer of ions. In fact, convectional flows do not affect exchange of
ion in Nernst layer, but it can affect thickness of Nernst layer so that can reduce
thickness of Nernst layer dN and increase concentration gradient. When these ions
pass from diffusion layer and electrical dual layer (Helmholtz Layer), they reach to
cathode surface and are turned into pure metal ions. Pure metal ions are turned into
adatoms through combining with electrons on cathode surface, adatoms start
moving on surface with the aim of being adsorbed in active areas as well as
forming a very strong chemical bond.
At this stage, metal atoms are operated and distributed appropriately, aimed at
creating a crystal lattice. This stage includes nucleation and coating growth stages.
Controlling stages of reactions rate should be reduced or omitted in order to
increase rate of reactions on cathode surface. When rate controlling stage is under
control of material transfer, increase of over-potential will accelerate reaction. The
total over-potential is sum of concentration potential (gc), activation or charge
transfer potential (gD), crystallization potential (gK) and resistance potential (gW).
In metal electrical plating process, a great number of these over-potentials affect
rate of reaction.
gtot ¼ gc þ gD þ gK þ gW
Electrolyte type, density of cathodic current and type of coating metal are
considered as factors effective on determination of amount of over-potential. Over-
potentials of charge transfer and concentration is of paramount significance,
playing the highest constructive role in this regard. From among these two factors,
metal ion transfer from double layers is a critical stage and over-potential of
charge transfer can control rate [62, 95–107].
4.12 Concentration Over-Potential
Concentration over-potential originates from this fact that in electrolysis process,

metal ion concentration in whole solution cathode surface differs from each other.
This concentration in cathode surface is less than whole solution in such a way that
metal cations are consumed on cathodic surface with higher speed than providing
them from whole solution and are precipitated as metal atom. Existence of such
over-potential will cause precipitation of metal as powder on surface of cathode
and will decrease quality of coating.
Concentration over-potential includes reaction over-potential and penetration
over-potential. Reaction over-potential is occurred when metal ions, in their route
for reaching cathode, participate in chemical reactions and these reactions should
be so slow to control speed. For example, hydration and dehydration or formation
or decomposition of complex compounds is samples of these types of over-
potential which can control speed before charge transfer reaction. Penetration over-
potential is related to the penetration of metal ion before discharge of its electrical
charge. In fact, existence of a concentration gradient will form a penetration layer.
This over-potential is reached to its maximum amount when concentration is

reached zero on electrode (cathode) surface. Reduction of thickness of penetration
layer through mixing of solution is one method for eliminating or decreasing this
kind of over-potential.
4.13 Charge Transfer Over-Potential
Charge transfer in cathode with metal ion hydrated in metal-solution interface is

prerequisite for precipitation of metal with electrochemical method. The driving
force of such process is linear potential difference between metal surface and
solution-metal interface. In this process, hydrated layer at environs of metal ion
will be eradicated or will be split enough in such a way that metal ion can pass
from Helmholtz layer, aimed at performing charge transfer due to approaching
the cathode surface. In cathode, electrons pass from Helmholtz layer and charge
transfer process is made. Any delay in charge transfer process is known as
activation over-potential or charge transfer over-potential. We face such over-
potential type in all electrical plating reactions.
4.14 Crystallization Over-Potential
Metal deposition reaction is carried out through electroplating method at two stages.
The first stage includes formation of crystal nuclei in certain points of cathode which
these nuclei are sustainable thermodynamically. The next stage is growth of estab-
lished nuclei. These two stages are known as crystallization over-potential. We should
consider that nucleation has usually more share at this type of over-potential than
growth, because activation energy is for nucleation more than growth. It should be
noted that conversion of metal atoms to crystalline lattice is carried out in specified
growth points of cathode surface in such a way that after discharge of metal ions in
specified points of cathode surface, these atoms should penetrate towards growth
areas, aimed at setting up crystalline lattice. Crystallization over-potential would be
important when nucleation and growth stages can control rate. For example, if
penetration of metal atoms on cathode surface is slow, such circumstances will be
generated. The difference in concentration of adsorbed atoms at growth points can
cause emergence of difference in crystallization over-potential in these points.
4.15 Ohm or Resistance Over-Potential
In fact, this type of over-potential is potential loss, beyond double layer and unlike
other over-potentials, this type of potential follows Ohm Law in such a way that
there exists a linear relation between this type of over-potential and current. For
4.15 Ohm or Resistance Over-Potential 129
example, resistance of electrolyte at Nernst penetration layer is a result of exis-

tence of a film of reactants or reaction products on cathode surface. Such layer can
be a solid layer or fluid with low electrical conductivity which covers all surfaces
of cathode. Hence, accessing to metal ions on cathode surface is prevented [103,
108–123].
4.16 Pulse Electrochemical Deposition Method
Pulse Electrochemical Deposition process has been paid more attention in recent
years. Some researchers have reported reduction of porosity value of gold cover
by pulse current. Precipitation of palladium with very minute and smooth
granule and with less hydrogen has been reported by some researchers.
Electrochemical depositions, free from chrome and rhodium crack have been
produced by pulsed electrolysis. Pulsed electrochemical depositions of copper
which resulted in more smaller and compressed granule have also been reported
by some of researchers.
Some researchers have obtained nickel electrochemical depositions from
electrolytes free from additives by pulse currents. It should be noted that a wide
spectrum of shapes of pulse fluctuation current waves can be produced by new
electronic devices. Shapes of pulse current waves can be classified into two
general categories. The first category is related to mono-polar pulse currents while
the second category is related to bipolar pulse currents (anode and cathode).
Variables of pulse electrochemical deposition include maximum current density
(Jp), on-pulse time (Ton), off-pulse time (Toff). Parameter Jm in the figure indicates
average current density. Regarding Jp, Ton and Toff parameters, all other amounts
of pulse current parameters can be calculated as follows:
Pulse frequency: f = 1/(Ton ? Toff)
Work period: h ¼ Ton =ðTon þ Toff Þ
Average current density: Jm ¼ Jp h
The theory related to pulse plating (electroplating) is simple. The cathode layer
is kept rich with metal ions and impurities are decreased as much as possible.
During on-pulse time (Ton), when current is connected, metal ions are reduced on
cathode. When current is disconnected (off-pulse time), any type of concentration
gradient, appeared during on-pulse time (Ton), will be eradicated and there is
possibility of separation of gas bubbles and impurities which have been adsorbed
on cathode and this process is repeated once again. In pulsed electrochemical
deposition method, related parameters can be changed in wide scale indepen-
dently. In electrochemical deposition method with D.C. current, current density is
the only changeable parameter. Consequently, creation of various situations faces
more restriction. There are impurities which have been adsorbed on cathode and
then this process is repeated once again. In electrochemical deposition method
with pulse current, related parameters is changeable in a wide range indepen-

dently. In electrochemical deposition method with direct current, current density is
the sole changeable parameter and consequently, creation of various situations
faces more restriction.
In the beginning of on-pulse time of first pulse, nucleation of precipitation
granules are happened as a result of penetration of metal ions through electrolyte.
This nucleation process is carried on preferably on high-energy areas, which are
mainly grain boundary and these nuclei grow with continuation of time. With the
inception of second on-pulse time, penetration of metal ions and precipitation of
them on grain boundary, formed from first pulse, is appeared. Hence, since current
is turned on or turned off alternatively and new nucleation is appeared at full-
energy areas during on-pulse time of each cycle, hence, new granules grow con-
tinuously in line with new grain boundaries of electroplated metal. On the other
hand, during off-pulse time of cycle, concentration of existing solved components
in the vicinity of cathode surface is decreased as a result of cathodic reduction
reactions of metal ions. Hence, each concentration gradient in the vicinity of
cathode surface will be decreased during off-pulse time of cycle and even is
omitted and consequently, metal concentration on surface returns to the normal
concentration of solution’s volume [124–136].
4.17 Charging and De-Charging of Double Layer in Pulse

Electroplating
In an electrochemical process, a current, which is supplied by a power supply (It) is

divided into two parts. One part is related to non-Faradic current or capacity
current (Ic) which is spent for charge of dual layer while the other part is Faradic
current (IF) which is used for reducing and precipitating of metal. The sum of these
two currents is equal to total current.
It ¼ IF þ Ic
Dual layer charging requires spending time. The necessary time for reaching full
potential from zero potential, according to imposed current (or time of reaching
It = IF state) is known as double-layer charging time (tc). Decharge time (td) is
necessary time in which electrode potential reach an amount according to zero
current and/or a state in which equation IF = 0 holds. In electroplating with direct
current, electrical double-layer charge and de-charge is carried out in the begin-
ning and end of electroplating respectively. At this state, capacity current can be
ignored compared to Faradic current. However, in pulsed electroplating, regarding
existing time cut, electrical double-layer charge and de-charge is carried out
alternatively at time intervals (based on Ton and Toff). Therefore, it seems neces-
sary that rate and share of capacity current should be specified with regard to total
current in each pulse. In pulsed electroplating, the ideal state is brought about at
4.17 Charging and De-Charging of Double Layer in Pulse Electroplating 131
Ton tc condition. At this state, electrical double-layer has enough opportunity to

be charged and de-charged and current is imposed fully. In practice, ideal state is
not accessible and charging time occupies a portion of pulse length and meager
change is observed in pulse shape.
If charging time is larger than on-pulse time, (Ton \ tc), potential will never
reach the desired amount and always the equation IF \ It will be hold during
electroplating. The similar phenomenon also is occurred at the end of each pulse.
If de-charging time is larger than off-pulse time (Toff \ Td), then double electrical
layers will not be de-charged fully and the equation IF = 0 will not be hold. Under
such circumstance, giving the name of pulsed electroplating to the system is not
accurate, because current only shows fluctuation in a way that work conditions is
much more similar to electroplating with direct current. Hence, in pulsed elec-
troplating, observing two conditions for assuring connection of pulse seems
necessary.
1. On-pulse time should be larger than charging time (Ton [ tc).
2. Off-pulse time should be larger than de-charging time (Toff [ td).
In case of given charging and de-charging time, minimum allowable amount is
determined for Ton and Toff (largest frequency) in which pulse state is completely
observed. For calculation of charging and de-charging time in pulse electroplating,
moreover high calculations, getting access to enough information, like capacity of
double layer, over-potential of cathode reaction, electrolyte constituents, electrode
geometrical shape, electroplating current density, and electrode crystalline struc-
ture seems necessary. The principles of calculation of charging and de-charging
time of electrical double layer are based on Butler-Volmer equation.

anFg ð1 aÞnFg

JF ¼ J0 exp exp
RT RT
where JF is density of Faradic current (A/cm2), J0 is exchange current density

(A cm2), a is charge transfer constant, n is the number of electrons, F is Faraday
constant (96,500 C), g is over-potential, R is gas constant (J/mol K) and T is
absolute temperature (K). Calculation of charging or de-charging time based on
numerical methods is time-consuming and complicated. Puippe has proposed the
following equation as a fast and acceptable method for calculation of charging or
de-charging time based on maximum current density.
17 120
tc ¼ ; td ¼
Jp Jp
In the above equation, tc and td are in terms of microsecond and Jp is in A/cm2.

Studies made in this regard on many systems showed that charging time is within
the range of tens to hundredth of microseconds while de-charging time is within
the range of multi-thousand microseconds. We should bear in mind that con-
sumption of a part of total current for charging double layer (capacity current) in
the beginning of each pulse does not affect efficiency of total current, because this
amount of current is compensated in double-layer de-charging mode and at the

off-pulse time (Toff) [78, 137–139].
4.18 Nanostructured Coating Properties
In terms of production methods, it can be stated that electrochemical coating

method is regarded as one of the oldest methods for imposing nanostructured
coatings. Of course, creation of nanostructure coating has been made without any
knowledge in many cases. Before 1980s, not any subject has been mentioned in the
field of creation of nanostructure coating by this method. Various research
activities have been made in the field of creation of nanostructure coating as size as
10 nm by electrochemical deposition method. In the field of coating of pure
metals, it can be referred to the coating of nickel, cobalt, palladium and copper.
With regard to duplex alloys, it can be referred to creation of nickel–phosphor
alloy coating, nickel–iron coating, zinc–nickel coating, palladium–iron coating
and cobalt–tungsten coating [140–144].
Triple alloys of nickel–iron–chrome have been coated successfully with this
method. Even, in various resources, it has been mentioned that multilayer, com-
posite and ceramic coatings have been coated with granules smaller than 100 nm.
With various studies made in this regard on nanostructure coating, it is observed
that amount of hole and/or vacancy is very little in these materials. In some
research activities made in this regard, it has been observed that converting into
nanostructure mode is made when the ratio of triple junctions to grain boundary is
moving towards infinity. Properties of nanostructure costing can be classified into
two major categories. The first category is the properties which are dependent on
size of crystal or cluster (grain size). These properties include strength, softness,
stiffness, resistance against erosion, friction coefficient, electrical resistance, dis-
solving in solid state, hydrogen dissolving and penetration of it inside material and
also resistant against local corrosions and stress corrosion. Unlike these properties,
there are other material properties which do not depend on grain size such as
volume density, thermal expansion, Young Modulus and resistance against envi-
ronment of salt spray test. In continuation, some of these properties will be studied
[145–157].
4.18.1 Mechanical Properties
As a general principle, it should be said that plastic deformation of a nanostructure

coating strictly depends on its grain size. Various tests in environment temperature
have shown that with decreasing grain size beyond certain limit, Hall-Petch
equation doesn’t apply and contrary to expectation, material will become softer. It
has been observed that this affair occurs when amount of triple junctions shows
4.18 Nanostructured Coating Properties 133
remarkable growth. This subject accords with ‘‘Triple Line Softening Effect’’
theory. Some other mechanical properties of these coatings can be justified with
studying behavior of this material and considering the triple junctions. Reduction
of granule size has remarkable effect on improvement of resistance against erosion
in nanostructure and composite materials. Of course, most research activities have
been made on double-phase and/or composite nanostructures and not appropriate
research activities have been made with relation to pure nano-crystalline metals.
Research activities made on frictional behavior of multilayer nano-coats show that
their behaviors have been more affected with chemical composition of materials
and their nano-microstructure has not any effect on their frictional behavior.
Erosion behavior, under high stresses, is severely affected with chemical com-
position of materials and their nano-microstructure has not any remarkable affect
on their frictional behavior. Study of erosion behavior under low and average
loading condition in nano-materials shows that because of higher stiffness, erosion
resistance of these materials is more than that of materials with large size. With
regard to creep in nanostructured materials, since grain boundary’s slip is regarded
as one of the mechanisms of creep, creep rate in nanostructured materials is more
than microcrystal materials [144, 145, 147, 148, 153–155, 158–163].
4.18.2 Catalyst Properties
Superficial topography of solids plays a key role in distribution of energy in

surface of materials, especially when irregularities are observed on atomic level. In
fact, superficial activities are increased with the decrease of grain size. Nano-
structure catalysis, similar to very minute particles, enjoy high surface/volume
ratio and create unique catalytic properties.
4.18.3 Electrical Properties
In nanostructured materials, due to presence of high fraction of grain boundaries,

electrical resistance is very high which this property is considered as an advantage
for manufacturing of soft magnetic materials.
4.18.4 Anti-Corrosive Properties
In spite of this fact that corrosive properties of nanostructure coating is of para-

mount significance, very few research activities have been made in this regard.
Nano-crystalline materials provide new approach for improvement of properties,
without any change in chemical composition. Small size of grain and high
volumetric fraction of grain boundary can cause different corrosion behavior with
respect to multi-crystalline materials. Effect of reduction of grain size on increase
of resistance against local corrosion of stainless steel has been studied. As it is
observed, potential of passive film fracture is equal to (0.3 VSCE) for stainless steel
with normal grain size of 30 micron and (1.15 VSCE) for stainless steel with the
same chemical composition and surface grain size of 25 nm. In fact, fracture
potential of passive film for nanostructure has turned more positive approx.
850 mV. It can be concluded that nanostructure has caused increase of resistance
against local corrosion. This subject has been studied for aluminum metal and
accords with the above mentioned results. Its main reason has been explained as
uniform distribution of imperfections in passive film. Presence of a great number
of these imperfections results in more distribution of chloride ion on metal surface
[164–177].
Density of chloride ion in each imperfection, extant in nanostructure, due to its
distribution in imperfections of grain boundary in comparison with coarse struc-
ture, is reduced tremendously which will cause that local condensation of chloride
ion in imperfections extant in grain boundary require a stronger driving force and
consequently, more anodic potential is required for growth of a stable hole.
Potentiostatic and potentiodynamic tests, made on special nanostructure nickel and
multi-crystalline nickel in bi-normal sulphuric acid, shows that sample with nano
structure shows the same active, passive, transpassive behavior of normal metal.
But, difference of these two materials is disclosed in open-circuit potential and also
in passive currents. Nanostructure sample in passive part shows higher current
density which can be related to higher corrosion rate than normal metal.
This high corrosion rate can be related to the existence of high grain boundary
and triple junctions. These regions are corrosive-prone due to having high energy.
This difference in current density is observed less in high potentials, because in
this situation, effect of structure is not longer important due to high corrosion rate.
The other difference in diagrams is observed on open-circuit potential. Increase in
degree of open-circuit potential is related to the catalytic role of nanometer
structure in hydrogen-reduction reaction. In research activities it is observed that
multi-crystalline nickel has been corroded locally but nanostructure nickel has
been corroded uniformly. The main reason is related to eradication of passive layer
formed on nanostructure metal surface due to existence of high imperfections
inside it.
Hence, passive layer formed on nanostructure nickel, has been eradicated fully
but passive layer, existing on multi-crystalline nickel is eradicated locally and on
grain boundary. Therefore, corrosion will be continued locally. Due to distribution
of chloride ion, tendency to creation of local corrosion is very low. However,
reduction of sensitivity with regard to local corrosion, for preventing from sudden
destruction, can be beneficial. The salt spray tests, carried out on nickel, show that
creation of nanostructure has not significant effect on corrosion resistance prop-
erties and multi-crystalline and nanostructure samples have protected steel equally
in test conditions.
Also, in another research, it has been observed that sensitivity to corrosion of

grain boundary and stress corrosion of grain boundary has been lessened for coating
of nanostructure nickel by electrochemical method. It has been observed that
material is resistant against pitting corrosion and also its sensitivity has been
reduced against crevice corrosion. Other tests have been shown that nanostructure
nickel is resistant against alkaline environments and reduction acids. These reports
indicate that more amounts of grain boundary and triple junction in nano-crystalline
samples, will increase the amounts of atoms which participate in reaction and
consequently, they create places for electrochemical activity [168, 171, 178–182].
To prepare high dielectric thin film of polymer-based materials, nanometer
sized barium titanate (BaTiO3) particles, which should have high dielectric
coefficients and low energy dissipation factors due to nano-size effects, were
dispersed in polyvinylidene fluoride (PVDF) or siloxane-modified polyamideimide
(SPAI) [183]. The BaTiO3 particles with crystal sizes of 10.5–34.6 nm were
synthesized with a complex alkoxide method. Polymer/N-methyl-2-pyrrodinone
solution suspending the BaTiO3 particles was spin-coated on ITO glass substrates
to prepare polymer-based composite films with thickness of submicron meters.
The BaTiO3 particles were dispersed more homogeneously in the PVDF film than
in the SPAI film. The good dispersion of the particles in the PVDF film brought
about a smooth surface of the film that had a root mean square roughness less than
20 nm at a particle volume fraction of 30%. The roughness was less than one-tenth
of the roughness of the SPAI composite film. An increase in the BaTiO3 crystal
size from 10.5 to 34.6 nm in the PVDF film at a particle volume fraction of 30%
increased the dielectric constant of the film from 20.1 to 31.8. The BaTiO3–PVDF
composite film attained high dielectric constant that had more than twice the
dielectric constant of the BaTiO3–SPAI composite film. The dissipation factor of
the PVDF composite film was as low as 0.05 at 104 Hz.
Ferroelectric lead zirconate titanate and barium titanate (BaTiO3) are candi-
dates for capacitor materials because of their high dielectric constants. The
titanates, however, require high temperature processing, which is not compatible
for embedding the capacitors in the printed circuit board of a resin substrate. To
realize low temperature processing, a number of attempts have been devoted, one
of which is the application of a nano-crystalline seeding technique. Previous work
with this technique reported that high dielectric nano-composite films of titanates
could be fabricated at a temperature as low as 350C. Fabrication of ceramic–
polymer composites is another attempt, and is receiving attention since this
technique combines the low temperature processing of polymers and the high
dielectric constant of ceramics. Traditional approach for preparation of such
composite films is to mix a dielectric polymer solution and submicron- or micron-
sized ferroelectric particles, and evaporate the solvent of the polymer solution.
Since a composite film at high particle contents has a roughness of at least the
ceramic particle size, the film thickness has to be much larger than the particle size
to achieve uniform film thickness. Consequently, the thickness of composite films
containing such large particles exceeded 1 lm, and it was difficult to achieve high
capacitance densities. In addition, fabrication of the films in integrated circuits
requires a surface roughness much less than a 100 nm. Therefore, to meet the
demands of film thickness and smoothness, it is strongly required to prepare
composite films that disperse ceramic nanoparticles.
Ceramics such as BaTiO3 with particle sizes larger than several 10 nm have
ferroelectric properties. However, when their sizes approach to nanometers, they
tend to have para-electric properties that result in low dissipation factor. These
properties are suitable for dielectric materials. Composite films of BaTiO3 nano-
particle/polymer were spin-coated on ITO substrates with NMP solvent [183]. The
BaTiO3 particles that were synthesized via hydrolysis reaction of complex alk-
oxide were homogeneously dispersed in PVDF, whereas the particles aggregated
in SPAI. A root mean square roughness of the BaTiO3–PVDF composite film
attained less than 20 nm at a particle volume fraction of 30%. The BaTiO3–PVDF
films had high dielectric constants compared to the BaTiO3–SPAI film, which
might be related to difference in the dispersibility of the BaTiO3 particles in the
Fig. 4.6 TEM images of BaTiO3 particles prepared at a 0.12 kmol/m3 metal, 10 kmol/m3 H2O
and 70C, b 0.06 kmol/m3 metal, 20 kmol/m3 H2O and 70C, c 0.12 kmol/m3 metal, 20 kmol/m3
H2O and 70C, and d 0.06 kmol/m3 metal, 20 kmol/m3 H2O and 50C. Pure ethanol solvent was
used for the samples a, b and d, and 50% (v/v) benzene/ethanol solvent was used for the sample
c, reprinted with kind permission from Konno [183]
Fig. 4.7 Dielectric constant

(open circle) and dissipation
factor (filled circle) of
BaTiO3–PVDF composite
films measured at 104 Hz as a
function of BaTiO3 crystal
size. BaTiO3 volume fraction:
30%, spin speed: 3,000 rpm
and drying temperature:
150C, reprinted with kind
permission from Konno [183]
Fig. 4.8 Thickness of

BaTiO3–PVDF (filled circle)
and BaTiO3–SPAI composite
films (open circle) as a
function of volume fraction
of particles. The BaTiO3
crystal size: 27.3 nm, spin
speed: 3,000 rpm and drying
temperature: 150C, reprinted
with kind permission from
Konno [183]
film. The dielectric constant of the composite films increased with an increase in
the BaTiO3 crystal size and with BaTiO3 volume fraction in the composite film.
The dielectric constant reached 31.8 for the 30 vol%–BaTiO3–PVDF film with a
BaTiO3 crystal size of 27.3 nm, which was four times larger than the dielectric
constant of the PVDF film without BaTiO3 and corresponded to a capacitance
density as large as 0.63 nF/mm2. Figure 4.6 illustrates TEM images of BaTiO3
particles. Different solvents were used for the samples. Size effect can be seen in
Fig. 4.7 that shows dielectric constant and dissipation factor of BaTiO3–PVDF
composite films measured at 104 Hz as a function of BaTiO3 crystal size.
Thickness of BaTiO3–PVDF and BaTiO3–SPAI composite films as a function of
volume fraction of particles can also be seen in Fig. 4.8.
References
1. Huang, R., Guo, L.H.: Lack of nano size effect on electrochemistry of dopamine at a gold
nanoparticle modified indium tin oxide electrode. Sci. China Chem. 53, 1778–1783 (2010)
2. Billy, E., Maillard, F., Morin, A., Guetaz, L., Emieux, F., Thurier, C., Doppelt, P., Donet, S.,
Mailley, S.: Impact of ultra-low Pt loadings on the performance of anode/cathode in a
proton-exchange membrane fuel cell. J. Power Sour. 195, 2737–2746 (2010)
3. Wang, X.M., Xia, Y.Y.: Synthesis, characterization and catalytic activity of an ultrafine Pd/
C catalyst for formic acid electrooxidation. Electrochim. Acta 54, 7525–7530 (2009)
4. Okubo, M., Hosono, E., Kudo, T., Zhou, H.S., Honma, I.: Size effect on electrochemical
property of nanocrystalline LiCoO2 synthesized from rapid thermal annealing method. Solid
State Ion. 180, 612–615 (2009)
5. Malheiro, A.R., Perez, J., Villullas, H.M.: Well-alloyed PtFeC nanocatalysts of controlled
composition and same particle size: oxygen reduction and methanol tolerance.
J. Electrochem. Soc. 156, B51–B58 (2009)
6. Leontyev, I.N., Chernyshov, D.Y., Guterman, V.E., Pakhomova, E.V., Guterman, A.V.:
Particle size effect in carbon supported Pt-Co alloy electrocatalysts prepared by the
borohydride method: XRD characterization. Appl. Catal. A Gen. 357, 1–4 (2009)
7. Lee, J.I., Jeong, Y.H., No, H.C., Hannebauer, R., Yoo, S.K.: Size effect of nanometer
vacuum gap thermionic power conversion device with CsI coated graphite electrodes. Appl.
Phys. Lett. 95 (2009)
8. Gu, Y., St-Pierre, J., Joly, A., Goeke, R., Datye, A., Atanassov, P.: Aging studies of Pt/
glassy carbon model electrocatalysts. J. Electrochem. Soc. 156, B485–B492 (2009)
9. Campbell, F.W., Belding, S.R., Baron, R., Xiao, L., Compton, R.G.: Hydrogen peroxide
electroreduction at a silver-nanoparticle array: investigating nanoparticle size and coverage
effects. J. Phys. Chem. C 113, 9053–9062 (2009)
10. Borghols, W.J.H., Wagemaker, M., Lafont, U., Kelder, E.M., Mulder, F.M.: Size effects in
the Li4+xTi5O12 spinel. J. Am. Chem. Soc. 131, 17786–17792 (2009)
11. Alanyalioğlu, M., Bayrakğeken, F., Demir, U.: Preparation of PbS thin films: a new
electrochemical route for underpotential deposition. Electrochim. Acta 54, 6554–6559
(2009)
12. Kozhina, G.A., Ermakov, A.N., Fetisov, V.B., Fetisov, A.V., Fishman, A.Y., Petrova, S.A.,
Zakharov, R.G., Shunyaev, K.Y., Rassokhin, S.V.: Influence of the transition to nanoscaled
state on electrochemical properties of LaMnO3+d oxide. In: Defect and Diffusion Forum,
pp. 354–360. (2008)
13. Guo, Y.G., Hu, J.S., Wan, L.J.: Nanostructured materials for electrochemical energy
conversion and storage devices. Adv. Mater. 20, 2877–2887 (2008)
14. Babu, P.K., Chung, J.H., Oldfield, E., Wieckowski, A.: CO surface diffusion on platinum
fuel cell catalysts by electrochemical NMR. Electrochim. Acta 53, 6672–6679 (2008)
15. Aliofkhazraei, M., Ahangarani, S., Sabour Rouhaghdam, A.: Effect of the duty cycle of
pulsed current on nanocomposite layers formed by pulsed electrodeposition. Rare Met. 29,
209–213 (2010)
16. Rafailovic, L.D., Artner, W., Nauer, G.E., Minic, D.M.: Structure, morphology and thermal
stability of electrochemically obtained Ni-Co deposits. Thermochimica Acta 496, 110–116
(2009)
17. Chun, J.Y., Chun, J.H.: A negative value of the interaction parameter for over-potentially
deposited hydrogen at Pt, Ir, and Pt-Ir alloy electrode interfaces. Electrochem. Commun. 11,
744–747 (2009)
18. Mao, Z., Ma, J., Wang, J., Sun, B.: The effect of powder preparation method on the
corrosion and mechanical properties of TiN-based coatings by reactive plasma spraying.
Appl. Surf. Sci. 255, 3784–3788 (2009)
19. Lee, L., He, D., Carcea, A.G., Newman, R.C.: Exploring the reactivity and nanoscale
morphology of de-alloyed layers. Corros. Sci. 49, 72–80 (2007)
References 139
20. Mandin, P., Cense, J.M., Picard, G., Lincot, D.: Simplified kinetic modelling and numerical
simulation of a metal oxide chemical bath electro deposition process at a rotating electrode.
Electrochim. Acta 52, 1296–1308 (2006)
21. Cavallotti, P.L., Nobili, L., Vicenzo, A.: Phase structure of electrodeposited alloys.
22. Seo, J.H., Kim, U.K., Yim, T.H., Park, Y.B.: Textures and grain growth in nanocrystalline
Fe–Ni alloys. In: Materials Science Forum, pp. 3483–3488. (2005)
23. Gulivets, A.N., Zabludovsky, V.A., Baskevich, A.S., Shtapenko, E.P., Ganitch, R.P.:
Structural transitions of Ni-P films electrodeposited by pulsed current. Trans. Inst. Met.
Finish. 82, 147–149 (2004)
24. Glinkina, I.V., Durov, V.A., Mel’nitchenko, G.A.: Modelling of electrolyte mixtures with
application to chemical equilibria in mixtures—prototypes of blood’s plasma and
calcification of soft tissues. J. Mol. Liq. 110, 63–67 (2004)
25. Switzer, J.A., Kothari, H.M., Bohannan, E.W.: Thermodynamic to kinetic transition in
epitaxial electrodeposition. J. Phys. Chem. B 106, 4027–4031 (2002)
26. Fang, B., Zhou, C., Liu, X., Duan, S.: Performance of a novel Ni/Nb cathode material for
molten carbonate fuel cells (MCFC). J. Appl. Electrochem. 31, 201–205 (2001)
27. Wu, Q., Barkey, D.: Faceting and roughening transitions on copper single crystals in acid
sulfate plating baths with chloride. J. Electrochem. Soc. 147, 1038–1045 (2000)
28. Vaškelis, A., Norkus, E.: Autocatalytic processes of copper(II) and silver(I) reduction by
cobalt(II) complexes. Electrochim. Acta. 44, 3667–3677 (1999)
29. Bruet, H., Bonino, J.P., Rousset, A., Chauveau, M.E.: Structure of zinc-nickel
alloyelectrodeposits. J. Mater. Sci. 34, 881–886 (1999)
30. Chmielewski, M., Grzeszczuk, M., Kalenik, J., Kpas-Suwara, A.: Evaluation of the potential
dependence of 2D-3D growth rates and structures of polypyrrole films in aqueous solutions
of hexafluorates. J. Electroanal. Chem. 647, 169–180 (2010)
31. Gopalakrishnan, N., Elanchezhiyan, J., Bhuvana, K.P., Balasubramanian, T.: Nucleation
and characterization of Zn1-xMnxO thin films deposited on different substrates. Phys.
B Condens. Matter 404, 1563–1567 (2009)
32. Vasilakopoulos, D., Bouroushian, M., Spyrellis, N.: Electrocrystallisation of zinc from
acidic sulphate baths; A nucleation and crystal growth process. Electrochim. Acta 54, 2509–
2514 (2009)
33. Chen, S., Liu, W., Huang, Z., Liu, X., Zhang, Q., Lu, X.: The simulation of the
electrochemical cathodic Ca–P deposition process. Mater. Sci. Eng. C 29, 108–114 (2009)
34. Frank, S., Roberts, D.E., Rikvold, P.A.: Effects of lateral diffusion on morphology and
dynamics of a microscopic lattice-gas model of pulsed electrodeposition. J. Chem. Phys.
122, 1–10 (2005)
35. Berthier, F., Legrand, B., Creuze, J., Tétot, R.: Atomistic investigation of the Kolmogorov-
Johnson-Mehl-Avrami law in electrodeposition process. J. Electroanal. Chem. 561, 37–52
(2004)
36. Berthier, F., Legrand, B., Braems, I., Creuze, J., Tétot, R.: Voltammetry and
electrodeposition in the presence of attractive interactions: II. From Monte Carlo
simulations to the KJMA-ECNT approach. J. Electroanal. Chem. 573, 377–389 (2004)
37. Berthier, F., Legrand, B., Creuze, J., Tétot, R.: Ag/Cu (0 0 1) electrodeposition: beyond the
classical nucleation theory. J. Electroanal. Chem. 562, 127–134 (2004)
38. Budevski, E., Staikov, G., Lorenz, W.J.: Electrocrystallization nucleation and growth
phenomena. Electrochim. Acta. 45, 2559–2574 (2000)
39. Pignard, S., Goglio, G., Radulescu, A., Piraux, L., Dubois, S., Declemy, A., Duvail, J.L.:
Study of the magnetization reversal in individual nickel nanowires. J. Appl. Phys. 87, 824–
829 (2000)
40. Moina, C.A., De Oliveira-Versic, L., Vazdar, M.: Magnetic domain states in nano-sized Co
nuclei electrodeposited onto monocrystalline silicon. Mater. Lett. 58, 3518–3522 (2004)
41. Rynders, R.M., Alkire, R.C.: Use of in situ atomic force microscopy to image copper
electrodeposits on platinum. J. Electrochem. Soc. 141, 1166–1173 (1994)
42. Khazrayie, M.A., Aghdam, A.R.S.: Aghdam, Si3N4/Ni nanocomposite formed by

electroplating: effect of average size of nanoparticulates. Transactions of Nonferrous
Metals Society of China (English Edition), vol. 20, pp. 1017. (2010)
43. Yang, F., Kung, S.C., Cheng, M., Hemminger, J.C., Penner, R.M.: Smaller is faster and
more sensitive: the effect of wire size on the detection of hydrogen by single palladium
nanowires. ACS Nano 4, 5233–5244 (2010)
44. Akinbulu, I.A., Khene, S., Nyokong, T.: The effects of point of substitution on the formation
of manganese phthalocyanine-based molecular materials: surface characterization and
electrocatalysis. Thin Solid Films 519, 911–918 (2010)
45. Inguanta, R., Vergottini, F., Ferrara, G., Piazza, S., Sunseri, C.: Effect of temperature on the
growth of a-PbO2 nanostructures. Electrochim. Acta. 55, 8556–8562 (2010)
46. Guo, L., Thompson, A., Searson, P.C.: The kinetics of copper island growth on ruthenium
oxide in perchlorate solution. Electrochim. Acta 55, 8416–8421 (2010)
47. Lahiri, A., Tadisina, Z.: Synthesis, thermodynamic and magnetic properties of pure
hexagonal close packed nickel. Mater. Chem. Phys. 124, 41–43 (2010)
48. Weston, D.P., Harris, S.J., Shipway, P.H., Weston, N.J., Yap, G.N.: Establishing
relationships between bath chemistry, electrodeposition and microstructure of Co–W
alloy coatings produced from a gluconate bath. Electrochim. Acta 55, 5695–5708 (2010)
49. Best, A.S., Bhatt, A.I., Hollenkamp, A.F.: Ionic liquids with the bis(fluorosulfonyl)imide
anion: electrochemical properties and applications in battery technology. J. Electrochem.
Soc. 157, A903–A911 (2010)
50. Garfias-García, E., Romero-Romo, M., Ramřez-Silva, M.T., Morales, J., Palomar-Pardavé,
M.: Eletrochemical nucleation of polypyrrole onto different substrates. Int. J. Electrochem.
Sci. 5, 763–773 (2010)
51. Alvarez, A.E., Salinas, D.R.: Formation of Cu/Pd bimetallic crystals by electrochemical
deposition. Electrochim. Acta 55, 3714–3720 (2010)
52. Kirkwood, D., Zoldan, V.C., Pasa, A.A., Zangari, G.: Evolution of surface roughness in
electrodeposited Co-Ni-P and Co-Ni films. J. Electrochem. Soc. 157, D181–D186 (2010)
53. Hamlaoui, Y., Tifouti, L., Remazeilles, C., Pedraza, F.: Cathodic electrodeposition of
cerium based oxides on carbon steel from concentrated cerium nitrate. Part II: Influence of
electrodeposition parameters and of the addition of PEG. Mater. Chem. Phys. 120, 172–180
(2010)
54. Wang, W., Qian, S.Q., Zhou, X.Y.: Microstructure and oxidation-resistant of ZrO2/Ni
coatings applied by high-speed jet electroplating. J. Mater. Sci. 45, 1617–1621 (2010)
55. Damian, A., Maroun, F., Allongue, P.: Electrochemical growth and dissolution of Ni on
bimetallic Pd/Au(1 1 1) substrates. Electrochim. Acta 55, 8087–8099 (2010)
56. Kim, K.H., Roh, D.K., Song, I.K., Lee, B.C., Baeck, S.H.: Enhanced performance as a
lithium-ion battery cathode of electrodeposited V2O5 thin films by e-beam irradiation.
J. Solid State Electrochem. 14, 1801–1805 (2010)
57. Jung, A., Natter, H., Hempelmann, R., Diebels, S., Koblischka, R., Hartmann, U., Lach, E.:
Study of the magnetic flux density distribution of nickel coated aluminum foams. J. Phys.
Conf. Ser. 200 (2010)
58. Ye, W., Yan, J., Ye, Q., Zhou, F.: Template-free and direct electrochemical deposition of
hierarchical dendritic gold microstructures: growth and their multiple applications. J. Phys.
Chem. C 114, 15617–15624 (2010)
59. Mahmoudian, M.R., Alias, Y., Basirun, W.J.: Electrodeposition of (pyrrole-co-phenol) on
steel surfaces in mixed electrolytes of oxalic acid and DBSA. Mater. Chem. Phys. 124,
1022–1028 (2010)
60. Vegunta, S.S.S., Ngunjiri, J.N., Flake, J.C.: Electrochemical patterning of organic
monolayers on silicon. J. Electrochem. Soc. 157, D509–D513 (2010)
61. Solmaz, R., Döner, A., Karda, G.: Preparation, characterization and application of alkaline
leached CuNiZn ternary coatings for long-term electrolysis in alkaline solution. Int.
J. Hydrogen Energy 35, 10045–10049 (2010)
References 141
62. El-Cheick, F.M., Rashwan, F.A., Mahmoud, H.A., El-Rouby, M.: Gold nanoparticle-
modified glassy carbon electrode for electrochemical investigation of aliphatic di-carboxylic
acids in aqueous media. J. Solid State Electrochem. 14, 1425–1443 (2010)
63. Cherevko, S., Chung, C.H.: Impact of key deposition parameters on the morphology of
silver foams prepared by dynamic hydrogen template deposition. Electrochim. Acta 55,
6383–6390 (2010)
64. Song, Y., Ma, Y., Wang, Y., Di, J., Tu, Y.: Electrochemical deposition of gold-platinum
alloy nanoparticles on an indium tin oxide electrode and their electrocatalytic applications.
65. Ivanova, O.S., Zamborini, F.P.: Electrochemical size discrimination of gold nanoparticles
attached to glass/indium-tin-oxide electrodes by oxidation in bromide-containing
electrolyte. Anal. Chem. 82, 5844–5850 (2010)
66. Ballarin, B., Gazzano, M., Tonelli, D.: Effects of different additives on bimetallic Au-Pt
nanoparticles electrodeposited onto indium tin oxide electrodes. Electrochim. Acta 55,
6789–6795 (2010)
67. Mirzamohammadi, S., Kiarasi, R., Aliov, M.K., Sabur, A.R., Hassanzadeh-Tabrizi, A.:
Study of corrosion resistance and nanostructure for tertiary Al2O3/Y2O3/CNT pulsed
electrodeposited Ni based nanocomposite. Trans. Inst. Met. Finish. 88, 93–99 (2010)
68. Kirkpatrick, D.C., Antwi, C., Martin, R.S.: Use of recordable compact discs to fabricate
electrodes for microchip-based analysis systems. Anal. Methods 2, 811–816 (2010)
69. Lai, Y., Lin, Z., Chen, Z., Huang, J., Lin, C.: Fabrication of patterned CdS/TiO2
heterojunction by wettability template-assisted electrodeposition. Mater. Lett. 64, 1309–
1312 (2010)
70. Sakairi, M., Goto, Y., Fushimi, K., Kikuchi, T., Hideaki, T.: Fabrication of Cu micro-rods
with Co-axial dual capillary solution flow type droplet cell and electrodeposition with the
cell. Electrochemistry 78, 118–121 (2010)
71. Rheem, Y.: Electrodeposition of GMR Ni/Cu multilayers in a recirculating electrochemical
flow reactor. Korean J. Mater. Res. 20, 90–96 (2010)
72. Pan, J., Ji, L., Sun, Y., Wan, P., Cheng, J., Yang, Y., Fan, M.: Preliminary study of alkaline
single flowing Zn-O2 battery. Electrochem. Commun. 11, 2191–2194 (2009)
73. Weber, C., Gauda, E., Mizaikoff, B., Kranz, C.: Developmental aspects of amperometric
ATP biosensors based on entrapped enzymes. Anal. Bioanal. Chem. 395, 1729–1735 (2009)
74. Du, J., Roukes, M.L., Masmanidis, S.C.: Dual-side and three-dimensional microelectrode
arrays fabricated from ultra-thin silicon substrates. J. Micromech. Microeng. 19 (2009)
75. Gawlik, G., Jagielski, J.: Ion-induced transformations of a W-Si interface. Vacuum 83,
S111–S113 (2009)
76. Hager, C.E., Jones, K.A., Derenge, M.A., Zheleva, T.S.: Activation of ion implanted Si in
GaN using a dual AIN annealing cap. J. Appl. Phys. 105 (2009)
77. Ratcliff, E.L., Jenkins, J.L., Nebesny, K., Armstrong, N.R.: Electrodeposited, ‘‘textured’’
poly(3-hexyl-thiophene) (e-P3HT) films for photovoltaic applications. Chem. Mater. 20,
5796–5806 (2008)
78. Dulal, S.M.S.I., Charles, E.A.: Optimisation of electrochemical process parameters for giant
magnetoresistance of electrodeposited Ni–Co(Cu)/Cu multilayers. Trans. Inst. Met. Finish.
86, 260–266 (2008)
79. Tang, W., He, A., Liu, Q., Ivey, D.G.: Fabrication and microstructures of sequentially
electroplated Sn-Rich Au-Sn alloy solders. J. Elec. Materi. 37, 837–844 (2008)
80. Dulal, S.M.S.I., Charles, E.A.: Electrodeposition and composition modulation of Co–
Ni(Cu)/Cu multilayers. J. Alloys Compd. 455, 274–279 (2008)
81. El Bahraoui, T., Errahmani, H., Belghazi, Y., Berrada, A., Dinia, A., Schmerber, G., Lassri,
H., Cherkaoui El Moursli, F., Hajji, F.: Structural and magnetic properties of
electrodeposited (Co/CoxZn1-x)n thin films. J. Mag. Mag. Mater. 316, 8–12 (2007)
82. Harper, J.F.: Electrophoresis of surfactant-free bubbles. J. Colloid Interf. Sci. 350, 361–367
(2010)
83. Yang, R., Wang, F., Blunk, R.H., Angelopoulos, A.P.: Competing effects of silanol surface
concentration and solvent dielectric constant on electrostatic layer-by-layer assembly of
silica nanoparticles on gold. J. Colloid Interf. Sci. 349, 148–152 (2010)
84. Laanait, N., Yoon, J., Hou, B., Vanysek, P., Meron, M., Lin, B., Luo, G., Benjamin, I.,
Schlossman, M.L.: Communications: monovalent ion condensation at the electrified liquid/
liquid interface. J. Chem. Phys. 132 (2010)
85. Guerrero-García, G.I., González-Tovar, E., Olvera De La Cruz, M.: Effects of the ionic size-
asymmetry around a charged nanoparticle: unequal charge neutralization and electrostatic
screening. Soft Matter 6, 2056–2065 (2010)
86. Tong, C.H., Zhu, Y.J.: Finite size effect of ions and dipoles close to charged interfaces.
Chin. Phys. B 19 (2010)
87. Biesheuvel, P.M., Bazant, M.Z.: Nonlinear dynamics of capacitive charging and
desalination by porous electrodes. Phys. Rev. E Stat. Nonlinear Soft Matter Phys. 81 (2010)
88. Sun, Y., Jacobson, K.B., Golovlev, V.: Label-free detection of biomolecules on microarrays
using surface-colloid interaction. Anal. Biochem. 361, 244–252 (2007)
89. Kumar, T.V.V., Prabhakar, S., Raju, G.B.: Adsorption of oleic acid at sillimanite/water
interface. J. Colloid Interf. Sci. 247, 275–281 (2002)
90. Nishimura, S., Kodama, M., Yao, K., Imai, Y., Tateyama, H.: Direct surface force
measurement for synthetic smectites using the atomic force microscope. Langmuir 18,
4681–4688 (2002)
91. Nishimura, S., Yao, K., Kodama, M., Imai, Y., Ogino, K., Mishima, K.: Electrokinetc study of
synthetic smectites by flat plate streaming potential technique. Langmuir 18, 188–193 (2002)
92. Pattanaik, M., Bhaumik, S.K.: Adsorption behaviour of polyvinyl pyrrolidone on oxide
surfaces. Mater. Lett. 44, 352–360 (2000)
93. Nishimura, S., Kodama, M., Noma, H., Inoue, K., Tateyama, H.: The use of AFM for direct
force measurements between expandable fluorine mica. Colloids Surf. A Physicochem. Eng.
Aspects 143, 1–16 (1998)
94. Kubota, K., Jameson, G.J.: A study of the electrophoretic mobility of a very small inert gas
bubble suspended in aqueous inorganic electrolyte and cationic surfactant solutions.
J. Chem. Eng. Jpn 26, 7–12 (1993)
95. Xiao, A., Yang, J., Zhang, W.: Mesoporous cobalt oxide film prepared by electrodeposition
as anode material for Li ion batteries. J. Porous. Mater. 17, 583–588 (2010)
96. Rezaei, B., Damiri, S.: Electrodeposited silver nanodendrites electrode with strongly
enhanced electrocatalytic activity. Talanta 83, 197–204 (2010)
97. Ren, X., Wei, Q., Hu, S., Wei, S.: The recovery of zinc from hot galvanizing slag in an
anion-exchange membrane electrolysis reactor. J. Hazard. Mater. 181, 908–915 (2010)
98. Van Parys, H., Telias, G., Nedashkivskyi, V., Mollay, B., Vandendael, I., Van Damme, S.,
Deconinck, J., Hubin, A.: On the modeling of electrochemical systems with simultaneous
gas evolution. Case study: the zinc deposition mechanism. Electrochim. Acta 55, 5709–
5718 (2010)
99. Tsuda, T., Boyd, L.E., Kuwabata, S., Hussey, C.L.: Electrochemistry of copper(I) oxide in
the 66.7–33.3 mol % urea-choline chloride room-temperature eutectic melt. J. Electrochem.
Soc. 157, F96–F103 (2010)
100. Fu, C., Zhou, H., Xie, D., Sun, L., Yin, Y., Chen, J., Kuang, Y.: Electrodeposition of gold
nanoparticles from ionic liquid microemulsion. Colloid Polym. Sci. 288, 1097–1103 (2010)
101. Dziewoński, P.M., Grzeszczuk, M.: Impact of the electrochemical porosity and chemical
composition on the lithium ion exchange behavior of polypyrroles (ClO4-, TOS-, TFSI-)
prepared electrochemically in propylene carbonate. Comparative EQCM, EIS and CV
studies. J. Phys. Chem. B 114, 7158–7171 (2010)
102. Son, S.H., Lee, H.K., Park, S.C.: Kinetics of rhodium electrodeposition for semiconductor
interconnect applications. Surf. Interface Anal. 42, 1244–1246 (2010)
103. Ang, J.Q., Nguyen, B.T.T., Huang, Y., Toh, C.S.: Ion-selective detection of non-
intercalating Na+ using competitive inhibition of K+ intercalation in Prussian blue nanotubes
sensor. Electrochim. Acta 55, 7903–7908 (2010)
References 143
104. Popczyk, M.: The hydrogen evolution reaction on electrolytic nickel-based coatings
containing metallic molybdenum. In: Materials Science Forum, pp. 1036–1041. (2010)
105. Arotiba, O.A., Owino, J.H., Baker, P.G., Iwuoha, E.I.: Electrochemical impedimetry of
electrodeposited poly(propylene imine) dendrimer monolayer. J. Electroanal. Chem. 638,
287–292 (2010)
106. Raoof, J.B., Ojani, R., Kiani, A., Rashid-Nadimi, S.: Fabrication of highly porous Pt coated
nanostructured Cu-foam modified copper electrode and its enhanced catalytic ability for
hydrogen evolution reaction. Int. J. Hydrogen Energy 35, 452–458 (2010)
107. Afonso, M.L., Gomes, A., Carvalho, A., Alves, L.C., Wastin, F., Gonçalves, A.P.:
Electrochemical behaviour of uranium (IV) in DMF at vitreous carbon. Electrochim. Acta
54, 7318–7323 (2009)
108. Park, J.Y., Ponnapati, R., Taranekar, P., Advincula, R.C.: Carbazole peripheral poly(benzyl
ether) dendrimers at the air-water interface: electrochemical cross-linking and
electronanopatterning. Langmuir 26, 6167–6176 (2010)
109. Shpaisman, N., Givan, U., Patolsky, F.: Electrochemical synthesis of morphology-
controlled segmented CdSe nanowires. ACS Nano 4, 1901–1906 (2010)
110. Yi, Z., Banzet, M., Offenhäusser, A., Mayer, D.: Fabrication of nanogaps with modified
morphology by potential-controlled gold deposition. Phys. Status Solid Rapid Res. Lett. 4,
73–75 (2010)
111. Zeng, D.M., Jiang, Y.X., Zhou, Z.Y., Su, Z.F., Sun, S.G.: In situ FTIR spectroscopic studies
of (bi)sulfate adsorption on electrodes of Pt nanoparticles supported on different substrates.
112. Rafailovic, L.D., Artner, W., Nauer, G.E., Minic, D.M.: Structure, morphology and thermal
stability of electrochemically obtained Ni–Co deposits. Thermochimica Acta 496, 110–116
(2009)
113. Li, X.Z., Wei, X.W., Ye, Y.: A simple method for forming amorphous rare earth-transition
metal alloy nanotube arrays. J. NonCryst. Solids 355, 2233–2238 (2009)
114. Park, K., Xiao, F., Yoo, B.Y., Rheem, Y., Myung, N.V.: Electrochemical deposition of
thermoelectric SbxTey thin films and nanowires. J. Alloys Compd. 485, 362–366 (2009)
115. Xu, F., Lu, Y., Xie, Y., Liu, Y.: Controllable morphology evolution of electrodeposited ZnO
nano/micro-scale structures in aqueous solution. Mater. Des. 30, 1704–1711 (2009)
116. Caban, K.: Overpotential deposition of copper on gold micro- and nanoelectrodes. J. Solid
State Electrochem. 13, 733–744 (2009)
117. Tang, S.C., Meng, X.K., Vongehr, S.: An additive-free electrochemical route to rapid
synthesis of large-area copper nano-octahedra on gold film substrates. Electrochem.
Commun. 11, 867–870 (2009)
118. Yang, B., Lu, N., Huang, C., Qi, D., Shi, G., Xu, H., Chen, X., Dong, B., Song, W., Zhao,
B., Chi, L.: Electrochemical deposition of silver nanoparticle arrays with tunable density.
Langmuir 25, 55–58 (2009)
119. Salimi, A., Noorbakhash, A., Sharifi, E., Semnani, A.: Highly sensitive sensor for picomolar
detection of insulin at physiological pH, using GC electrode modified with guanine and
electrodeposited nickel oxide nanoparticles. Biosens. Bioelectron. 24, 792–798 (2008)
120. Starosvetsky, D., Sezin, N., Kovler, M., Ein-Eli, Y.: End-point detection of copper super-
filling in small features under a potentiostatic mode of operation. Electrochim. Acta 53,
7884–7889 (2008)
121. Marquardt, B., Eude, L., Gowtham, M., Cho, G., Jeong, H.J., Chatelet, M., Cojocaru, C.S.,
Kim, B.S., Pribat, D.: Density control of electrodeposited Ni nanoparticles/nanowires inside
porous anodic alumina templates by an exponential anodization voltage decrease.
Nanotechnology 19 (2008)
122. Yun, Y., Dong, Z., Shanov, V.N., Doepke, A., Heineman, W.R., Halsall, H.B.,
Bhattacharya, A., Wong, D.K.Y., Schulz, M.J.: Fabrication and characterization of
carbon nanotube array electrodes with gold nanoparticle tips. Sens. Actuators B Chem.
133, 208–212 (2008)
123. Rodriguez, B.B., Hassel, A.W.: Passivity of a nanostructured directionally solidified NiAl-
Re alloy as substrate for electrodeposition of gold. J. Electrochem. Soc. 155, K31–K37
(2008)
124. Basile, F., Benito, P., Fornasari, G., Rosetti, V., Scavetta, E., Tonelli, D., Vaccari, A.:
Electrochemical synthesis of novel structured catalysts for H2 production. Appl. Catal.
B Environ. 91, 563–572 (2009)
125. Atta, N.F., El-Kady, M.F., Galal, A.: Palladium nanoclusters-coated polyfuran as a novel
sensor for catecholamine neurotransmitters and paracetamol. Sensors and Actuators, B:
Chemical 141, 566–572 (2009)
126. Chu, C.W., Jang, J.S.C., Chiu, S.M., Chu, J.P.: Study of the characteristics and corrosion
behavior for the Zr-based metallic glass thin film fabricated by pulse magnetron sputtering
process. Thin Solid Films 517, 4930–4933 (2009)
127. Liu, T.S., Kang, T.F., Lu, L.P., Zhang, Y., Cheng, S.Y.: Au-Fe(III) nanoparticle modified
glassy carbon electrode for electrochemical nitrite sensor. J. Electroanal. Chem. 632, 197–
200 (2009)
128. Li, M., Ni, F., Wang, Y., Xu, S., Zhang, D., Chen, S., Wang, L.: Sensitive and facile
determination of catechol and hydroquinone simultaneously under coexistence of resorcinol
with a Zn/Al layered double hydroxide film modified glassy carbon electrode.
Electroanalysis 21, 1521–1526 (2009)
129. Dansby-Sparks, R., Chambers, J.Q., Xue, Z.L.: Trace vanadium analysis by catalytic
adsorptive stripping voltammetry using mercury-coated micro-wire and polystyrene-coated
bismuth film electrodes. Anal. Chim. Acta 643, 19–25 (2009)
130. Yilmaz, S.: Adsorptive stripping voltammetric determination of zopiclone in tablet dosage
forms and human urine. Colloids Surf. B Biointerfaces 71, 79–83 (2009)
131. Feng, D., Wang, F., Chen, Z.: Electrochemical glucose sensor based on one-step
construction of gold nanoparticle-chitosan composite film. Sensors and Actuators, B:
Chemical 138, 539–544 (2009)
132. Habib, M.A., Gan, S.W., Rahman, M.: Fabrication of complex shape electrodes by localized
electrochemical deposition. J. Mater. Process. Technol. 209, 4453–4458 (2009)
133. Llayaraja, M., Mohan, S., Gnanamuthu, R.M., Saravanan, G.: Nanocrystalline zinc-nickel
alloy deposition using pulse electrodeposition (PED) technique. Trans. Inst. Met. Finish. 87,
145–148 (2009)
134. Chekmeneva, E., Díaz-Cruz, J.M., Ariño, C., Esteban, M.: A novel differential pulse
voltammetric method on rotating Au-disk electrode for the study of Hg2+ binding.
J. Electroanal. Chem. 629, 169–179 (2009)
135. Rybakova, N., Souto, M., Andriyko, Y., Artner, W., Godinho, J., Nauer, G.E.: Morphology
and mechanical properties of TiB2 coatings deposited from chloride-fluoride melts by pulse
electroplating. J. Electrochem. Soc. 156, D131–D137 (2009)
136. Kawashita, M., Hayakawa, T., Takaoka, G.H., Miyazaki, T.: Structure and adhesion of
hydroxyapatite films electrochemically deposited onto titanium substrates under short-pulse
current in metastable calcium phosphate solution. In: Key Engineering Materials,
pp. 377–380. (2009)
137. Dulal, S.M.S.I., Charles, E.A.: Effect of interface number on giant magnetoresistance.
J. Phys. Chem. Solids 71, 309–313 (2010)
138. Rodger, D.C., Fong, A.J., Li, W., Ameri, H., Ahuja, A.K., Gutierrez, C., Lavrov, I., Zhong,
H., Menon, P.R., Meng, E., Burdick, J.W., Roy, R.R., Edgerton, V.R., Weiland, J.D.,
Humayun, M.S., Tai, Y.C.: Flexible parylene-based multielectrode array technology for
high-density neural stimulation and recording. Sensors and Actuators, B: Chemical 132,
449–460 (2008)
139. Nabirahni, D.M.A., Tang, P.T., Leisner, P.: The electrolytic plating of compositionally
modulated alloys and laminated metal nano-structures based on an automated computer-
controlled dual-bath system. Nanotechnology 7, 134–143 (1996)
References 145
140. Moafi, H.F., Shojaie, A.F., Zanjanchi, M.A.: The comparative study of photocatalytic self-
cleaning properties of synthesized nanoscale titania and zirconia onto polyacrylonitrile
fibers. J. Appl. Polym. Sci. 118, 2062–2070 (2010)
141. Piasecki, T., Nitsch, K.: Study of sprayed coatings and compound materials by impedance
spectroscopy. Surf. Coat. Technol. 205, 1009–1014 (2010)
142. Gan, M., Tomar, V.: Role of length scale and temperature in indentation induced creep
behavior of polymer derived Si–C–O ceramics. Mater. Sci. Eng. A 527, 7615–7623 (2010)
143. Alessandri, I.: Plasmonic heating assisted deposition of bare Au nanoparticles on titania
nanoshells. J. Colloid Interf. Sci. 351, 576–579 (2010)
144. Boccaccini, A.R., Erol, M., Stark, W.J., Mohn, D., Hong, Z., Mano, J.F.: Polymer/bioactive
glass nanocomposites for biomedical applications: a review. Compos. Sci. Technol. 70,
1764–1776 (2010)
145. Xia, X., Wang, H., Huang, F., Cai, Y., Wei, Q.: Surface characterization of aromatic
thermotropic liquid crystalline fiber deposited by nanostructured silver. Fibers Polymers 11,
813–818 (2010)
146. Alleg, S., Ibrir, M., Fenineche, N.E., Bensalem, R., Suol, J.J.: Microstructure and magnetic
properties of HVOF thermally sprayed Fe75Si15B10 coatings. Surf. Coat. Technol. 205, 281–
286 (2010)
147. Haseeb, A.S.M.A., Hasan, M.M., Masjuki, H.H.: Structural and mechanical properties of
nanostructured TiO2 thin films deposited by RF sputtering. Surface and Coatings
Technology 205, 338–344 (2010)
148. Nathanael, A.J., Mangalaraj, D., Ponpandian, N.: Controlled growth and investigations on
the morphology and mechanical properties of hydroxyapatite/titania nanocomposite thin
films. Compos. Sci. Technol. 70, 1645–1651 (2010)
149. Wang, L.P., Wang, W., Di, L., Lu, Y.N., Wang, J.Y.: Protein adsorption under electrical
stimulation of neural probe coated with polyaniline. Colloids Surf. B Biointerfaces 80, 72–
78 (2010)
150. Guo, H., Zhu, Y., Qiu, S., Lercher, A.J., Zhang, H.: Coordination modulation induced
synthesis of nanoscale Eu1-xTbxmetal-organic frameworks for luminescent thin films. Adv.
Mater. 22, 4190–4192 (2010)
151. Akhavan, O.: Thickness dependent activity of nanostructured TiO2/a-Fe2O3 photocatalyst
thin films. Appl. Surf. Sci. 257, 1724–1728 (2010)
152. Zhu, W., Liu, X., Liu, H., Tong, D., Yang, J., Peng, J.: Coaxial heterogeneous structure of
TiO2 nanotube arrays with CdS as a superthin coating synthesized via modified
electrochemical atomic layer deposition. J. Am. Chem. Soc. 132, 12619–12626 (2010)
153. Samyn, P., Deconinck, M., Schoukens, G., Stanssens, D., Vonck, L., Van Den Abbeele, H.:
Modifications of paper and paperboard surfaces with a nanostructured polymer coating.
Prog. Org. Coat. 69, 442–454 (2010)
154. Se˛se˛n, M., Khudhayer, W., Karabacak, T., Kosa˛r, A.: Compact nanostructure integrated
pool boiler for microscale cooling applications. Micro Nano Lett. 5, 203–206 (2010)
155. Cranford, S.W., Ortiz, C., Buehler, M.J.: Mechanomutable properties of a PAA/PAH
polyelectrolyte complex: rate dependence and ionization effects on tunable adhesion
strength. Soft Matter 6, 4175–4188 (2010)
156. Yu, Y., Addai-Mensah, J., Losic, D.: Synthesis of self-supporting gold microstructures with
three-dimensional morphologies by direct replication of diatom templates. Langmuir 26,
14068–14072 (2010)
157. Lin, Z.Q., Lai, Y.K., Hu, R.G., Li, J., Du, R.G., Lin, C.J.: A highly efficient ZnS/CdS@TiO2
photoelectrode for photogenerated cathodic protection of metals. Electrochim. Acta 55,
8717–8723 (2010)
158. Bae, G., Kang, K., Kim, J.J., Lee, C.: Nanostructure formation and its effects on the
mechanical properties of kinetic sprayed titanium coating. Mater. Sci. Eng. A 527, 6313–
6319 (2010)
159. Liu, M., Tan, M., Liu, G., Wang, H., Xue, F., Deng, X., Li, D.: The effects of
modulation period, modulation ratio, and deposition temperature on microstructure and
mechanical properties of ZrB2/W multilayers. Sci. China Technol. Sci. 53, 2350–2354
(2010)
160. Homhuan, P., Chaiyakun, S., Thonggoom, R., Panich, N., Tungasmita, S.: Growth and
structural characterizations of nanostructured chromium-zirconium-nitride thin films for
tribological applications. Mater. Trans. 51, 1651–1655 (2010)
161. Baklanova, N.I., Zaitsev, B.N.: The study of nanostructured interfacial coatings on SiC
fibers by atomic force microscopy. In: Key Engineering Materials, pp. 542–545. (2010)
162. Faustini, M., Nicole, L., Boissière, C., Innocenzi, P., Sanchez, C., Grosso, D.:
Hydrophobic, antireflective, self-cleaning, and antifogging sol-gel coatings: an example
of multifunctional nanostructured materials for photovoltaic cells. Chem. Mater. 22,
4406–4413 (2010)
163. Li, C., Wang, Y., Guo, L., He, J., Pan, Z., Wang, L.: Laser remelting of plasma-sprayed
conventional and nanostructured Al2O3-13 wt.%TiO2 coatings on titanium alloy. J. Alloys
Compd. 506, 356–363 (2010)
164. Kasatkin, E.V., Potapova, G.F., Erusalimchik, I.G., Stryuchkova, Y.M.: Wear-resistant
nanostructured platinum-titanium anodes: I. STM and STS measurements on model
ECAPTA specimen. Prot. Met. Phys. Chem. Surf. 46, 559–565 (2010)
165. Qian, L., Shen, W., Shen, B., Qin, G.W., Das, B.: Nanoporous gold-alumina core-shell films
with tunable optical properties. Nanotechnology 21 (2010)
166. Chen, W., Gao, W.: Sol-enhanced electroplating of nanostructured Ni-TiO2 composite
coatings—the effects of sol concentration on the mechanical and corrosion properties.
167. McCrea, J.L.: Industrial implementation of nanostructured cobalt as an alternative to hard
chrome. Surf. Eng. 26, 149–152 (2010)
168. Aliofkhazraei, M., Rouhaghdam, A.S., Laleh, M., Shanaghi, A.: Enhancement of corrosion
protection of micro-arc oxidation by applying nanostructured TiO2 thin film via the ‘‘sol-
gel’’ method. Anti Corros. Methods Mater. 57, 75–82 (2010)
169. Zois, D., Lekatou, A., Vardavoulias, M.: Preparation and characterization of highly
amorphous HVOF stainless steel coatings. J. Alloys Compd. 504, S283–S287 (2010)
170. Reisgen, U., Balashov, B., Stein, L., Geffers, C.: Nanophase hardfacing new possibilities for
functional surfaces. In: Materials Science Forum, pp. 870–875. (2010)
171. Aliofkhazraei, M., Rouhaghdam, A.S., Ghobadi, E., Mohsenian, E.: Electrodeposition and
mechanical and corrosion resistance properties of tertiary Ni–W/Al2O3/CNT nanocomposite
coatings. In: Advanced Materials Research, pp. 12–16. (2010)
172. Bociaga, D.: Nanostructured protective carbon layer on the jeweller’s metallic material-in
vitro verification. J. Nanosci. Nanotechnol. 10, 1191–1195 (2010)
173. Zheludkevich, M.L., Poznyak, S.K., Rodrigues, L.M., Raps, D., Hack, T., Dick, L.F.,
Nunes, T., Ferreira, M.G.S.: Active protection coatings with layered double hydroxide
nanocontainers of corrosion inhibitor. Corros. Sci. 52, 602–611 (2010)
174. Weston, D.P., Harris, S.J., Capel, H., Ahmed, N., Shipway, P.H., Yellup, J.M.:
Nanostructured Co–W coatings produced by electrodeposition to replace hard Cr on
aerospace components. Trans. Inst. Met. Finish. 88, 47–56 (2010)
175. Zhang, S., Li, Q., Chen, B., Yang, X.: Preparation and corrosion resistance studies of
nanometric sol-gel-based CeO2 film with a chromium-free pretreatment on AZ91D
magnesium alloy. Electrochim. Acta 55, 870–877 (2010)
176. Li, C.L., Wu, F.B., Lee, J.W., Tsai, Y.Z., Chang, L.C.: Characteristics of Cr2N/Cu
multilayered thin films with different bilayer thickness. Surface and Coatings Technology
204, 941–946 (2009)
177. Sherik, A.M., Nabulsi, K.M.: Applications of nanotechnology in oil and gas. Int. J. Nano
Biomater. 2, 409–415 (2009)
178. Aliofkhazraei, M., Sabour Rouhaghdam, A.: Study of anodic voltage on properties of
complex nanocrystalline carbonitrided titanium fabricated by duplex treatments. Mater.
Res. Innov. 14, 177–182 (2010)
References 147
179. Aliofkhazraei, M., Hassanzadeh-Tabrizi, S.A., Sabour Rouhaghdam, A., Heydarzadeh, A.:
Nanocrystalline ceramic coating on c-TiAl by bipolar plasma electrolysis (effect of
frequency, time and cathodic/anodic duty cycle). Ceram. Int. 35, 2053–2059 (2009)
180. Aliofkhazraei, M., Sabour Rouhaghdam, A., Heydarzadeh, A., Elmkhah, H.: Nanostructured
layer formed on CP–Ti by plasma electrolysis (effect of voltage and duty cycle of cathodic/
anodic direction). Mater. Chem. Phys. 113, 607–612 (2009)
181. Aliofkhazraei, M., Sabour Rouhaghdam, A., Heydarzadeh, A.: Strong relation between
corrosion resistance and nanostructure of compound layer of treated 316 austenitic stainless
steel. Mater. Charact. 60, 83–89 (2009)
182. Aliofkhazraei, M., Rouhaghdam, A.S., Denshmaslak, A., Jafarian, H.R., Sabouri, M.: Study
of bipolar pulsed nanocrystalline plasma electrolytic carbonitriding on nanostructure of
compound layer for CP–Ti. J. Coat. Technol. Res. 5, 497–503 (2008)
183. Kobayashi, Y., Tanase, T., Tabata, T., Miwa, T., Konno, M.: Fabrication and dielectric
properties of the BaTiO3-polymer nano-composite thin films. J. Eur. Ceram. Soc. 28, 117–
122 (2008)
Chapter 5
Size Effect in Mechanical Properties
5.1 Introduction
Research studies have shown that when particles’ size reaches to the dimensions
of nanometer, remarkable improvement will be observed in strength of com-
posite. For example, remarkable increase was observed in hardness of nickel-
alumina composite when size of improving particles was decreased from 10 lm
to 10 nm. Shape, size and surface of nanoparticles play important role in
properties of nanocomposite. In recent years, nanocomposites have been used
widely due to their better magnetic, mechanical, optical and physical properties.
Interface volume, layer thickness, superficial energy and interface are the
parameters which have noticeable effects on nanostructure thin films [1–12].
Figure 5.1 shows schematics of particles used in nanocomposites and degree of
proportion of surface area to their volume. As an example of particulate
nanomaterials, Ohno et al. [13] studied the size effect of TiO2-SiO2 nano-hybrid
particles. The well-dispersed primary TiO2-SiO2 nano-hybrid particles were
successfully prepared by using the super critical drying of the molecular-
designed nano-hybrid precursor. The particle diameter of the resultant hybrid
particles was about 140 nm. The crystal size of titania on the surface of the silica
core particle was determined to be 7 nm from the result of TEM and XRD
analysis. The crystal structure was anatase. The band gap energy was measured
form the ultraviolet–visible spectrum. As a result, the band gap energy of the
nano-hybrid particles were 0.13 eV blue shifted compared with that of the
anatase crystal without the quantum size effect. Therefore, we concluded that
nano-hybrid particles has the possibility to control the quantum size effect, if we
can successfully develop the well handling method for nano-materials. Figure 5.2
illustrates the surface morphology of the obtained TiO2-SiO2 nano-hybrid par-
ticles with super critical drying process [13].

150 5 Size Effect in Mechanical Properties of Nanostructured Coatings
Fig. 5.1 Various types of

nanoparticles and degree of
surface area to their volume
5.2 Nanocomposite Coating Production Method
Extant physical vapor deposition (PVD) and chemical vapor deposition (CVD)
processes for the provision of nanocomposite coatings can be applied for the
production of nanocomposite coatings through improvement of process parameters
or through the application of initial powder with nanostructure. Application of
various nanoparticles provided from steam, liquid and/or solid methods have
accelerated development of nanocomposite coatings with resistant against friction
and oxidation. Under various PVD accessible processes, deposition through ion
ray is effective especially for making metallic nitride nano-crystallization coatings
with higher stick and controlled microstructure. Process with less dependency
parameters than PVD is salient advantage of deposition through ion ray. Energy
and Flux can improve ion bombardment, size and direction of crystallography of
grain as well. Ever increasing requirement for advanced materials with the aim of
tolerating practical conditions has caused that many research works carried out in
the field of very hard coatings. Recently, special research activities have been
carried out on designing very hard coatings with superior strength, high stiffness
and toughness. Formation of multilayer or super elasticity structures with various
elasticity modules between layers is one of designing principles.
Thickness of each layer should be in nano dimension, aimed at preventing from
operation of unwanted supply source between layers. Production of films with
pleasant stiffness amounts will be possible through layer to layer sit. Formation of
nanocomposite of a nanocomposite layer with microstructures, including crystal-
line network, is the other method of design with grains in nano dimensions
envisioned in an amorphous background. Plating method is the other methods of
production of nanocomposite coatings. Since this method is economical, it enjoys
5.2 Nanocomposite Coating Production Method 151
Fig. 5.2 The surface morphology of the obtained TiO2-SiO2 nano-hybrid particle with super
critical drying process: a agglomerate state, b primary TiO2-SiO2 nano-hybrid particle, c titania
crystals on the surface of the silica core particle and d the first Fourier transform (FFT) image
obtained from the titania crystals on the silica particle, reprinted with kind permission from
Ohno [13]
many capabilities for production of nanocomposite coatings in industrial scale.

This method is carried out based on accepted composite plating principles in a way
that process parameters in this method are not much more complicate; rather, their
controls are made easily [14–26].
5.3 Provision of Nanocomposite Coatings with Plating Method
During recent years, successful coexistence of very minute particles, like

metallic powders, silicon carbide, oxides, diamonds and polymers, has been
reported with metallic or alloy field and their accordance structures and
Table 5.1 Various types of nanocomposite coatings obtained through electro-deposition method
Methods of Type of nanostructured materials
electrodeposition
Nanoparticles in a Nano- Nanotubes/ Nanocrystalline
metallic matrix multilayer nanowires materials
Direct current (DC) Ni/Alumina Ni–Cr Co nanowires Ni-W alloy
Pulsed direct current Ni-W/CNT
(PDC)
Pulsed reverse Multilayered
current (PRC) composites
Potentiostatic (P)
Pulsed potetiostatic
(PP)
properties have been studied by various researchers. Not only structure and
properties of nanocomposite coatings depends on density, size, distribution and
nature of improved particles nature, but also it depends on type of used solution,
current density plating parameters, temperature, and degree of pH, etc. Nano-
composite plating includes revival of metallic ions from suspension electrolyte
and insoluble powders like oxides (SiO2, TiO2, Al2O3), carbides (SiC), nitrides
(Si3N4), polymers (PTFE, Polytetrafluoroethylene). This activity will result in
entering very minute particle to the growing metallic or alloy substrate. High
superficial energy and inclination of nanoparticle to agglomeration in high
conductor metallic electrolyte will bar congruousness of distribution of particles.
For this reason, many research activities have been done in the field of nano-
composite coatings entitled ‘‘Congruous Distribution of Very Minute Particles in
Metallic Substrate and Avoiding their Agglomeration in Electrolyte’’, aimed at
boosting volumetric percentage of nanoparticle in coating. Table 5.1 shows
schematic of various types of nanocomposite coatings which have been prepared
through plating.
5.4 Plating of Nickel-Alumina Nanocomposite Coating
Due to the application of nickel as protective coating, nickel nanocomposite

coatings, containing ceramic nanoparticle with high hardness and resistance to
erosion, have been taken into consideration seriously. Hardness and resistance of
deposited coatings of nickel nanocomposite strictly depends on degree of ceramic
particles extant in nickel background. Al2O3, WC, MoS2, TiO2, Cr2O3, ZrO2 and
diamond are of ceramic powders which have been used in manufacturing of
nanocomposites with nickel background. Up to the present time, more research
activities have been made on nanocomposite coatings of Ni/Al2O3 and Ni/SiC
[27–37].
5.4 Plating of Nickel-Alumina Nanocomposite Coating 153
5.5 Effects of Participation of Alumina Nanoparticle

in Nickel Coating
Participation of alumina nanoparticle will improve hardness and resistance of

coating against friction remarkably. Final tension will boost traction and tension of
submit in comparison with nickel, depending on degree of participation of parti-
cles in coating, partly twofold or more than two fold. Resistance against friction is
boosted upon increase of density of alumina in coating. At any rate, ductility of
nickel-alumina nanocomposite coatings is less than sole nickel. Annealing of
nanocomposite in high temperature will increase ductility but will reduce their
strength. Resistant against corrosion of nickel is improved with alumina nano-
particle. Increase of hardness is made based on preventing grains from growing
and according to Hall-Petch Law.
Alumina hard nanoparticle will generally improve trio biological properties and
hardness of nickel composite layers by dispersant hardness mechanism. Alumina
nanoparticle can prevent nickel grain boundary from movement and also can
prevent grains from growing while conducting heat treatment operations. When
material is exposed foreign (external) tension, alumina particles can prevent from
unwanted movement in metal substrate. Consequently, plastic shape change will
be more complicated. Hence, hardness of nanocomposite layers is increased while
resistance against friction is improved. Also, resistance against friction is
improved due to the reduction of grains size of metal substrate, containing alumina
nanoparticle at grain boundary.
5.6 Plating of Nickel-Alumina Nanocomposite Coating
In systems with simple counting ions, zeta potential is regarded as a criterion for
gradient of electrical potential, when surface potential is fixed. The pH, which its
zeta potential is equal to zero, is called Iso Electric Point. To enrich loading of
hydrated surface by OH– and H3O+, increase or decrease of pH from Iso Electric
Point will first boost absolute fraction of zeta potential. Iso electric point for
alumina is pH = 9 i.e. alumina particles will have negative superficial load in the
electrolyte with pH more than 9. In the same direction, alumina particles will have
positive superficial load at the pH with less than 9. Consequently, alumina
nanoparticle can be seeped simultaneously with nickel for formation of composite
layers without needing to specific additives. Because, pH of all composite plating
solutions of nickel is smaller than IEP for alumina and alumina particles at these
baths have positive superficial load. But, alumina nanoparticles are agglomerated
easily in electrochemical electrolyte due to their high superficial energy and this
activity will cause weak mechanical properties in nanocomposite coatings, for, it
prevents particles from being distributed equally. After carrying out operations,
physical distribution of nanoparticles at electrolyte solution by mixing and
ultrasonic operation and/or through distribution of chemical dispersants in elec-

trolyte is a mandatory activity. The more volumetric percentage of alumina
nanoparticles can be boosted in Ni/Al2O3 nanocomposite coating the more pro-
vided hardness of nanocomposite coat can be expected. Hence, this activity
requires getting familiarity with effective parameters in simultaneous electrical
deposition process of alumina and nickel [38–41]. For this reason, electroplating
variables and their effects in amount of participating alumina nanoparticles in coat
will be studied in next part.
5.7 Size Effect in Mechanical Properties of Two Dimensional

Nano-Films
He et al. [42] analyzed ultra-thin elastic films of nano-scale thickness with an

arbitrary geometry and edge boundary conditions. An analytical model is proposed
to study the size-dependent mechanical response of the film based on continuum
surface elasticity. By using the transfer-matrix method along with an asymptotic
expansion technique of small parameter, closed-form solutions for the mechanical
field in the film is presented in terms of the displacements on the mid-plane. The
asymptotic expansion terminates after a few terms and exact solutions are
obtained. The mid-plane displacements are governed by three two-dimensional
equations, and the associated edge boundary conditions can be prescribed on
average. Solving the two-dimensional boundary value problem yields the three-
dimensional response of the film. The solution is exact throughout the interior of
the film with the exception of a thin boundary layer having an order of thickness as
the film in accordance with the Saint–Venant’s principle.
The surface of a solid is a region with small thickness which has its own atom
arrangement and property differing from the bulk. For a solid with a large size, the
surface effects can be ignored because the volume ratio of the surface region to
the bulk is very small. However, for small solids with large surface-to-bulk ratio
the significance of surfaces is likely to be important. This is extremely true for
nano-scale materials or structures. Recently, mechanical experiments of nano-
scale bars and plates indicate that the effective elastic properties of these minute
structural elements strongly depend on their size. The understanding and modeling
of such a size-dependent phenomenon has become an active subject of much
research. Classical elasticity lacks an intrinsic length scale, and thus cannot be
used to model the size effect. Atomistic simulation, though very powerful in
pursuing the details at microscopic level, seems too complex for practical appli-
cations as it needs tremendous computation. An efficient approach has been
developed by upon the continuum concept of surface stress. They examined uni-
directional tension and pure bending of nano-scale bars and plates, and found more
remarkable size effect in bending than in tension. The results are in excellent
agreement with their atomistic simulation by embedded atom method for face-
centered cubic aluminum and the Stillinger–Weber model for silicon.
5.7 Size Effect in Mechanical Properties of Two Dimensional Nano-Films 155
From the continuum point of view, a surface is regarded as a negligibly thin

object adhering to the underlying material without slipping, and the material
constants for both are different. A generic and mathematical exposition on surface
elasticity has been presented by some researchers. In their work, surface stress
depends on deformation. The equilibrium and constitutive equations of the bulk
solid are the same as those in the classical elasticity, but the boundary conditions
must ensure the force balance of the surface object. This model has been applied
by several authors.
He et al. [42] concluded that a continuum model based on surface elasticity is
proposed to analyze the size-dependent mechanical response of ultra-thin elastic
films of nano-scale thickness. Being expressed in terms of displacements of the
mid-plane, the governing equations are two-dimensional and the associated
boundary conditions are specified at the edge of the film in an average manner as
in the classical plate theory. Once the two-dimensional equations are solved, the
three-dimensional mechanical field that is exact in Saint–Venant’s sense is
generated directly. The asymptotic analysis developed for solving the two-
dimensional equations can be regarded to yield exact solutions because the
expansion terminates after a few terms. The solution procedure is illustrated by
analyzing a clamped circular film under a concentrated force. The result is
consistent with the other existing studies and it approaches the classical plate
solution without surface stress effects. It is concluded that the size-dependence is
due to the dependence of surface stress on strain. Ignoring this strain-dependence
of surface stress will lead to the disappearance of size effect. The presence of
surface Lamé constants and residual surface tension under unconstrained con-
ditions increases and decreases the film stiffness, respectively. Figure 5.3 shows
Fig. 5.3 Through-the-

thickness distribution of the
dimensionless transverse
shear stress at r = R/2,
reprinted with kind
permission from Lim [42]
through-the-thickness distribution of the dimensionless transverse shear stress at

r = R/2.
The effect of the material micro-structural interfaces increases as the surface-
to-volume ratio increases. Abu Al-Rub [43] showed that interfacial effects have a
profound impact on the scale-dependent yield strength and strain hardening of
micro/nano-systems even under uniform stressing. This is achieved by adopting a
higher-order gradient-dependent plasticity theory that enforces microscopic
boundary conditions at interfaces and free surfaces. Those nonstandard boundary
conditions relate a microtraction stress to the interfacial energy at the interface. In
addition to the nonlocal yield condition for the material’s bulk, a microscopic yield
condition for the interface is presented, which determines the stress at which the
interface begins to deform plastically and harden. Hence, two material length
scales are incorporated: one for the bulk and the other for the interface. Different
expressions for the interfacial energy are investigated. The effect of the interfacial
yield strength and interfacial hardening are studied by analytically solving a one-
dimensional Hall–Petch-type size effect problem. It is found that when assuming
compliant interfaces the interface properties control both the material’s global
yield strength and rates of strain hardening such that the interfacial strength
controls the global yield strength whereas the interfacial hardening controls both
the global yield strength and strain hardening rates. On the other hand, when
assuming a stiff interface, the bulk length scale controls both the global yield
strength and strain hardening rates. Moreover, it is found that in order to correctly
predict the increase in the yield strength with decreasing size, the interfacial length
scale should scale the magnitude of both the interfacial yield strength and inter-
facial hardening.
The emerging areas of micro and nanotechnologies exhibit important strength
differences that result from continuous modification of the material micro-struc-
tural characteristics with changing size, whereby the smaller is the size the
stronger is the response. For example, experimental works have shown increase in
strength by decreasing: (a) the particle size of particle-reinforced composites while
keeping the volume fraction constant; (b) the diameter of micro-wires under tor-
sion; (c) the thickness of thin films under bending or uniaxial tension; (d) the
indentation depth in micro/nano-indentation tests; (e) the grain size of nano-
crystalline materials (the well-known Hall–Petch effect); the void size in nano-
porous media; and several others. Therefore, accurate identification of the
mechanical properties of micro/nano-systems (e.g. micro/nano thin films, micro/
nano wires, micro/nano-composites) is essential for the design, performance, and
development of, for example, micro/nano electronics and micro/nanoelectrome-
chanical systems (MEMS/NEMS) to be used, for example, as actuators or sensors
(e.g. pressure, inertial, thermal, and chemical sensors, position detectors, accel-
erometers, magnetometers, micromirrors, etc.). The mechanical properties of
small-scale structures are different from those of the conventional or bulk coun-
terparts because they are very sensitive to the micro-structural features of the
material such as the grain size, the finite number of grains, the boundary layer
thickness, texture, and dislocation structure. Therefore, when one or more of the
Fig. 5.4 Illustration of

strengthening in micro/nano-
systems. a Stress–strain
diagrams for various sizes,
and b increase in the yield
strength and/or the rate of
strain hardening as size
decreases, reprinted with kind
permission from Abu Al-Rub
[43]
dimensions of these systems begin to approach that of their microstructural fea-

tures, the material mechanical properties (e.g. yield strength, strain hardening,
fracture toughness) begin to exhibit a dependence on the structure size as sche-
matically shown in Fig. 5.4. In metallic systems this translates to plastic yielding
occurring at increased stresses over their bulk counterparts. The small sizes
involved limit the conventional operation of dislocations and the application of
classical continuum mechanics concepts; thus, a fundamental question arises:
since the initial yield stress (i.e. onset of plasticity) in micro/nano-systems is size-
dependent, a question that needs to be addressed, what yield strength should be
used in the design of these systems?
Size effects in micro/nano-systems could not be explained by the classical
continuum mechanics since no length scale enters the constitutive description.
A multiscale continuum theory, therefore, is needed to bridge the gap between the
classical continuum theories and micromechanical theories. Since the increase in
strength with decreasing scale can be related to proportional increase in the strain
gradients, which accommodate the evolution of geometrically necessary disloca-
tions (GNDs), the gradient plasticity theory has been successful in addressing the
size effect problem. This success stems out from the incorporation of a micro-
structural length scale parameter through functional dependencies on the plastic
strain gradient of nonlocal media. Furthermore, for mathematical consistency, in
the gradient-dependent framework, additional boundary conditions have to be
specified at interfaces and free surfaces allowing one to include interfacial effects.
However, recently many researchers who are engaged in nano/micro character-
ization have questioned the ability of the gradient plasticity theory in predicting
the Hall–Petch-like size effect; i.e. the increase in the yield strength with
decreasing the grain size under macroscopically homogeneous stressing or
straining (i.e. under uniaxial tension or compression). This is attributed to lack of
the physical understanding of the nature of the non-classical boundary conditions
that the gradient plasticity theory enforces at the material free surfaces and
interfaces. Free surfaces and interfaces of a material confined in a small volume
can strongly affect the mechanical properties of the material. Free surfaces in
submicron and nano-systems can be sources for development of defects and its
propagation towards the interior. Hard, soft, or intermediate interfaces between
distinct phase regions can also be locations for dislocations’ blocking and pile-ups
that give rise to strain gradients to accommodate the GNDs. The increase in the
initial yield stress with decreasing thickness observed in tensile tests of various
thin films in the size range of 100–500 nm may be taken as a hint in this direction.
The free surfaces of the thin film and the interface between the film and substrate,
therefore, can have a significant effect on the strength of the thin film. Lower-order
strain gradient plasticity theories which neglect the application of the corre-
sponding higher-order boundary conditions at interfaces and free surfaces indeed
fail to predict boundary layer effects. Therefore, the focus of this paper is laid on
the effect of dimensional constraints on the yield strength and plastic flow and to
show that higher-order gradient plasticity theories (as opposed to lower-order
theories) can be used successfully to interpret size effects under macroscopically
homogeneous stressing or straining conditions.
Dislocation pile-ups, which result in local plastic strain gradients, could be
encountered at free surfaces and interface depending on the level of surface/
interfacial energy which increases as the surface-to-volume ratio increases. In
other words, it is expected that as the characteristic size decreases, the higher is
the surface/interfacial energy and the more significant is the effect of the
boundary layer thickness on the strength of the system. Therefore, size effect can
be explained by constrained plastic slipping due to grain boundaries and inter-
faces which result in a nonuniform straining, thereby setting up strong gradients
of strain. Plastic deformation in small-scale structures, accommodated by dislo-
cation nucleation and movement, is therefore strongly affected by interfaces.
Until now, little attention is devoted to interfacial strengthening effects (e.g. film-
substrate interface, phase or grain boundaries, inclusion’s interface, void free
surface, nano-wires free surfaces, etc.) on the scale-dependent plasticity in small-
scale systems. Interface and boundary conditions for higher-order variables are
generally modeled as infinitely stiff or completely free; and the references quoted
therein). These conditions are very difficult to be satisfied in reality, particularly,
for systems with large surface-to-volume ratios. However, recently there have
been few attempts to model intermediate (i.e. not free and not stiff) boundary
conditions for higher-order variables within the higher-order strain gradient
plasticity framework.
Abu Al-Rub [43] studied the effect of interface properties (yield strength and
hardening) on the scale-dependent behavior of small-scale systems within the
framework of higher-order gradient plasticity theory. It is shown that the addi-
tional microscopic boundary conditions, which are supplemented by the gradient
approach, allows one to predict size effects under uniform stressing. This is
achieved by relating the microtraction stress at interfaces to an interfacial energy
that depends on the plastic strain at the interface. Furthermore, by examining linear
and nonlinear expressions for this interfacial energy, it is shown that an interfacial
yield condition, besides the nonlocal yield condition for the bulk, can be formu-
lated. This condition governs the emission/transmission of dislocations across the
interface and is expressed in terms of the microtraction stress, the interfacial yield
strength, the interfacial hardening, and the interfacial length scale. Therefore, two
internal length scales are incorporated in the present formalism, one for the bulk, ‘,
and the other for the interface, ‘I.
It is shown that the higher-order gradient plasticity theory when supplemented
by interfacial energy effects, at least for the one-dimensional example presented
here, can qualitatively describe many features of the size effect due to GNDs,
including the strengthening, the development of boundary layers, and the strain
hardening. The qualitative modeling of the strengthening is explained by the
interfacial yield strength, whereas the strain hardening is described by accounting
for the interfacial hardening effect. Four different forms for the interfacial energy
(or equivalently the interfacial yield condition) in terms of the plastic strain at the
interface are examined: (a) a linear one which allows the interface to yield in a
perfectly plastic manner without hardening; (b) a quadratic form which allows the
interface to harden but yields at the same time as the bulk; (c) a combination of (a)
and (b) such that the interfacial yield strength and interfacial hardening can be
altered independently; and (d) a combination of (a) and (b) such that the interfacial
yield strength and interfacial hardening are both scaled with the interfacial length
scale. It is found through (a) that that interfacial yield strength controls the overall
yield strength (i.e. onset of plasticity) of the specimen. Moreover, an analytical
expression for the interfacial yield stress at which interface deforms plastically is
derived. This is one of the most interesting features of the present formulation.
From this expression, it is concluded that the yield strength of ultra-fine grained
materials is controlled by the interfacial strength of the grain boundary. Moreover,
it is found through (b) that interfacial hardening controls the increase in the
plasticity tangent hardening modulus and in the flow stress with decreasing size.
The expression in (c) shows that the interfacial hardening contributes to the global
yield strength as well as to the strain hardening rates (i.e. flow stress). However, it
is shown that the expression in (c) yields incorrect decrease in the yield strength
when increasing the interface stiffness. This is corrected by adapting the expres-
sion in (d) which shows that by increasing the interfacial hardening, stiffer
interfaces are formed that in turn increases the yield strength of the material due to
dislocation networking at the interface which obstructing further emission/trans-
mission of dislocations across the interface. Therefore, it is concluded that the
interfacial length scale should scale the effect of both the interfacial yield strength
and interfacial hardening. Moreover, one should be careful when choosing a
proper form for the interfacial energy such that it should at least qualitatively
confirms with the experimental observations of size effect behavior.
It is concluded that the increase in the material’s yield strength and strain
hardening rates with decreasing size is determined by the weakest link of bulk
and interface. If the interface is compliant then the properties of the interface
control the yield strength and hardening rates of the material (i.e. controlled by
the interfacial length scale ‘I). On the other hand, if the interface is rigid, the
yield strength and hardening rates are controlled by the bulk behavior (i.e.
controlled by the bulk length scale ‘). Therefore, for intermediate interfaces, a
competition between those two mechanisms exists. Interfacial effect is an
important aspect for further development of gradient-dependent plasticity that is
capable of modeling size effects in micro/nano-systems that are initially sub-

jected to macroscopically uniform stresses or strains. It is shown that the exis-
tence of both gradients and interfacial energies contribute to the observed size
effects. Moreover, it is emphasized that in the absence of the interfacial energy,
the material would support uniform fields and hence the constitutive gradient-
dependence would have no influence. Therefore, strain gradients come into play
if the boundaries are assumed to constrain the plastic flow. Therefore, if con-
tinuum theories are to be used to predict plastic behavior at the micron or
submicron length scales, a higher-order theory with interfacial energies is likely
to be required.
Also, it would be interesting to compare the results provided by the present
theory and its rate form counterpart obtained in two- or three-dimensional appli-
cations. In a forthcoming work, a detailed Finite Element implementation of the
proposed model will be presented and used to simulate size effect in small-scale
structures under various loading conditions (e.g. bending, torsion, cyclic loading).
Moreover, it is interesting to validate the present conclusions by performing
detailed discrete dislocation dynamics. It is noteworthy that several researchers
have questioned the ability of strain gradient plasticity theory to explain the
observed size effect in nano/micro pillars or columns when subjected to
Fig. 5.5 Size effects due to interfacial yield strength only without interfacial hardening. The
interfacial yield strength is varying according to a and c, d1 = 0.1 and b and d, d1 = 0.45. a,
b Normalized plastic strain distribution along d for r 0 ¼ 2: c, d Normalized stress–strain
relations. Different sizes are represented by ‘/d = 0.1, 0.5, 1, 1.5, 2, reprinted with kind
permission from Abu Al-Rub [43]
macroscopically homogenous deformation. These debates are attributed to the

absence of strain gradients in these systems when subjected to uniform straining or
stressing. Moreover, it has been argued that this type of size effect is due to
dislocation starvation; i.e. the rate at which dislocations multiply is less than that
rate at which dislocations escape and annihilate from the pillar surface as the size
decreasing to hundreds of nanometers.
Finally, more than 50 years of research on grain boundaries has established
their impact on the overall strength of materials, yet experimental studies on
their yield strength or Young’s modulus are rare in the literature. This is because
grain boundaries are random networks of interfaces that are only a few nano-
meters wide and cannot be isolated and characterized by conventional tensile,
bending, indentation tools. Therefore, the fundamental understanding on the
interfaces in materials will impact grain boundary engineering, an evolving
research direction towards optimized materials design. Figure 5.5 shows size
effects due to interfacial yield strength only without interfacial hardening while
Fig. 5.6 illustrates size effects due to interfacial yield strength and interfacial
hardening for d1 = d2 = d.
Fig. 5.6 Size effects due to interfacial yield strength and interfacial hardening for d1 = d2 = d.
Both the interfacial yield strength and hardening is varying simultaneously according to a and c,
d = 0.45 and b and d, d = 1. a, b Normalized plastic strain distribution along d for r 0 ¼ 2: c,
d Normalized stress–strain relations. Different sizes are represented by ‘/d = 0.1, 0.5, 1, 1.5, 2,
reprinted with kind permission from Abu Al-Rub [43]
5.8 Studying Effective Factors on Simultaneous Deposition

of Alumina Nanoparticles with Nickel
5.8.1 Effect of Density of Alumina Nanoparticles in Electrolyte

Bath
Guglielmi Model has specified that density of particles in bath affects on degree of
participation of these particles in coat. With the increase of their density in
electrolyte, the degree of their attraction will be increased on cathode surface and
consequently, it will cause increase of participation of these nanoparticles in
nickel-based coating. In Celice model, which has been posed based on possibility
of passage of particle from penetrated layer, with the increase of density of alu-
mina nanoparticles in electrolyte solution, possibility of passing them from pen-
etrated layer is increased and consequently, degree of participation of
nanoparticles will be increased in nanocomposite coat. Some researches have been
made on effect of pulse current variables on hardness and resistance of friction of
nickel-alumina composite coating he attained similar results. These results have
been shown in Fig. 5.7. It is observed that alumina density increase at bath has
boosted hardness of composite coating which is related to more participation of
alumina particles in coating. In another research on electrical deposition of Ni/
Al2O3 with revolving multidimensional electrode, effect of density of alumina
particles was studied on particles volumetric percentage in coating [39, 44–57].
Fig. 5.7 Effect of alumina concentration in bath on hardness of nickel-alumina composite

coatings electroplated with a direct current (DC) with 5 A/dm2, b pulse current 5 A/dm2 and duty
cycle 20% and frequency 75 Hz
5.8 Studying Effective Factors on Simultaneous Deposition 163
5.8.2 Effect of Electroplating Current Density
According to Guglielmi Model, it was specified that degree of participation of

neutral particles in coating will be decreased in tandem with increase of density
of plating current. This subject was studied by Guglielmi in simultaneous leakage
of Ni/TiO2 and Ni/SiC particles. This proportion has been increased in tandem
with increase of current density, i.e. degree of participation of particles has been
reduced in composite coating. But, effect of current density has been studied on
degree of participation of alumina particles in nickel-alumina composite coating.
The obtained results accord with Guglielmi Model, indicating reduction of degree
of alumina particles in coating due to the increase of current density. Reduction on
participation of alumina particles with current density increase can be correlated to
electrochemical potential which affects on attraction of alumina particles on
substrate surface. Higher current will create higher cathodic deposition potential
and cause double layer more negative coupled with repulsion of alumina particles.
Consequently, less alumina will participate in nickel base. Figure 5.3 indicates
results on effect of current on degree of participating alumina in Ni/Al2O3 nano-
composite coating. According to Fig. 5.3, it is specified that hardness of nickel-
alumina composite coatings is reduced with the increase of density of current.
In fact, density of current can have two various impacts: density of current can
affect on degree of alumina entered nickel base which will increase hardness of
composite coatings and also can change in microstructure. Change of micro-
structure will cause hardness change. Figure 5.8 indicates that composite coatings
deposited in density of lower currents contain more alumina particles than coatings
deposited in density of higher currents. This issue accords with many of reports
developed at different papers.
Fig. 5.8 Effect of density of direct current on hardness degree of electroplated nickel-alumina
composite coating from bath containing 80 g/1 alumina
5.8.3 Distribution of Alumina Nanoparticles
Coating neutral nanoparticles in deposited layer is hard due to agglomeration of

nanoparticles in electrolyte than particles with micro dimensions, because, when
ceramic particles turn into fine particles, superficial forces will be increased and
consequently they will increase agglomeration activities. The particles distributed
in an electrolyte solution are based on Brownian motion. When two particles
approach or near each other, the energies, which exist between two particles, will
determine whether particles will be isolated or agglomerated from each other.
Generally, agglomeration of particle is occurred due to the gravity energy larger
than repulsion energy between particles. Size of net involved forces in creation of
agglomerated structure depends on condition and nature of system clearly.
Knowledge of structure of interface region is regarded as a very important factor in
comprehension of sustainability of distribution of sold particles with electrolyte.
For fair and appropriate distribution of alumina in nickel-sulfamate bath, a change
in inner-particle interface region is required by physical or chemical methods.
5.8.3.1 Physical Distribution of Alumina Nanoparticle with Ultrasonic

Operations
Physical effect is occurred when absorbs destructive energy particles like ultra-
sonic waves. Disperse of ultrasonic waves in liquid environment produces very
high pressure (over thousand fold of atmosphere pressure), causing exertion of a
huge tension, which entangle bonding energy between particles. Air bubbles enter
inter-particle grooves from holes, aimed at reducing diameter of agglomerated
alumina particles.
5.8.3.2 Chemical Distribution of Alumina Nanoparticle with Dispersants Aid
Chemical effect happens when electrolyte, containing surfactants or molecules,

turns macro with the aim of forming electrostatic or Setric interface between
particles. Under such specific condition, these interfaces will result in repulsion
thanks to amalgamation of absorbed layer and reduction of entropy. When col-
loidal two-particle double layers start overlapping each other with the same load,
repulsion forces between them will confront with Van der Waals force. If repulsive
potential turns large enough for overcoming Van der Waals potential, it will result
in sustainability of electrical double layer [58–71].
A. Setric sustainability
Principally, Setric sustainability has been developed based on two mechanisms.
When two particles near or approach each other with attracted polymers, the
number of situations, which polymer creates, is reduced due to the participation of
other particles. This activity will result in reduction of entropy. Secondly, density
of polymer is increased at overlapping region which will result in Osmotic

Repulsion between particles in suspension.
B. Electrostatic sustainability
Suspension sustainability can be obtained with combination of electrostatic and
Setric forces. This activity will be obtained through the following three methods:
1. With the participation of particles with electric load and one neutral polymer
molecule,
2. With the participation of neutral particles and one polymer molecule with
electric load,
3. With the participation of particles with electric load and one loaded polymer
molecule,
Presence of particles with electric load creates repulsive potential with long
range and presence of polymer will create repulsive potential with short range
when particles near or approach each other.
C. Getting familiarity with chemical dispersants
In the processes followed with suspensions, a number of fundamental and basic
interactions can be applied for affecting inter-particle forces. These forces include
Van der Waals attraction forces and electrical double-layer repulsive forces. The
two forces emerge when solution ions with loaded agent group attracted surface of
particles and/or isolation of solution ions is made from surfaces of particles. Setric
forces are created by large-size molecules which have been struck to surface of
particles. In the same direction, large loaded molecules, which are polyelectrolyte,
will create repulsive electro-setric forces. Combination of interaction of Van der
Waals and double-layer repulsion is basic of renowned DLVO theory which will
provide network interaction energy. In addition, attraction forces are affected by
change of dispersant environment. The largest effect is made on Van der Waals
attraction through change of solution for solvability with up-to-down dielectric
coefficient. General explanation for mechanism of particles superficial load in
polar solutions depends on congregation of ion species in interface. Dispersants
can be organic chemicals with low molecular weight, carrying agent groups for
stabilizing on surface and marking specific part. That part of specific section is
better to be severely polar additional group especially the groups like acid car-
boxylic and those groups which increase negative load of surface in proton dis-
persant environment in pH above 3.
Citric acid or Maleic acid is regarded as examples of the said group. Other
organic dispersants include polymer and polyelectrolyte with molecular weight
less than 2,000 for polyelectrolyte containing high load and 10,000 for polymers.
The separable agent or typical polar groups for dispersants include as follows:
Hydroxyl (–OH), carboxyl (–COOH), sulfanate (–SO3-), sulfate 9-OSO3-),
ammonium (–NH4+), ammonia (–NH2), amino (–NH-) and poly oxy ethylene
(–CH2CH2O-). Setric sustainability enjoys major share in non-ion large molecules
in solid/solvable system. Better output can be observed or Setric sustainability in
non-ion large molecules in comparison with the compounds having low molecular
weight. Some of common dispersants have been shown in Table 5.2.
Table 5.2 Common dispersants used in ceramic processing

Low molecular weight High molecular weight
Sodium borate Poly(acrylic acid) PAA
Sodium carbonate Poly(methacrylic acid) (PMAA)
Sodium pyrophosphate Ammonium polyacrylate
Sodium silicate Sodium polyacrylate
Citric acid Polyisobutene
Ammonium citrate Menhaden fish oil
Sodium citrate Phosphate ester
Sodium tartrate Sodium polysulfonate
Sodium succinate
Glycerol trioleate
5.8.4 Effect of Density of Nickel Ions in Plating Bath
Nickel coating baths include as follows: (1) Watts bath, (2) sulfate bath, (3) chloride
bath, (4) nickel-sulfamate, (5) nickel fluorobrate. Nickel is usually deposited in
watts bath type. This method is yet used for most nickel plating whether as sub-
layer or thick geometrical sections. Hereunder are regarded as main components of
formation of bath: nickel-sulfamate as noncomplex (Ni2+), chloral nickel for
improvement of solvability of anode and increase of density of currents through
fracturing penetrated layer, boric acid for fixation of pH approximately 4 and
reducing inclination to hydrolysis due to reduction of establishing non-acid salts,
various additives for increasing of leveling surface, reduction of tension and
crystallization of coating. Full-chloride baths can be used for delicacy of grains and
granules in hard coatings and full sulfate baths can be applied while using lead non-
solvable anodes. Fluorobrate and sulfamate solutions have specific applications.
Using sulfamate baths in electroforming, which speed of plating is of paramount
importance, has been developed more.
Comparison of output of cathode current for various baths of nickel is as
follows:
• Watts nickel bath 98–90%
• Full chloride 98–99%
• Sulfamate 97–99%
• Fluorobrate 90–95%
The baths used for nickel-alumina nanocomposite coating are principally are as
follows: Watts baths, sulfamate and rarely chloride bath. The degree of effect of
nickel ion on agglomeration of alumina nanoparticles in electrolyte and also
degree of participation of alumina nanoparticles in nanocomposite coating is the
salient and the most significant point at these baths. Increase of metal ions in
electrolyte will cause reduction of distance of alumina nanoparticle electrical
double layers.
Consequently, repulsion force is reduced between particles. This activity will

cause facilitation of agglomeration of alumina nanoparticles in high-conductor
metal electrolyte. Using chemical and physical distribution has limited effect in
preventing from agglomeration of alumina nanoparticles, rather, using bath with
low nickel ion density will cause reduction of degree of agglomeration of alumina
nanoparticles. In some researches, it was specified that average diameter of
agglomerated alumina has been de-ionized in water without application of using
ultrasonic energy and nickel-sulfamate bath will be 183 and 1109 nm respectively.
That is to say that effect of solution ion power on agglomeration of particles can
not be ignored. They reduced the average diameter of agglomerated alumina
particles through the application of physical distribution (with imposed ultrasonic
energy) and chemical distribution (with adding surfactants to nickel bath) 280 and
448 nm respectively.
The size of alumina nanoparticles used by them stood at 80 nm which
electrical deposition was carried out in three nickel baths, (1) without surfactant
and ultrasonic operation, (2) with ultrasonic operation with 5 W/l for a period
of 40 min and (3) with adding Cetytrimethyl Ammonium Bromide (CTAB) as
surfactant. The diameter of agglomerated particles of alumina nanoparticles in
Ni bath without adding surfactant and conducting ultrasonic operation stands at
1109 nm. It will cause presence of very low degree of alumina 1.42% vol, with
agglomerated structure in coating. The diameter of alumina agglomerated par-
ticles was reduced to 280 and 448 nm in order through the application of
physical distribution with imposed ultrasonic energy and chemical distribution
through surfactant added to nickel bath. They used four baths with various
nickel densities for studying effect of nickel ion density on degree of
agglomeration. It is observed that average diameter of agglomerated alumina is
reduced in tandem with reduction of density of nickel ion in bath. Volumetric
percentage of alumina at this coat has reached from 8.37%, in a bath with high
nickel density, to maximum amount of 26.78%, in a bath with low nickel
density and has reduced slowly to 24.65% through more reduction of nickel
density in bath. Distribution of alumina particles in nickel-sulfamate bath will
be improved when density of electrolyte is low. It is not unnatural that volu-
metric percentage of alumina in nanocomposite coating (Ni/Al2O3) is increased
through reduction of nickel ion at this electrochemical reaction. But when
nickel ion density is very low, output of density of low current will result in
revival of hydrogen ion. Therefore, volumetric percentage of alumina in Ni/
Al2O3 coating has maximum amount i.e. approx. 26.78%. At this figure, dis-
tribution of particles in composite coating with low ion density is more con-
gruous than its distribution in dense solution. The average diameter of alumina
agglomerated in composite coating is reduced with the reduction of low nickel
ion density. The degree of fine and minute particles in coating will be increased
with dilution of solution. Figure 5.9 indicates effect of nickel electrolyte ion
density on degree of nanoparticles entered in coating. It is observed that
maximum of weight and volumetric percentage of alumina in coating happens
in [Ni] = 3% M density.
Fig. 5.9 Volumetric percentage of Al2O3 by image analysis and weight percentage by EDS
Fig. 5.10 Schematic of

effect of pH on viscosity of
alumina suspension
5.8.5 Effect of pH
Low pH is usually used in nickel baths. At the baths with low pH, nickel density is
kept constant with solving anode. With regard to the baths with low pH (high
sulfate), cathode has more inclination to be turned into a hole. Unlike baths with
high pH type, baths with low pH does not need more care. pH used in papers for
plating nickel-alumina nanocomposite stands at 3.5–4.5 output. The degree of pH
has salient effect on viscosity of suspension. With regard to oxides, viscosity is
changed with zeta potential. Alumina suspension viscosity is increased with the
increase of pH up by specified amount. After pH, viscosity will be reduced with
pH increase. An amount of pH, in which its viscosity is reached to maximum
amount, nears iso-electric point for suspension. Figure 5.10 shows viscosity
changes of alumina suspension based on pH.
With due observance to Fig. 5.10, it is specified that the more pH rate is
reduced, the more alumina suspension viscosity will be reduced. In nanocomposite
plating, the more rate of bath viscosity is less, the more neutral particles can be
transferred to surface of cathode. Hence, pH reduction will help greatly to more
presence of alumina nanoparticles in nanocomposite coating (Ni/Al2O3). Since
iso-electric point of alumina in pH is 9 (pH = 9), with more reduction of pH,
alumina particles surface load in electrolyte will turn more positive. This activity
will cause enlargement of electrical double layer. Consequently, double layer
repulsion forces will be increased. Moreover boosting electrolyte sustainability,
alumina particles inclination for agglomeration will be reduced. This subject will
result in more presence of alumina nanoparticles in nickel-alumina nanocomposite
coating. We should bear in mind that cathode has more inclination to be turned as
hole at the baths with low pH degree. For this reason, neither pH degree should be
lessened nor increased.
5.8.6 Pulse Current Effect
Imposed current is regarded as one of the other parameters which has major effect
on microstructure and morphology of deposited composite coatings. This subject
has shown that more and better control can be imposed on properties of coatings
by improvement of their microstructure through the application of pulse current for
electrical deposition of metals and alloys. Consequently, metals and alloys’ pulse
deposition are of paramount significance due to the possibility of change of their
properties by accurate setting of pulse parameters. Nickel pulse deposition has
attracted the attention of many to itself. Some researchers have recently studied
effect of pulse plating on roughness of deposited nickel thin films surface. Pulse
plating of metals and alloys has been also studied. Reports show that selection of
imposed pulse parameters affects alloy deposition compound tremendously. It has
been reported that remarkable reduction is appeared in internal tension of electrical
depositions while using imposed current as compared with common direct current
at the same density. Some other researchers studied pulse plating parameters on
resistance against corrosion of nickel depositions. Their results show that nickel
deposition by pulse current imposition can produce nickel coatings with less
porosity and resistant against corrosion better in comparison with direct current
plating.
Using TEM has shown that distribution of nanoparticles size in deposited films
under Direct Current (DC) condition is naturally the same distribution of size of
nano powders used in deposition. This subject is of paramount significance with
relation to obtaining composite films. When films deposited from the same bath
under pulse direct current (PDC), large nanoparticles or part of particle which has
been agglomerated, may not coat by growth of sprout during a pulse on a film.
Therefore, it may exclude before any pulse is occurred which does not necessarily
cause continuous growth of juvenile. The initial results on electric deposition
(PDC) of nickel-alumina composite films show that smaller nanoparticles are

coated as larger particles while PDC plating. Hence, a selection of size of nano-
particle is occurred.
Some researchers studied effect of pulse deposition parameters on hardness and
resistance against nickel-alumina composite friction. They indicate that degree of
higher hardness is obtained at duty cycle and lower frequencies. This subject
points this matter that reduction of duty cycle and frequency will cause presence of
more particles of alumina particles, and consequently, hard coat is obtained. Low
duty cycle is meant an off-time more when not current passes from electrolyte and
such issue will create more chance for ceramic particles for attaining double
layers. Hence, more alumina will be participated in coat. Frequency of pulse
current also has similar effect. In low frequencies, there is low number of cycles,
resulted in creation of a better situation for alumina particles. Finally, hard coat is
deposited in low-frequency pulses. Effect of duty cycle and pulse frequency has
been studied on degree of participating alumina particles [28, 72–85].
In study of reverse pulse plating of nanocomposite thin film, some researchers
have studied effect of duty cycle on presence of alumina particles in copper
nanocomposite thin films. Although they have not studied effect of pulse frequency
on degree of participation of alumina, they showed that reduction of duty cycle
will increase presence of alumina nanoparticle in nanocomposite coating. Metal-
lographic test of nickel-alumina composite coating deposited in duty cycle and
various frequencies specify that morphology of these coatings is severely affected
with the selection of pulse parameters. In Table 5.3, effect of pulse parameters has
been shown on rate of participating alumina particles and hardness of composite
coatings.
Deposition in low duty cycle will cause increase of proportion of large particles
in coating, as the pulse off-time is more in low duty cycle. Consequently, large
particles can reach cathode surface through effect of mass transfer in pulse off-time
period. Increase of duty cycle of two various effects is on presence of particles in
coating:
1. Remarkable reduction of degree of participation of particles in coating
2. Participation of smaller particles more than large-size particles
Some researchers have recently explained that selection of particles size is
occurred while PDC plating clearly. In deposited samples with DC, ceramic
Table 5.3 Laboratory data related to obtained results for nanocomposite Ni/alumina
electroplating
Coating thickness Duty cycle Frequency Vol.% of Hardness VHN
(microns) (%) (Hz) alumina (kg/mm2)
15 20 50 35 364
20 80 50 13 250
10 60 20 15 280
12 60 80 11 238
particles larger than 100 nm are observed clearly and simultaneous deposited
particles have been agglomerated. For the sample provided under PDC condition
(right hand), any particle larger than 100 nm and agglomerated particle similar to
what is observed in DC, is not found. In addition, the average base grain size
stands at 20 nm. The research activities on simultaneous deposition of alumina
nano-wisckers in nanocomposite coating in pulse method specified that rate of
alumina nano-wisckers coated in composite coating is increased with reduction of
frequency and more congruity is obtained in distribution of nano-wisckers in
coating with lower frequencies.
5.9 Size Dependency of Tensile and Fatigue Strength

in Ultra-Thin Films
Tensile and fatigue tests of ultra-thin copper films were conducted using a micro-
force testing system by Zhang et al. [86]. Fatigue strength as a function of film
thickness was measured under the constant total strain range control at a frequency
of 10 Hz. The experimental results exhibit that both yield strength and fatigue
lifetime are dependent on film thickness. Fatigue damage behavior in the 100 nm
thick Cu films with nanometer-sized grains is different from that in the microm-
eter-thick copper films with large grains observed before. A comparison of the
present results with those reported in literatures is conducted. Possible fatigue
strengthening mechanism in the ultra-thin copper films is discussed.
Fatigue of thin metal films is a key issue for the long-term service of mic-
rodevices. Previous investigations of fatigue of thin metal foils show a tendency of
the improved fatigue strength with decreasing foil thickness. Especially, several
studies on thin metal films, such as thin Ag films and Cu films, have demonstrated
that fatigue properties of these metal films are significantly different from those of
the bulk materials. When the film thickness approaches 200 nm, interface-induced
fatigue damage becomes more prevalent. In these studies, the film thickness and
grain size are usually ranged from several micrometers to sub-micrometers.
However, little is known about fatigue damage and strength of metal films with
nanometer-scale thickness and grain size. Zhang et al. [86] present the evaluation
of tensile yield strength and fatigue lifetime of ultrathin Cu films with a thickness
of about 100 nm or less and nanometer-sized grains. Figure 5.11 shows tensile
yield strength of the ultrathin Cu films as a function of film thickness and Fig. 5.12
shows the mechanical energy loss versus the number of cycles of the 60 nm thick
Cu films and the number of cycles to fatigue damage (Nf) as a function of film
thickness.
Zhang et al. [86] concluded that the yield strength of the ultra-thin Cu films
further increases with decreasing film thickness down to several tens of nano-
meters. A comparison of fatigue lifetimes between the ultra-thin films and those
in the literature indicates that the fatigue resistance of the ultra-thin Cu films is
Fig. 5.11 a Tensile yield

strength of the ultrathin Cu
films as a function of film
thickness, reprinted with kind
permission from Zhang [86]
Fig. 5.12 a The mechanical

energy loss vs. the number of
cycles of the 60 nm thick Cu
films; b the number of cycles
to fatigue damage (Nf) as a
function of film thickness,
reprinted with kind
permission from Zhang [86]
5.9 Size Dependency of Tensile and Fatigue Strength in Ultra-Thin Films 173
higher than those of the micrometer-thick films, but somewhat less than that of
the sub-micrometer-thick films. It is suggested that the activated GB-related
deformation mechanism is responsible for the potential decrease in the fatigue
resistance in the nanometers thick films compared with the sub-micrometer-thick
films.
5.10 Application of Coating for Strength Enhancement
Researchers produced nano-composite materials made of steel alloy, with very few
molecules in their particles which can be used in buildings to increase strength and
other similar cases. There existed a common physical mechanism which con-
tributes to control alloy hardness. Hardness increase causes malleability, foliating,
and tabularization decrease. Using nano-composites in these alloys it is possible to
decrease these shortages to a high extent. This is caused by an increase in con-
trolling mechanisms for each material property in nano scales.
This method involves creating an alloy in frozen glass structure. Grinding
obtained product make it possible to produce a particular powder which make
bonds with other materials and create a very dense coating during heating process.
Under this conditions particles diameter is about 50 nm. The process can generate
very strong bonds in substances. Available steels are of strength about 10% of
those calculated through theoretical methods, once using this method enables us to
reach strengths about 40–45% of calculated one. This method also contributes to
obtain better corrosion resistant properties.
Experiments show that steel nano-coating is harder than traditional steel. This
coating can be performed either construction of main data or after that. The
method is very cheap compared with other conventional ones. This material can
also be used for aluminum coating which significantly enhances its strength, while
adds no mentionable weight to that. Also, empirical observations show that this
type of coatings makes bonds with aluminum, while conventional Fe–Al coating is
not easily performed. It is expected this method be of frequent applications
[87–101].
5.11 Nano-Coating Use in Dressing Industry
Some clothes producers have used a nano-protector coating to coat clothes’ sur-
face. These include coatings resistant against pollution, decay, abrasion, and fire;
however, they do not bring a good feeling to customers while wearing them. LLC
Nano-Tex uses these coatings in United States. Also, U-Right uses this kind of
coating, developed by Sweden researchers, in its products. The coating is used in
clothes fabric as well as its other parts.
5.11.1 Making WC/Co–Ni Nano-Coating Using Electrodeposition
WC/Co–Ni coating is broadly used for its high hardness and low friction ratio in
coating process of variant pieces; while in conventional methods thermo-aerosol
method is applied. Through this method a bid deal of WC is used which leads to
increase of piece weight and decrease of its prices. Inframat Company, with
contribution of National Science Foundation (NSF), has developed coating with
WC/Co–Ni nano-particles. Cr–C/W coating is used in some similar methods.
Cr compounds are convenient to create hardness but are environmentally
hazardous due to CRVI release. New substitute material for mentioned materials
should have their high hardness and the other coating properties. In new methods,
WC nano-coatings are coated via electrolyte method with Ni-Co matrix. Coating
with this method creates an equal thickness and does not involve any high cost
mechanical methods for compellation of coating process. Through new method a
lower ratio of WC is consumed. This considerably decreases pieces’ weight and
cost, as well as friction ratio and surface hardness.
5.11.2 Using (Me-Ti1-xAlxN)/(a-Si3N4) Nanocomposite Coatings
Aluminum and titanium alloys and (Me-Ti1-xAlxN)/(a-Si3N4) nano-composite

coatings are used for cutting tools coating. These coatings are of unique features
make them suitable for these tools, including:
• High rate of hardness (25–38 GPa)
• Hardness in high temperatures (in 800C about 30–40%)
• Resistance against oxidization (15-20 lg/cm2), TiCN, and TiN, respectively, at
800, 400, and 550C
• Thermal conductivity
There are some other issues while using these alloys which must be dealt,
including:
• Optimization of fuel processes
• Optimization of crystalline structure to prevent creation of columnar structure
for improvement of pieces resistant against corrosion
• Making multi-layers
• Adding other materials such as
– Cd and Y to enhancement of strength against oxidization
– Zr, V, and B to enhancement of strength against wear and corrosion
– Si for increase of hardness and resistance against chemical agents
Among most important achievements of TiAlCN detecting layer one can name
nano-coating and increase of Al ratio in coatings. Using nano-coating of this alloy,
as well as multi-stage coating with nano thickness, decreases different features of
5.11 Nano-Coating Use in Dressing Industry 175
the surface including hardness, scratch resistance, and oxidization. Through this
new method, nano-composite coating is used for multi-stage coatings. During this
method different materials such as Al, Si, and Ti, which cannot be mixed with each
other, serve as detector layer. They mix one another in plasma state and placed in
amorphous Si3N4 matrix. At high temperatures (up to 1100C), this obtained nano-
composite is of high hardness (40–50 GPa). This kind of nano-composite coating
is required for nano-composite coating of highly efficient melting pieces.
Regarding this coating’s high efficiency compared with other materials and
methods, their application is persistently increasing.
5.12 Size Dependency in Nanocomposite Layers
Properties of Si3N4/Ni electroplated nanocomposite layer such as roughness of

obtained layer and distribution of nanometric particulates have been studied [102].
All of the other effective factors for fabrication of nanocomposite coatings have
been fixed for better studying the effect of the average size of nanoparticulates.
The effects of the different average size of nanometric particulates (ASNP) from
submicron scale (less than 1 lm) to nanometric scale (less than 10 nm) have been
studied. The roughness illustrated a minimum level while the distribution of
nanometric particulates will be more uniform by decreasing the ASNP. The effects
of pulsed current on electrodeposition (frequency, duty cycle) and concentration of
nanoparticulates on electrodeposition bath on trend of obtained curves have been
discussed. Response Surface Methodology was applied for optimizing the effective
operating conditions of coatings. The levels studied were frequency range between
1,000 and 9,000 Hz, duty cycle between 10 and 90% and concentration of
nanoparticulates among 10–90 g l-1.
Figure 5.13 illustrates the effect of different ASNPs on the Ra of coatings.
Interpolated equation shows that there is a quadratic relation among the roughness
of obtained layer and ASNP. It can be concluded that the interaction among
Fig. 5.13 Effect of different

ASNPs on the Ra of
electroplated nanocomposite
Si3N4/Ni coatings [102]
nanoparticulates with low ASNP (approximately less than 90 nm) will increase the
roughness of obtained layer. The minimum roughness has been obtained for
the nanocomposite layer with ASNP equal to 93 nm. The effect of ASPN on the
distribution of nanometric particulates has been illustrated in Fig. 5.14. It can be
easily concluded that the gaussian shape of distribution curves are narrower for
lower amounts of ASPN. Also it can be seen that the distribution curves of
obtained layer for higher amount of ASPN are wider which means that although
the nanometric powders with narrow distribution of particulates around the spe-
cific ASPN have been used but the distribution of nanometric particulates in
obtained nanocomposite layer is not as same as the distribution of used nanometric
particulates for large amounts of ASPN. So, in this point of view, it is better to use
the nanometric particulates for fabrication of nanocomposite layer, with lower
amounts of ASPN.
In another study, hard silica/epoxy nanocomposite coatings were prepared by
spinning method on the surface of AA6082 aluminum alloy with addition of CdTe
quantum dots as the second phase in hard nanocomposite coating with different
ratios in respect to main phase (silica nanoparticulates). Wear tests have been done
on the coatings for investigation of the possible enhanced or inverse effects of
addition QDs on properties of hard nanocomposite. It has been shown that by
adding QD nanoparticulates the electrical conductivity of layers is completely
controllable without adverse effect on wear resistance. Figure 5.15 shows the
effect of different SiO2/QD ratios on the wear rate of obtained layers. Wear rate
illustrates an optimum level and increasing the SiO2/QD ratio after this level will
decrease wear rate significantly. QD nanoparticulates are softer than SiO2-
nanoparticulates and this behavior in wear rate was predictable, somehow
Fig. 5.14 Distribution curve of electroplated nanocomposite Si3N4/Ni coatings with ASPN equal
to a 9 nm, b 72 nm, c 168 nm, d 499 nm [102]
5.12 Size Dependency in Nanocomposite Layers 177
determining the optimum level will affect considerations for possible industrial
usage especially for achieving desirable wear rate and electrical conductivity
together, in economical point of view [103].
In another study, ultra hard ceramic based matrix nanocomposite layers of
tungsten carbide (WC) on matrix of titanium carbide were fabricated in an organic
electrolyte. The dependence of WC amount in nanocomposite coatings was
investigated in relation to the temperature of electrolyte, WC concentration in
bath, current density and stirring rate. It was shown that volume percentage of WC
in the layer can be affected by these parameters. Increasing of the WC nanopar-
ticles concentration in the electrolyte in a constant stirring rate will lead to an
increase in content of nanoparticles in the nanocomposite layers. Concentration of
WC nanoparticles in the bath illustrated specific level for increasing of tungsten
percentage in the nanocomposite layers [104].
Fig. 5.15 Effect of SiO2/QD

ratio on wear rate of different
silica/epoxy nanocomposite
layers [103]
Fig. 5.16 X-ray diffraction pattern of WC/TiC nanocomposite layer fabricated by plasma
electrolysis [104]
The XRD and GAXRD pattern (Fig. 5.16) confirms the formation of a TiC/WC
nanocomposite layer. The concentration of WC nanoparticles was increased
slightly by decreasing GAXRD angle which means that the amount of WC nano-
particles was increased toward the top surface of nanocomposite layer. Average
grain sizes was determined by Scherer equation around 51, 58, 72 and 89 nm for the
layers by 1, 5 and 10 of glancing angle and also simple XRD, relatively.
Tungsten carbide nanoparticles probably act as new sites for grain growth and
hence decrease the final size of grains. Roughness values of the nanocomposite
layers were calculated to be approximately between 1.6 and 4.9l. Figure 5.17
illustrates the changes of roughness with the change in the concentration of WC
nanoparticles in the electrolyte. The increase of roughness is due to the agglom-
eration of WC nanoparticles on the surface of the treated sample. Concentration of
WC nanoparticles in the electrolyte has an optimum level for achieving the mini-
mum roughness on the surface of the nanocomposite layer at higher current den-
sities. In fact, the increase of nanoparticles concentration in the electrolyte and the
increase of the current densities have similar effects on surface roughness. Higher
current densities will lead to big sparks with more damaging effects and their effects
will show themselves on low concentrations of nanoparticles in the electrolyte.
Electrodeposition of tertiary Alumina/Yitria/carbon nanotube (Al2O3/Y2O3/
CNT) nanocomposite layer by using pulsed current has been also studied. The
Fig. 5.17 Relation among

surface roughness of coating
and WC nanoparticle
concentration in electrolyte in
different current densities
[104]
Fig. 5.18 Relation between

average size of nanoparticles
and wear rates for
electrodeposited tertiary
nanocomposite layer [105]
5.12 Size Dependency in Nanocomposite Layers 179
effects of some process variables have been experimentally studied and statistical
methods were used to achieve the minimum wear rate and average size of nano-
particles. It has been revealed that by changing the size of nanoparticles, wear
properties of coatings will change significantly. In the case of average size of
nanoparticles ranking of effective factors by their relative contributions is the same
as for wear rate which shows strong relation between these two measured prop-
erties of coatings [105]. This relation can be seen in Fig. 5.18.
References
1. Baji, A., Mai, Y.W., Wong, S.C., Abtahi, M., Chen, P.: Electrospinning of polymer
nanofibers: effects on oriented morphology, structures and tensile properties. Compos. Sci.
Technol. 70, 703–718 (2010)
2. Beitollahi, A., Hosseini-Bay, H., Sarpoolaki, H.: Synthesis and characterization of Al2O3-
ZrO2 nanocomposite powder by sucrose process. J. Mater. Sci. Mater. Electron. 21, 130–
136 (2010)
3. Bouvy, C., Chelnokov, E., Marine, W., Sporken, R., Su, B.L.: Quantum size effect and very
localized random laser in ZnO@mesoporous silica nanocomposite following a two-photon
absorption process. J. Non Cryst. Solids 355, 1152–1156 (2009)
4. Hasheminejad, S.M., Avazmohammadi, R.: Size-dependent effective dynamic properties of
unidirectional nanocomposites with interface energy effects. Compos. Sci. Technol. 69,
2538–2546 (2009)
5. He, J.H., Yuan, S.L., Yin, S.Y., Liu, K.L., Li, P., Wang, C.H., Liu, L., Li, J.Q., Tian, Z.M.:
Analysis of exchange bias effect of NiO+NiFe2O4 composites. J. Magn. Magn. Mater. 322,
79–83 (2010)
6. Ifuku, S., Morooka, S., Morimoto, M., Saimoto, H.: Acetylation of chitin nanofibers and
their transparent nanocomposite films. Biomacromolecules 11, 1326–1330 (2010)
7. Jeon, B.S., Cho, E.J., Yang, H.M., Sun, J.S., Huh, Y.M., Kim, J.D.: Controlled aggregates of
magnetite nanoparticles for highly sensitive MR contrast agent. J. Nanosci. Nanotechnol. 9,
7118–7122 (2009)
8. Koroleva, E. Y., Nuzhnyy, D., Pokorny, J., Kamba, S., Kumzerov, Y. A., Vakhrushev, S. B.,
Petzelt, J.: The negative phonon confinement effect in nanoscopic sodium nitrite.
Nanotechnology 20, (2009)
9. Liu, P.C., Hsieh, J.H., Li, C., Chang, Y.K., Yang, C.C.: Dissolution of Cu nanoparticles and
antibacterial behaviors of TaN-Cu nanocomposite thin films. Thin Solid Films 517, 4956–
4960 (2009)
10. Nadeem, K., Traussnig, T., Letofsky-Papst, I., Krenn, H., Brossmann, U., Würschum, R.:
Sol-gel synthesis and characterization of single-phase Ni ferrite nanoparticles dispersed in
SiO2 matrix. J. Alloys Compd. 493, 385–390 (2010)
11. Yang, F.: Size effect on the effective bulk modulus of nanocomposites with core-shell
nanospherical inclusions. Mater. Sci. Eng. A 527, 3913–3917 (2010)
12. Zhang, W.X., Wang, T.J., Chen, X.: Effect of surface/interface stress on the plastic
deformation of nanoporous materials and nanocomposites. Int. J. Plast. 26, 957–975 (2010)
13. Ohno, T., Tagawa, S., Itoh, H., Suzuki, H., Matsuda, T.: Size effect of TiO2-SiO2 nano-
hybrid particle. Mater. Chem. Phys. 113, 119–123 (2009)
14. Beyene, H.T., Chakravadhanula, V.S.K., Hanisch, C., Elbahri, M., Strunskus, T.,
Zaporojtchenko, V., Kienle, L., Faupel, F.: Preparation and plasmonic properties of
polymer-based composites containing Ag-Au alloy nanoparticles produced by vapor phase
co-deposition. J. Mater. Sci. 45, 5865–5871 (2010)
15. Chen, Z., Cao, Y., Qian, J., Ai, X., Yang, H.: Facile synthesis and stable lithium storage
performances of Sn-sandwiched nanoparticles as a high capacity anode material for
rechargeable Li batteries. J. Mater. Chem. 20, 7266–7271 (2010)
16. El-Sheikhy, R.A., Al-Shamrani, M.A.: General analytical concept and design methodology
to producing a clay-based polymer nanocomposite. Ceramic Transactions 165–174 (2010)
17. Jee, A.Y., Lee, M.: Surface functionalization and physicochemical characterization of
diamond nanoparticles. Curr. Appl. Phys. 9, e144–e147 (2009)
18. Jaworek, A.: Electrostatic micro- and nanoencapsulation and electroemulsification: A brief
review. J. Microencapsul. 25, 443–468 (2008)
19. Bo, Y., Lei, S., Nangeng, W., Xiaohan, L., Limin, W., Jian, Z.: A facile method for
fabrication of ordered porous polymer films. Macromolecules 41, 6624–6626 (2008)
20. Vertlib, V., Dietiker, M., Plötze, M., Yezek, L., Spolenak, R., Puzrin, A.M.: Fast assembly
of bio-inspired nanocomposite films. J. Mater. Res. 23, 1026–1035 (2008)
21. Perkas, N., Amirian, G., Dubinsky, S., Gazit, S., Gedanken, A.: Ultrasound-assisted coating
of nylon 6,6 with silver nanoparticles and its antibacterial activity. J. Appl. Polym. Sci. 104,
1423–1430 (2007)
22. Shim, B.S., Starkovich, J., Kotov, N.: Multilayer composites from vapor-grown carbon
nano-fibers. Compos. Sci. Technol. 66, 1171–1178 (2006)
23. Arkhireeva, A., Hay, J.N.: Ormosil nanocomposite materials as modifiers for acrylic coating
systems. J. Nanosci. Nanotechnol. 6, 360–371 (2006)
24. Nolte, A.J., Rubner, M.F., Cohen, R.E.: Creating effective refractive index gradients within
polyelectrolyte multilayer films: molecularly assembled rugate filters. Langmuir 20, 3304–
3310 (2004)
25. Musil, J., Vlček, J., Regent, F., Kunc, F., Zeman, H.: Hard nanocomposite coatings prepared
by magnetron sputtering. In: Key Engineering Materials, pp. 613–622. (2002)
26. Matthews, A.: Developments in PVD tribological coatings (IUVSTA highlights seminar-
vacuum metallurgy division). Vacuum 65, 237–238 (2002)
27. Glasgow, C., Chew, J., Sherman, A.: Microcomposite coating can replace chrome plating.
Adv. Mater. Process. 168, 22–24 (2010)
28. Frade, T., Bouzon, V., Gomes, A., da Silva Pereira, M.I.: Pulsed-reverse current
electrodeposition of Zn and Zn–TiO 2 nanocomposite films. Surf. Coat. Technol. 204,
3592–3598 (2010)
29. Vlasa, A., Varvara, S., Pop, A., Bulea, C., Muresan, L.M.: Electrodeposited Zn–TiO2
nanocomposite coatings and their corrosion behavior. J. Appl. Electrochem. 40, 1519–1527
(2010)
30. Konwar, U., Karak, N., Mandal, M.: Vegetable oil based highly branched polyester/clay
silver nanocomposites as antimicrobial surface coating materials. Prog. Org. Coat. 68, 265–
273 (2010)
31. Wang, L., Wan, S., Wang, S.C., Wood, R.J.K., Xue, Q.J.: Gradient DLC-based
nanocomposite coatings as a solution to improve tribological performance of aluminum
alloy. Tribol. Lett. 38, 155–160 (2010)
32. Marita, Y., Yaacob, I.I.: Synthesis and characterization of nickel-iron-silicon nitride
nanocomposite. In: Advanced Materials Research, pp. 1360–1363. (2010)
33. Taniguchi, T., Shimoyama, N.: Preparation of tintable polysiloxane hard coating material.
Kobunshi Ronbunshu 67, 76–81 (2010)
34. Kizilkaya, C., Karatas, S., Apohan, N.K., Güngör, A.: Synthesis and characterization of
novel polyimide/SiO2 nanocomposite materials containing phenylphosphine oxide via sol-
gel technique. J. Appl. Polym. Sci. 115, 3256–3264 (2010)
35. Zhang, G., Li, B., Jiang, B., Chen, D., Yan, F.: Microstructure and mechanical properties of
multilayer Ti(C, N) films by closed-field unbalanced magnetron sputtering ion plating.
J. Mater. Sci. Technol. 26, 119–124 (2010)
36. Huang, S.H., Hsieh, T.E., Chen, J.W.: BGA cutter improvement utilizing nano-TiAlN
coating layers synthesized by cathodic arc ion plating process. Surf. Coat. Technol. 204,
988–991 (2009)
References 181
37. Fukumoto, N., Ezura, H., Suzuki, T.: Synthesis and oxidation resistance of TiAlSiN and
multilayer TiAlSiN/CrAlN coating. Surf. Coat. Technol. 204, 902–906 (2009)
38. Thiemig, D., Bund, A., Talbot, J.B.: Influence of hydrodynamics and pulse plating
parameters on the electrocodeposition of nickel-alumina nanocomposite films. Electrochim.
Acta 54, 2491–2498 (2009)
39. Peipmann, R., Thomas, J., Bund, A.: Electrocodeposition of nickel-alumina nanocomposite
films under the influence of static magnetic fields. Electrochim. Acta 52, 5808–5814 (2007)
40. Viswanathan, V., Agarwal, A., Ocelik, V., De Hosson, J.T.M., Sobczak, N., Seal, S.: High
energy density processing of a free form nickel-alumina nanocomposite. J. Nanosci.
Nanotechnol. 6, 651–660 (2006)
41. Aruna, S.T., Diwakar, S., Jain, A., Rajam, K.S.: Comparative study on the effect of current
density on Ni and Ni-Ni-Al2O3 nanocomposite coatings produced by electrolytic deposition.
Surf. Eng. 21, 209–214 (2005)
42. He, L.H., Lim, C.W., Wu, B.S.: A continuum model for size-dependent deformation of
elastic films of nano-scale thickness. Int. J. Solids Struct. 41, 847–857 (2004)
43. Abu Al-Rub, R.K.: Interfacial gradient plasticity governs scale-dependent yield strength and
strain hardening rates in micro/nano structured metals. Int. J. Plast. 24, 1277–1306 (2008)
44. Balaraju, J.N., Kalavati, Rajam, K.S: Electroless ternary Ni-W-P alloys containing micron
size Al2O3 particles. Surf. Coat. Technol. 205, 575–581 (2010)
45. Badarulzaman, N.A., Purwadaria, S., Mohamad, A.A., Ahmad, Z.A.: The production of
nickel-alumina composite coating via electroplating. Ionics 15, 603–607 (2009)
46. Spanou, S., Pavlatou, E.A., Spyrellis, N.: Ni/nano-TiO2 composite electrodeposits: textural
and structural modifications. Electrochim. Acta 54, 2547–2555 (2009)
47. Thiemig, D., Bund, A.: Influence of ethanol on the electrocodeposition of Ni/Al2O3
nanocomposite films. Appl. Surf. Sci. 255, 4164–4170 (2009)
48. de Hazan, Y., Werner, D., Z’Graggen, M., Groteklaes, M., Graule, T.: Homogeneous Ni-P/
Al2O3 nanocomposite coatings from stable dispersions in electroless nickel baths. J. Colloid
Interface Sci. 328, 103–109 (2008)
49. Wang, C., Zhong, Y., Ren, W., Lei, Z., Ren, Z., Jia, J., Jiang, A.: Effects of parallel
magnetic field on electrocodeposition behavior of Ni/nanoparticle composite electroplating.
Appl. Surf. Sci. 254, 5649–5654 (2008)
50. Ciubotariu, A., Benea, L., Lakatos-Varsanyi, M., Dragan, V.: Electrochemical impedance
spectroscopy and corrosion behaviour of Al2O3-Ni nano composite coatings. Electrochim.
Acta 53, 4557–4563 (2008)
51. Thiemig, D., Lange, R., Bund, A.: Influence of pulse plating parameters on the
electrocodeposition of matrix metal nanocomposites. Electrochim. Acta 52, 7362–7371
(2007)
52. Bund, A., Thiemig, D.: Influence of bath composition and pH on the electrocodeposition of
alumina nanoparticles and nickel. Surf. Coat. Technol. 201, 7092–7099 (2007)
53. Zhou, Y., Peng, X., Wang, F.: Size effect of Al particles on the oxidation of electrodeposited
Ni-Al composite coatings. Oxid. Met. 64, 169–183 (2005)
54. Amutha, K., Marikkannu, K.R., Vasudevan, T.: Electrodeposition of nickel-(activated)
alumina composites on mild steel. Bull. Electrochem. 21, 379–383 (2005)
55. Tu, W.Y., Xu, B.S., Dong, S.Y., Jiang, B., Du, L.Z.: Effect of n-Al2O3 on electrochemical
nucleation and chemical binding interaction in nickel electrodeposition. Trans. Nonferr.
Met. Soc. China (English Edition) 15, 889–896 (2005)
56. Szczygiel, B., Kolodziej, M.: Composite Ni/Al2O3 coatings and their corrosion resistance.
57. Alirezaei, S., Monirvaghefi, S.M., Salehi, M., Saatchi, A., Kargosha, M.: Effect of alumina
content on wear behaviour of Ni-P-Al2O3(a) electroless composite coatings. Surf. Eng. 21,
60–66 (2005)
58. Kole, M., Dey, T.K.: Viscosity of alumina nanoparticles dispersed in car engine coolant.
Exp. Therm. Fluid Sci. 34, 677–683 (2010)
59. Zhang, Z., Pinnavaia, T.J.: Mesoporous gamma-alumina formed through the surfactant-
mediated scaffolding of peptized pseudoboehmite nanoparticles. Langmuir: ACS J. Surf.
Colloids 26, 10063–10067 (2010)
60. Hosseini, S.M., Moghadassi, A.R., Henneke, D.E.: Henneke, A new dimensionless group
model for determining the viscosity of nanofluids. J. Therm. Anal. Calorim. 100, 873–877
(2010)
61. An, B., Wang, W., Ji, G., Gan, S., Gao, G., Xu, J., Li, G.: Preparation of nano-sized a–Al2O3
from oil shale ash. Energy 35, 45–49 (2010)
62. Ratkovich, A., Penn, R.L.: Zinc oxide nanoparticle growth from homogenous solution:
influence of Zn:OH, water concentration, and surfactant additives. Mater. Res. Bull. 44,
993–998 (2009)
63. Sun, L., Zhang, C., Chen, L., Liu, J., Jin, H., Xu, H., Ding, L.: Preparation of alumina-
coated magnetite nanoparticle for extraction of trimethoprim from environmental water
samples based on mixed hemimicelles solid-phase extraction. Anal. Chim. Acta 638, 162–
168 (2009)
64. Li, X., Zhu, D., Wang, X., Wang, N., Gao, J.: Thermal conductivity enhancement for
aqueous alumina nano-suspensions in the presence of surfactant. J. Enhanc. Heat Transf. 16,
93–102 (2009)
65. Ko, H., Chang, S., Tsukruk, V.V.: Porous substrates for label-free molecular level detection
of nonresonant organic molecules. ACS Nano 3, 181–188 (2009)
66. Burton, P.D., Lavenson, D., Johnson, M., Gorm, D., Karim, A.M., Conant, T., Datye, A.K.,
Hernandez-Sanchez, B.A., Boyle, T.J.: Synthesis and activity of heterogeneous Pd/Al2O3
and Pd/ZnO catalysts prepared from colloidal palladium nanoparticles. Top. Catal. 49, 227–
232 (2008)
67. Kannan, P., Young, R.J., Eichhorn, S.J.: Debundling, isolation, and identification of carbon
nanotubes in electrospun nanofibers. Small 4, 930–933 (2008)
68. Zhang, J., Shi, F., Lin, J., Wei, S.Y., Chen, D., Gao, J.M., Huang, Z., Ding, X.X., Tang, C.:
Nanoparticles assembly of boehmite nanofibers without a surfactant. Mater. Res. Bull. 43,
1709–1715 (2008)
69. Park, S., Seo, D., Lee, J.: Preparation of Pb-free silver paste containing nanoparticles.
Colloids Surf. A Physicochem. Eng. Aspects 313–314, 197–201 (2008)
70. Yong, K.P.: Preparation and characterization of alumina nanoparticles from alkoxides and
Na(AOT) surfactant. In: Materials Science Forum, pp. 785–788. (2007)
71. Shen, S.C., Ng, W.K., Chen, Q., Zeng, X.T., Chew, M.Z., Tan, R.B.H.: Solid-phase low
temperature steam-assisted synthesis of thermal stable alumina nanowires. J. Nanosci.
Nanotechnol. 7, 2726–2733 (2007)
72. Stoyanova, A., Tsakova, V.: Copper-modified poly(3,4-ethylenedioxythiophene) layers for
selective determination of dopamine in the presence of ascorbic acid: II. Role of the
characteristics of the metal deposit. J. Solid State Electrochem. 14, 1957–1965 (2010)
73. Cheng, M.Y., Chen, K.W., Liu, T.F., Wang, Y.L., Feng, H.P.: Effects of direct current and
pulse-reverse copper plating waveforms on the incubation behavior of self-annealing. Thin
Solid Films 518, 7468–7474 (2010)
74. Safaisini, R., Joseph, J.R., Lear, K.L.: Scalable high-CW-power high-speed 980-nm VCSEL
arrays. IEEE J. Quantum Electron. 46, 1590–1596 (2010)
75. Leisner, P., Fredenberg, M., Belov, I.: Pulse and pulse reverse plating of copper from acid
sulphate solutions. Trans. Inst. Met. Finish. 88, 243–247 (2010)
76. Vicenzo, A., Bonelli, S., Cavallotti, P.L.: Pulse plating of matt tin: effect on properties.
Trans. Inst. Met. Finish. 88, 248–255 (2010)
77. Wang, Z.X., Wang, S., Yang, Z., Wang, Z.L.: Influence of additives and pulse parameters
on uniformity of through-hole copper plating. Trans. Inst. Met. Finish. 88, 272–276 (2010)
78. Paatsch, W.: Hydrogen embrittlement in electroplating: avoidance using pulse plating.
Trans. Inst. Met. Finish. 88, 277–278 (2010)
79. Imaz, N., García-Lecína, E., Díez, J.A.: Corrosion properties of double layer nickel coatings
obtained by pulse plating techniques. Trans. Inst. Met. Finish. 88, 256–261 (2010)
References 183
80. Paatsch, W., Mollath, G.: Operating map—tool for plating functional layers. Trans. Inst.
Met. Finish. 88, 234–236 (2010)
81. Richoux, V., Diliberto, S., Boulanger, C.: Pulsed electroplating: a derivate form of
electrodeposition for improvement of (Bi1-xSbx)2Te3 thin films. J. Electron. Mater. 39,
1914–1919 (2010)
82. Farr, J.P.G.: Electroplating, electrode kinetics and electrocrystallisation. Trans. Inst. Met.
Finish. 88, 262–265 (2010)
83. Vasilakopoulos, D., Bouroushian, M.: Electrochemical codeposition of PMMA particles
with zinc. Surf. Coat. Technol. 205, 110–117 (2010)
84. Chandrasekar, M.S., Shanmugasigamani, Malathy, P.: Synergetic effects of pulse
constraints and additives in electrodeposition of nanocrystalline zinc: corrosion, structural
and textural characterization. Mater. Chem. Phys. 124, 516–528 (2010)
85. Ravi, S., Ganesh, K.V., Ramanathan, A., Annamalai, J., Jaiswal, P.K.: Development of nano
crystalline nickel coating for engineering applications. In: Key Engineering Materials,
pp. 487–492. (2010)
86. Zhang, G.P., Sun, K.H., Zhang, B., Gong, J., Sun, C., Wang, Z.G.: Tensile and fatigue
strength of ultrathin copper films. Mater. Sci. Eng. A 483–484, 387–390 (2008)
87. Lajoie, T.W., Ramirez, J.J., Kilin, D.S., Micha, D.A.: Optical properties of amorphous and
crystalline silicon surfaces functionalized with Agn adsorbates. Int. J. Quantum Chem. 110,
3005–3014 (2010)
88. Qiang, L., Weiping, L., Huicong, L., Liqun, Z.: Fabrication of nanostructured
electroforming copper layer by means of an ultrasonic-assisted mechanical treatment.
Chin. J. Aeronaut. 23, 599–603 (2010)
89. Mohebbi, M.S., Akbarzadeh, A.: Accumulative spin-bonding (ASB) as a novel SPD process
for fabrication of nanostructured tubes. Mater. Sci. Eng. A 528, 180–188 (2010)
90. Lu, Y., Wang, L.: Nanoscale modelling of mechanical properties of asphalt-aggregate
interface under tensile loading. Int. J. Pavement Eng. 11, 393–401 (2010)
91. Mozafari, M., Moztarzadeh, F., Rabiee, M., Azami, M., Maleknia, S., Tahriri, M.,
Moztarzadeh, Z., Nezafati, N.: Development of macroporous nanocomposite scaffolds of
gelatin/bioactive glass prepared through layer solvent casting combined with lamination
technique for bone tissue engineering. Ceram. Int. 36, 2431–2439 (2010)
92. Chu, J.P., Wang, Y.C.: Sputter-deposited Cu/Cu(O) multilayers exhibiting enhanced
strength and tunable modulus. Acta Mater. 58, 6371–6378 (2010)
93. Xia, K.: Consolidation of particles by severe plastic deformation: mechanism and
applications in processing bulk ultrafine and nanostructured alloys and composites. Adv.
Eng. Mater. 12, 724–729 (2010)
94. Bernstein, M., Gotman, I., Makarov, C., Phadke, A., Radin, S., Ducheyne, P., Gutmanas,
E.Y.: Low temperature fabrication of b-TCP-PCL nanocomposites for bone implants. Adv.
Eng. Mater. 12, B341–B347 (2010)
95. Savarala, S., Ahmed, S., Ilies, M.A., Wunder, S.L.: Formation and colloidal stability of
dmpc supported lipid bilayers on SiO2 nanobeads. Langmuir 26, 12081–12088 (2010)
96. Jung, M.H., Yun, H.G., Kim, S., Kang, M.G.: ZnO nanosphere fabrication using the
functionalized polystyrene nanoparticles for dye-sensitized solar cells. Electrochim. Acta
55, 6563–6569 (2010)
97. Hosseinkhani, H., Hosseinkhani, M., Hattori, S., Matsuoka, R., Kawaguchi, N.: Micro and
nano-scale in vitro 3D culture system for cardiac stem cells. J. Biomed. Mater. Res. A 94, 1–
8 (2010)
98. Vesce, L., Riccitelli, R., Soscia, G., Brown, T.M., Di Carlo, A., Reale, A.: Optimization of
nanostructured titania photoanodes for dye-sensitized solar cells: study and experimentation
of TiCl4 treatment. J. Non Cryst. Solids 356, 1958–1961 (2010)
99. Deka, H., Karak, N.: Influence of highly branched poly(amido amine) on the properties of
hyperbranched polyurethane/clay nanocomposites. Mater. Chem. Phys. 124, 120–128
(2010)
100. Cao, X., Pettitt, M.E., Wode, F., Sancet, M.P.A., Fu, J., Jian, J., Callow, M.E., Callow, J.A.,
Rosenhahn, A., Grunze, M.: Interaction of zoospores of the green alga ulva with bioinspired
micro- and nanostructured surfaces prepared by polyelectrolyte layer-by-layer self-
assembly. Adv. Funct. Mater. 20, 1984–1993 (2010)
101. Burg, B.R., Bianco, V., Schneider, J., Poulikakos, D.: Electrokinetic framework of
dielectrophoretic deposition devices. J. Appl. Phys. 107, (2010)
102. Khazrayie, M.A., Aghdam, A.R.S.: Si3N4/Ni nanocomposite formed by electroplating:
effect of average size of nanoparticulates. Trans. Nonferr. Met. Soc. China (English Edition)
20, 1017–1023 (2010)
103. Aliov, M.K., Sabur, A.R.: Formation of a novel hard binary SiO2/quantum dot
nanocomposite with predictable electrical conductivity. Mod. Phys. Lett. B 24, 89–96
(2010)
104. Aliofkhazraei, M., Sabour Rouhaghdam, A.: Fabrication of TiC/WC ultra hard
nanocomposite layers by plasma electrolysis and study of its characteristics. Surf. Coat.
Technol. (2010)
Chapter 6
Size Effect in Physical and Other
Properties of Nanostructured Coatings
6.1 Introduction
Rapid development of microelectronics in recent decades has been proven based on

miniaturization and integration of electronic parts and according to the predictions
of the ITRS1 institute, this fast development will also continue in the next decade.
In this regard, MOS field effect transistors or MOSFET2 is the main and basic
component of most of the electronic systems nowadays. Among the numerous
parameters of these systems, MOSFET gate length, which is a critical criterion of
integrated circuits, will decrease to about 10 nm in 2016 [1–6]. The predicted
process of decrement of the gate length by ITRS, has been shown in the
Figs. 6.1 and 6.2. The reasons for the dimensions decrease are as follow:
improvement of the part’s quality and performance, improvement of reliability,
decreasing the power loss, improving the output efficiency, and decreasing its price.
Moreover, the speed of an electronic circuit is one of the most important
factors. In order to increase the speed, parasitic capacity and serial resistances
must be minimized so that RC delay time decreases and the Clock Frequency
increase. Increment of the contact resistance in electronic parts has been one of the
main limitations of size decrement in the recent decades. Hence, using new
materials in joints has been considered in order to fix the circuit quality and
increase the speed. In order to do so, metal silicides have been used in the process
of metallization of joints and local systems. Selection of metal silicides has of
great importance due to these reasons: their low special resistance, their contact
resistances are low against both kinds of silicon, their high thermal stability, and
their processes are compatible with silicon standard technology.
Nowadays metal silicides are an important component of an electronic part. The
SALIIDE3 process leads to the formation of a uniform type of metal silicides
1
International Technology Roadmap for Semiconductors.
2
Metal Oxide Semiconductor Field Effect Transistor.
3
Self-aligned Silicide.

186 6 Size Effect in Physical and Other Properties of Nanostructured Coatings
Fig. 6.1 The approach of gate length decrease according to ITRS predictions
Fig. 6.2 Approach to decrease the thickness of silicide in joints according to ITRS predictions
formed simultaneously in the regions of gate, source, and drain; and it is so

successful due to its reliability and simplicity. Therefore, application of metal
silicides has been promoted in electronics industry. The most common silicides
used in electronic parts are PtSi, TiSi2, and CoSi2, although using C54–TiSi2
(phase with less special resistance) and CoSi2 in smaller parts (less than 0.2 and
0.04 lm respectively) is so difficult. In future parts we must use silicides layers
with very low thickness. The silicides layer’s thickness was about 20 nm in 2005,
and it is expected that it will be reached to 5.5 nm in the year 2015 [7–14].
Recently NiSi has attracted much attention and the latest progresses reference
to the vast efforts in order to the application of NiSi in MOS parts in future
technologies. NiSi is of great importance because of its low special resistance, low
contact resistance, potential to form in low thicknesses, and its consistency.
Therefore, it is inevitable to study its specifications.
Ohno et al. [15] described the control of the quantum size effect by controlling
the coating layer thickness in TiO2–SiO2 core–shell hybrid particles obtained by
the liquid phase deposition (LPD) method. The coating layer thickness of TiO2 on
SiO2 nano-particles was controlled by changing the [Ti]/[Si] ratio. The titania
coating thickness and crystallite size were estimated by transmission electron
microscope (TEM) and X-ray diffraction (XRD), respectively. The quantum size
effect of the obtained nano-hybrid particles was estimated by the band gap energy
shift, using ultraviolet–visible spectroscopy (UV–vis). As a result, we successfully
controlled the degree of the quantum size effect by controlling the coating layer
thickness in core–shell TiO2–SiO2 hybrid particles.
The nano-particles have attracted considerable attention because of their
potential application such as electronic, catalytic materials. The studies of nano
hybrid particles have provided important fundamental insights for new functional
materials such as photonic catalyst, high performance electronic materials and so
on. Therefore, a lot of studies have been carried out to prepare the organic/
inorganic hybrid particles. The quantum size effect has been widely studied for the
microelectronic devices because of their recent trend of downsizing. In addition,
several reports demonstrated that the quantum size effect resulted in the new
properties and/or the improved properties. In general, the quantum size effect is
expected for the nano-particles below 50 nm in many cases. However, there are
difficulties in manipulation and handling of such nano-particles, mainly due to the
agglomeration and the adhesion. Therefore, good handling method should be
developed for the nano-materials with quantum size effect in many fields, such as
electronics and so on. From this point of view, Ohno et al. [15] were proposed the
nano-coating of functional materials on the nano-particles. They successfully
prepared the TiO2–SiO2 hybrid particles by the modified sol–gel process.
However, the obtained hybrid particles were not core–shell materials with
homogeneous coating, and they couldn’t control the quantum size effect. There-
fore, they attempt to prepare the core–shell TiO2–SiO2 hybrid particles with
homogeneous coating by LPD. LPD is well known as film deposition process, and
some researchers applied the LPD method to prepare the TiO2-Polystyrene (PS)
Latex hybrid particles.
Ohno et al. [15] concluded the successful preparation of core–shell type TiO2–
SiO2 hybrid particles by LPD. The coating layer thickness and the crystallite size
were controlled by controlling the [Ti]/[Si]. In the case of the [Ti]/[Si] ratio of over
0.1, silica particles were completely coated by titania. The degree of the blue shift
of the band gap energy by the quantum size effect for the obtained particles was
approximately 0.13 eV larger than that of the pure titania, because of the existence
of the Ti–O–Si bond. If the Ti–O–Si bond effect was removed, the blue shift of the
band gap energy for core–shell type TiO2–SiO2 particles was nearly the same value
as that of the reported values for the pure titania. From these results, the quantum
size effect was successfully controlled by controlling the coating layer thickness of
core–shell type TiO2–SiO2 hybrid particles. Figure 6.3 illustrates the high reso-
lution TEM (HR-TEM) image of surface morphology for the obtained TiO2–SiO2
hybrid particle with different [Ti]/[Si] ratio and the surface area of the obtained
Fig. 6.3 The surface morphology of the obtained TiO2–SiO2 hybrid particle with different [Ti]/
[Si]: a [Ti]/[Si] = 0.1, b 0.3, c 0.5, d 0.75, e 1.0, and f high resolution TEM (HR-TEM) image of
the surface area of the obtained hybrid particle with [Ti]/[Si] = 0.1, reprinted with kind
permission from Ohno [15]
Fig. 6.4 Change in the

crystallite size as a function
of the coating layer thickness,
reprinted with kind
permission from Ohno [15]
hybrid particle with [Ti]/[Si] = 0.1. Also Fig. 6.4 shows change in the crystallite
size as a function of the coating layer thickness.
6.2 Silicides Specifications
Among different metal silicides, which are used in SALICIDE technology, TiSi2
has been vastly studied due to its widespread application in CMOS4 metallization.
For the gate length 0.25 lm and for less than that TiSi2 was replaced by CoSi2.
This substitution faces less resistance in low dimensions due to hard formation of
C54–TiSi2 phase [16–23].
6.2.1 SALICIDE Process
SALICIDE process leads to the simultaneous formation of a uniform type of metal

silicide in gate, source, and drain regions; and is of great importance in advanced
electronic parts technology nowadays. SALICIDE process, for example, using the
NiSi is described below. When gate is defined as a MOSFET, a Ni layer is layered
on top of the sub-layer. The first thermal process, usually RTP,5 at the low tem-
peratures (often between 260 and 310C) leads to the formation of Ni2Si in gate,
source/drain areas where Si, which is in direct contact with layered Ni, is formed.
4
Complementary Metal Oxide Semiconductor.
5
Rapid Thermal Process.
No interaction happens between Ni and the surrounding oxide environment.

After formation of Ni2Si, the extra Ni layer is removed through selective wet etch
method. The second thermal process usually forms NiSi in gate and source/drain
areas between 450 and 500C.
One of the advantages of Ni-SALICIDE is the application of single-stage
thermal process (usually about 400–500C). Practically, the problems related to
non-uniform formation of NiSi and formation on Si lines with more thickness
(thinner than wider lines) have made it necessary to use two-stage aniline process.
SALICIDE process is applicable for Co and Ti, although the main objective of
two-stage aniline process is different. The used temperatures for two-stage aniline
depend on the type of silicide. In Ti and Co mode, the first aniline typically forms
in thermal range of 650–700C for C49–TiSi2 and in 400–600C for Co2Si or
CaSo in order to prevent the formation of silicide on SiO2 which causes a short
circuit between the gate and source/drain electrodes. The second aniline is
important to form low-resistance silicide phases C54–TiSi2 (above 850C) and
CoSi2 (above 700C).
6.2.2 Necessary Conditions for Formation of Silicides
Decreasing serial resistance and common parasitic resistances in gate, and source/
drain areas is fundamental in order to improve the quality of the parts. Also, it is
necessary that SALICIDE process do not influence the part and its alloying profile.
The used metal in the formation of silicides must have the following basic
conditions;
• high conductivity
• Low contact resistance for both alloyed Si types
• Good chemical stability in contact with Si
• Suitable mechanical and thermal specifications
• Suitable thermal stability considering the morphology
• Compatibility with standard processes technology of Si including Etching and
Cleaning
• No need to extra thermal processes
• Void of harmful pollutions which decrease the efficiency of the part
Moreover, fundamental ideas to integrate the SALICIDE processes can be
summarized in three ideas:
1. On the gate: formation of phase in low dimensions in thin lines of poly-silicon
and small areas of single Si crystal in source/drain regions, morphologic and
thermal stability of gate electrode-Silicide/Poly-Si.
2. On the source/drain: contact resistance between the silicide and source/drain
and the integration of joint regions of source/drain.
6.2 Silicides Specifications 191
3. Between the gate and source/drain: the bridge between gate and source/drain
regions.
6.2.3 Transition from TiSi2 to NiSi
Except the application of silicide as a barrier layer in contact with the common
side of silicon and metal, Silicide was firstly used in LSI6 as a poly-side (the
electrode gate of poly silicon/silicide). The poly-side line MoSi2 was one of the
first applications of poly-side in DRAM7 in early 1980. Then the poly-side WSi2
was used for electrode gate of logic circuits LSI in mid 1980, due to its low
resistance compared with MoSi2. Application of TiSi2 due to its low resistance
compared with WSi2 and its low contact resistance with both types of silicon, and
also it’s high thermal stability goes back to early 1990.
When the MOS parts’ dimensions are minimized to 0.2 lm or less, the for-
mation of TiSi2 faces troubles. TiSi2 has two structural phases: C49 and C54. The
phase C54 is more sought to be used in these parts due to its lower special
resistance and higher stability. The resistance of C49 has been reported between
60–80 lXcm and that of C54 between 15–20 lXcm. When the dimensions of the
part decrease, the transition from C49 to C54 gets harder. The cause of this
difficult transition is connected with low density of C54 nucleuses inside the C49
network. Since the transition of C49 phase to C54 is a process controlled by
nuclear stage. On the Si lines, if the line thickness is less than the average distance
between two nucleuses of C54, the formation of C54 phase will be dominated in
single-manner development. This single-dimension development causes non-
complete transformation of C49 to C54 and increases the resistance. Decreasing
the dimensions of the part leads to the decrease of the temperature in which TiSi2
starts to form. One of the ways to prevent this is to develop C54–TiSi2 in thin
lines, and also making the Si amorphous with the signal ion. In another different
approach, the application of slow-fusible like Nb, Mo, Ta, and W has been sug-
gested to form C54–TiSi2.
The problems related to TiSi2 in late 1990, led to the replacement of TiSi2 by
CoSi2 in using lines thinner than 0.2 lm. CoSi2 has a lower resistance compared to
C54–TiSi2. Regarding the technology based on Co, it seems that Co-SALICIDE
has specifications like high formation temperature, oxygen impurities, high con-
sumption of Si in forming silicide, formation of pores and inter-facial irregulari-
ties. High consumption of Si creates thick layers and creates problems in forming
thin layers (less than 100 nm), so consumption of a suitable silicide free of all
these problems will be necessary in manufacturing future parts.
6
Large Scale Integration.
7
Dynamic Random Access Memory.
6.2.4 NiSi Salicide Technology (Self-Aligned Nickel Silicide)
It is expected that NiSi is a good alternative for TiSi2 and CoSi2 in technologies
which have 100 nm scale and smaller. In fact, NiSi has some fundamental
advantages for CMOS processes including:
1. Formation of silicide layers in low temperatures
2. Little consumption of silicon
3. Void of undesirable bridging specifications
4. Little mechanical tensions
5. Having no effect of thin line on surface resistance
6. Low contact resistance to both types of Si (n and P)
7. Independence of resistance of silicide layer from decrease of thickness of
connection lines
The formation of self-aligned silicide happens after the formation of source/
drain. Therefore, the temperature formation of silicide must be low enough to keep
the joint thin in under 100 nm CMOS technologies. NiSi has the lowest formation
temperature among all the silicides, and the thermal stability interval is
350–750C. For TiSi2, the thermal stability interval is very limited. Contact
resistance of TiSi2 is high before 800C, due to the presence of C49 crystal phase.
Between 850C and 950C it decreases due to the formation of phase with for-
mation of C54. Above the 950C, due to the accumulation of surface resistance, it
increases. In the other words, the contact resistance of NiSi gets stable and min-
imized between 350C and 750C. The increase of resistance above 750C is due
to the fusion of phase from NiSi to NiSi2. Therefore, NiSi is thermally suitable for
the technologies under 100 nm. In the other words, it must be kept in mind that the
temperatures of processes after the formation of silicide must not exceed 750C
[24–37].
6.3 Size Effect in Sensing Characterization
Tan et al. [38] prepared non-equilibrium nanocrystalline xSnO2-(1-x)a-Fe2O3

powders by using the mechanical alloying technique. The thick film screen
printing technology is then employed to fabricate these ethanol gas sensors. Their
particle size and structural properties are systematically characterized using X-ray
diffraction (XRD) and transmission electron microscopy (TEM). The gas sensing
characteristics are also measured. Based on the experimental results, it was
observed that particle size of the powders is drastically milled down to about
10 nm after 24 h of high-energy milling. A very high gas sensitivity value of 845
for 1000 ppm of ethanol gas in air has been obtained. New structural model for
these non-equilibrium nanocrystalline xSnO2-(1-x)a-Fe2O3 materials explains
both the lattice expansion of these high energy mechanically alloyed powders as
6.3 Size Effect in Sensing Characterization 193
well as the charge neutrality in terms of additional oxygen dangling bonds at the
nano-sized particle surfaces. It is those enormous oxygen-dangling bonds at the
particle surfaces that give rise to the high gas sensitivity. The sensors are found to
be 32.5 times more selective to the ethanol gas compared to CO and H2 gases.
The increase concern over safety in civilian homes and industrial activities has
generated great interest for reliable gas detection. Many thick film metal oxide
semiconductor gas sensors based on their resistive changes, such as SnO2 and
Fe2O3, have been commercially designed to detect toxic gases (e.g., CH4, CO, and
NO2). Nano-sized materials have been widely used to produce new semiconductor
gas sensors, owing to the great surface activity provided by their enormous surface
areas. Hence, they are expected to exhibit higher gas sensitivity. Being a promising
gas sensing material, nano-sized a-Fe2O3 powders have been prepared by various
methods, including chemical co-precipitation, sol–gel process, metallo-organic
deposition (MOD), and plasma enhanced chemical vapor deposition (PECVD).
These methods are basically chemical processing techniques to build homoge-
neous structure on an extremely fine scale of a few nanometers from the molecular
level. Tan et al. [38] used a different technique called the high-energy ball milling
technique to obtain nano-sized a-Fe2O3-based powders as the sensing materials.
In this technique, the decrease of the particle size into fine powders of a few
nanometers arises from the high-energy impacts during the collisions. This
method, which is also known as mechanical alloying, has recently been used
to prepare nano-sized SnO2-(a-Fe2O3)-based powders with the grain size down
to 8 nm for gas sensing. Such initially immiscible, mechanically alloyed SnO2-(a-
Fe2O3) materials are far from their equilibrium state. It is suggested that the
content of Sn4+ ions may play an important role in the gas sensitivity. However,
the sensing mechanism in this SnO2-(a-Fe2O3) system has not been well under-
stood because of the lack of a complete understanding of the microstructure of the
materials.
Tan et al. [38] have illustrated a promising method of using mechanical
alloying in the preparation of nano-sized a-Fe2O3 materials for gas sensing
applications. In particular, the sensor has shown good ethanol gas sensitivity
values of as high as 845 at 1000 ppm in air. The sensor is selective to ethanol gas
Fig. 6.5 Correlation

between grain size and
sensitivity for different
milling times, reprinted with
kind permission from
Tan [38]
over carbon monoxide and hydrogen gases. The gas sensitivity is also found to be
very stable. These excellent experimental results can be explained by the fact that
such mechanical alloying materials have nano-sized particle grains and exhibit
enormous oxygen dangling bonds at their particle surfaces. Figure 6.5 shows
correlation between grain size and sensitivity for different milling times while
Fig. 6.6 illustrates TEM micrograph for powders after different milling times.
Fig. 6.6 TEM micrograph

for powders after (a) 2 h and
(b) 120 h of milling,
reprinted with kind
permission from Tan [38]
6.4 NiSi Thermal Stability 195
6.4 NiSi Thermal Stability
6.4.1 NiSi Transition to NiSi2 in Dual Ni-Si System
Thermodynamically, the formation of silicide is a result of decrement in reaction’s

free energy. When a metal is heated by contacting the silicon, and silicide is
formed, the silicide phase is dependent on the formation temperature. In Ni-Si
system (Fig. 6.7) and in the temperatures around 200C, the NiSi2 is formed, in
temperatures around 350C the NiSi is formed, and in temperatures around 750C
NiSi2 is formed.
Contrary to the Ni2Si and NiSi situations, NiSi2 development is non-uniform.
Phase NiSi is stable to the temperature 750C, NiSi reacts with the silicon sub-
layer to form NiSi2 which looks like the development of islands in NiSi network.
An irregularity is seen in the common line of Silicide-Si. This irregularity is
caused by the development of branches in some parts of the layer. The concentric
development of the particles, reminds us of dendrite development inside the pillar
particles. By time, more NiSi aniline is transformed into NiSi2 and other NiSi2
particles develop in order to reach each other. These big particles seem to be
composed of smaller pillar particles. Numerous factors like temperature and the
structural condition of previous phase seem effective in defining the new phase.
NiSi layer consists of particles with different crystal structures (cubic and
orthorhombic). Adjacent particles are aligned optionally and cause the formation
of some big particles. In temperature 700C and after annealing, 5 min of swelling
effect of each particle is seen under the silicon layer, which makes the common
line of Si-Silicide have waves. This is direct effect of penetration of Ni network
from NiSi into Si sub layer in the process of formation of NiSi2. A large portion of
Ni transfer is in the form of network penetration compared with penetration into
the border of particles, and this can be due to the effects of swelling. The effects of
swelling also depends on the structure, for instance for orthorhombic structure, the
penetration ratio is low; therefore, the swelling ratio also decreases [24, 34, 35,
39–47].
6.4.2 Pt Effect in Increasing Thermal Stability
Pt and Ni have the same metallurgic behavior. In a crystallographic view, NiSi and
PtSi have orthorhombic MnP structure, which is belonging to Pnma spatial group.
Therefore, it can be expected that NiSi and PtSi are well solved in each other, and
Fig. 6.7 Stages of formation

of different phases based on
temperature (C)
so increase NiSi2 nucleus-formation temperature. Some researchers have studied

the effect of little (about 5%) in thermal stability of NiSi layer on the surface of
Si(111) and Si(100). XPS8 and XRD9 together show the increase of thermal sta-
bility until the temperature 850C. The constant negative section of NiSi for the
second sample has of high stability to 850C. Moreover, by increasing the tem-
perature, the difference between bonding energy decreases, which shows that Pt
has a constant distribution in NiSi structure. This result is also confirmed by XRD
spectrum and for the sample without platinum, NiSi2 is formed in the temperature
750C, but for other samples the formation of NiSi2 is delayed until the temper-
ature 900C.
XRD spectrum shows some of the high-pressure textures for NiSi, which lar-
gely decreases energy for the common line of NiSi/Si compared with poly crystal
NiSi layer without the Pt. As it was mentioned, PtSi and NiSi have the same
structures. Therefore, Gibbs free energy NiSi, G(NiSi) is largely decreased due to
the formation of NiSi(PtSi). On the other hand, Pt is not solved properly in NiSi2,
so it creates a little change in G(NiSi2). Hence, we can ascribe NiSi2 nucleus
thermal rise to the decrease of G(NiSi), and the rise of common line energy can be
attributed to the trend to the formation of NiSi with high-pressure texture on the Si.
In fact, the formation of NiSi2 is done because of the following reaction.
Ni1x Ptx Si þ ð1 xÞSi ! ð1 xÞNiSi2 þ xPtSi ð6:1Þ
This shows that the presence of PtSi together with NiSi2 will increase Dr in
comparison with the normal reaction NiSi þ Si ! NiSi2 . Besides, the formation of
Ni1x Ptx Si largely decreases Gibbs energy:
DG ðNi1x Ptx SiÞ ¼ ð1 xÞG ðNiSiÞ þ xGðP þ SiÞ TDSmix ð6:2Þ
Where:
DSmix ¼ R½x ln x þ ð1 xÞ lnð1 xÞ ð6:3Þ
So the change in Gibbs energy for the relation (6.1) will be as:
DG1 ¼ ð1 xÞ½GðNiSi2 Þ GðNiSiÞ GðSiÞ þ TDSmix ¼ ð1 xÞDG0 þ TDSmin
ð6:4Þ
For x = 0.05, the TDSmin will be about 2 kg/mol in 1100 K, which is of the DG0
degree. Therefore, the driving force to transform the reaction NiSi ! NiSi2 has
decreased.
Some researchers studied the Pt inter-layer effect in stabilizing the NiSi layer on
Si(111). The results show that by increasing the temperature, the direction of (200)
NiSiII(111)Si will change into the direction (002) NiSi11(m)Si. Such a
8
X-Ray Photoelectron Spectroscopy.
9
X-Ray Diffraction.
transformation can not be seen in the previous work. The texture of NiSi layer
from (200) NiSi11(111) into (002)NiSi11Si(111) will be transformed in high
temperature after aniline. NiSi2 nucleus will take place in NiSi texture after this
transformation. This transition in the texture will consume some kinetic energy of
atoms and the NiSi2 nucleus configuration will be delayed. The comparison of
surface resistance in two samples of Ni/Si and Ni/Pt/Si according to aniline
temperature in the Fig. 6.8 confirms the previous discussions on the delay on
formation of NiSi2.
As mentioned before, by decreasing the dimensions of micro electronic parts,
the thickness of joints will also decrease. For instance for a line thickness of
130 nm, the silicide layer will be about 34 nm. So, studying the thermal stability
will have great importance by decreasing the thickness of metal layers signaled on
Si and aniline. This has been studied by evaluating the following systems which
have been annealed in different temperatures.
A. Ni (50 nm)/Pt(4 m)/Si(100)
B. Ni(25 nm)/Pt(2 nm)/Si(100)
C. Ni(12.5 nm)/Pt(nm)/Si(100)
Studying NiSi(211) peak situation in the temperature 800C for one hundred
samples shows that Pt percentage in all the samples is a fixed value, therefore the
difference in transition from NiSi to NiSi2 in samples; is not only related to the
layers’ thickness. The effect of thickness of the layer on thermal stability of NiSi in
Ni/Pt/Si(100) system has been shown in Fig. 6.9. In the sample A in temperature
X
840C, the surface resistance is increased from 1.7 to 2.3 Sq . Considering the XRD
results, the increase in surface resistance is due to the formation of NiSi2. In the
sample B, transition temperature happens at 80C and in the sample C, it remains
Fig. 6.8 Changes of surface resistance according to baking temperature for Ni/Si and Ni/Pt/Si
systems
Fig. 6.9 Surface resistance according to different baking temperatures
with the surface resistance even after 880C. Therefore, we can understand that by
decreasing the thickness in Ni/Pt/Si(100) system, thermal stability is increased. As
we said before, the increase of platinum, decreases jDgj and this leads to increase
of activation energy for nucleus. Also decrease of jDgj will ultimately increase the
critical radius for the nucleus r .
As only the nucleuses with radiuses bigger than r are allowed to develop, when
the layer’s thickness is low, the development will be limited in the direction of
perpendicular with the layer’s surface, and the nucleus will be delayed. We can
have a numerical estimation from the value of r . For the normal reaction
NiSi þ Si ! NiSi2 , the quantity equals 2:35 kcal kJ
mol or 9:83 mol. Considering the
structure (cubic, CaF2) and constant network of NiSi2 (a = 5.4 Å), Gibbs free
energy in the unit of volume will be Dg0 ¼ 413 cmJ 2 . Considering the critical
radius:
2b Dri
r ¼ ð6:5Þ
3a Dg0
And also that Dr, change in inter-layer energy is of 104 cmJ 2 degree, the approx-
imate value of r for NiSi2 will be about some nanometers.
6.4.3 Pd Effect in Thermal Stability
Palladium, Pd, increases thermal stability of NiSi like Pt do. It is interesting to

compare how Pd and Pt increase thermal stability. Some researchers have dealt
with this issue by studying Ni/Pt/Si and Ni/Pd/Si systems. In their study, Ni’s
thickness has been chosen as 100 nm and Pt and Pd’s were equally picked as 8 nm.
For the sample having Pt, a high pressure peak NiSi(200) exists and this means
that there is a strong alignment in this structure. Such a texture is not seen in the
sample having Pd. Aniline in temperature 900C shows that in samples containing
Pd, transition is done fully, but in samples with pt, NiSi(002) phase exists next to
the formation of NiSi2, which prevents the completion of the transition. That is in
presence of Pt, the system shows more stability. These results are compatible with
the results produced by Raman analysis.
Pt and Pb both increase nucleus activation energy NiSi2, because PdSi and PtSi
have a similar structure with NiSi and form a solid solution. But this increase is
more for Pt, and it is because of justification direction NiSi(200)11Si(111). This
direction decreases inter-layer energy between NiSi and Si(111) which rises Dr
and DG , so that we have:
DG ðNi=Pt=SiÞ [ DG ðNi=Pd=SiÞ [ DG ðNi=SiÞ ð6:6Þ
Comparison of thermal stability of these three systems is there in Table 6.1 with
considering inter-layer energy effect r between NiSi and Si, and the driving force
jDGj for nucleus configuration. Increasing the inter-layer thickness Pd will
increase the system’s thermal stability. For example, with Pd thicker, it shows
more stability and when the thickness increases to 7 and 10 nm, nucleus config-
uration of NiSi2 will be delayed until 900C.
6.4.4 Ge Effect in Thermal Stability
Ge also increases temperature in nucleus configuration NiSi2. For system Ni/Ge/Si

the phase transition from NiSi to NiSi2, even at 900C will not complete in
comparison with NiSi (800C), and it proves a considerable rise in nucleus con-
figuration of NiSi2. A layer’s conductivity also depends on its morphology, since
after aniline at 800C, the NiSi layer is developed on Ge/Si evenly, and it gets
irregular and uneven by increasing temperature. The accumulation of atoms takes
place by forming NiSi2. The temperature for nucleus configuration in the reaction
of layer Ni with sub layer Si1-xGex increases too. In both cases, we could attribute
temperature rise to the entropy effect of NiSi–NiGe mixture. NiGe has a Mnp
structure, similar to that of NiSi, and so Ge is well solved in NiSi but not in NiSi2.
So, the level of free energy decreases as TDSmin and the pure value decreases,
consequently activation energy DG related to NiSi2 nucleus configuration also
increases.
Table 6.1 Comparison of thermal stability of NiSi with Pt and Pd barriers

r decrease jDGj decrease Thermal stability sequence
Ni/Pt/Si(111) Yes Yes 1
Ni/Pd/Si(111) No Yes 2
Ni/Si(111) No No 3
6.4.5 Co and Ir Effects in Thermal Stability
Some researchers have shown that using Ir and Co as penetration barriers, not only
improves thermal stability, but considerably decreases leaking flow in thin joints
with depth of 40 nm. In Ni/Si, the development of NiSi2 plates in the direction
(111) will increase surface resistance and leaking flow. The rise in stability and
little leak of the flow is probably due to the very even common line in samples
containing Ir and Co.
6.4.6 Capsulation and NiSi Thermal Stability
The contaminations caused by oxygen during silicide process might be resulted

from following sources: (1) aniline environment, (2) Oxygen accumulated during
metal’s layer signaling (3) inter-layer oxide in silicon/metal common line. Inter-
layer silicon oxide in the common line of Ni/Si decreases the reaction between Ni
and Si too. So taking methods to absorb oxygen from Si surface is necessary.
Ti Capsulation also decreases the inter-layer oxides. Also the Ti cap increases
regularity and thermal stability, and also decreases the leak in flow. Before
annealing, Ti surface is covered with a TiO2 oxide layer. During aniline at 500C,
two important things happen: First, Ti cap has more reaction with oxygen. Second,
Ti atoms in cap penetrate into Ni layer, and accumulate in the common line of Ni/
Si. Aniline at 600C not only forms NiSi, but also forms Ti–Ni–Si (TiNiSi and
(TiNix)Siy) and a layer of TiOSi2. The formation of NiSi at 600C shows the
restoration of SiO2 by Ti.
SiO2 cap layer also delays the surface resistance. For the capped samples, the
surfaces get more irregular with increasing temperature. The arrows show areas
not covered by silicide. The density of these areas is more for capped samples.
Using the cap layer also forms an even layer of silicide. Using the cap also
decreases the development of furrows, and the morphologic behavior of NiSi
layers’ surface, in cap case or without the cap, are bound with the furrows. In the
other words, using cap layer delays the appearance of thermal furrows and so the
accumulation of NiSi atoms, that is decreases the cap layer of surface energy NiSi.
Finally, one of the most important challenges in miniaturizing the parts in
electronic industry that is, increasing the resistance when the dimensions decrease
was studied here. By decreasing the thickness, the resistance increase in joints. We
also mentioned some specifications and capabilities in using TiSi2 (phase C54) and
CoSi2. TiSi2 has two structural phases of C49 (high resistance) and phase C54 (low
resistance). By decreasing the thickness of lines in joints; transition from high
resistance phase to low resistance phase becomes more difficult. Therefore, using
TiSi2 for dimensions lower than 200 nm faces the problem of resistance rise.
CoSi2 as an alternative for TiSi2 has some basic problems despite the low resis-
tance, including high consumption of silicon and high formation temperature
(550C). High consumption of silicon makes it more difficult to develop this layer
in nanometer dimensions. Silicide Nickel (NiSi) with low special resistance, even
in dimensions lower than 100 nm, and with less silicon consumption, lower for-
mation temperature (350C), etc. can be a good replacement for TiSi2 and CoSi2.
The only problem relating the limited thermal stability is due to the fusion into
a phase with the resistance more than NiSi2 at 750C, and the taking place of
Agglomeration phenomenon on the surface. We mentioned some of the studies by
researchers in recent years, like using different types of impurities or taking
penetration barriers to improve thermal stability of NiSi, and we studied the
reasons for thermal stability rise in the framework of classic theory of nucleus
configuration and the effect of entropy mixture [48–57].
6.5 Size Effect in Optical Properties of Nanostructured Films
Kale et al. [58] fabricated cadmium selenide nano-crystallites onto amorphous

glass substrate from an aqueous alkaline medium, using chemical bath deposition
method at room temperature. The samples are annealed in air for 4 h at various
temperatures and characterized by structural, optical and electrical properties. The
as-deposited CdSe layers grew in the nanocrystalline cubic phase, with optical
band gap, ‘Eg’ 2.3 eV and electrical resistivity of the order of 106 X cm. After
annealing metastable nanocrystalline cubic phase transformed into stable poly-
crystalline hexagonal phase. Depending upon temperature, decease up to 0.6 eV
and 103 X cm were observed in the Eg, and electrical resistivity, respectively.
These changes have been attributed to the increase in the grain size of the CdSe
crystallites.
Presently nanocrystalline materials have opened new chapter in the field of
electronic applications, since material properties could be changed by changing the
crystallite size and/or thickness of the film. New applications in various fields are
also emerging. Development of such materials, whose structural, electrical and
optical properties could be controlled, will be useful many ways. For example
optoelectronic devices, particularly solar energy conversion devices could be
modified accordingly.
The synthesis of binary metal chalcogenide of groups II–VI semiconductors in a
nanocrystalline form has been a rapidly growing area of research due to their
important non-linear optical properties, luminescent properties, quantum-size
effect and other important physical and chemical properties. The semiconductor
nanocrystallites belong to state of matter in the transition region between mole-
cules and solids. Their physical and chemical properties are found to be strongly
size dependent. The properties of materials prepared by different methods are
critically dependent on the nature of preparation technique and subsequent heat
treatments like annealing in air, vacuum or different gaseous environments like H2,
N2, Ar, etc. The micro-structural features of nanocrystallites are found to govern
their electro-optical behavior. Cadmium selenide (Eg = 1.7 eV) is one of the
promising semi-conducting material that has been studied for application in solar
cells, c ray detectors, thin film transistors, etc. A number of workers have chem-
ically prepared CdSe thin films. However, little attention has been paid to the
various properties of chemically deposited CdSe thin films.
Kale et al. [58] report on the room temperature chemical deposition of CdSe
thin films from an aqueous alkaline medium. In order to get good quality CdSe thin
films, the preparative parameters such as concentration of cadmium, deposition
time and pH were optimized. Freshly deposited thin films may contain many
defects such as voids, pinholes, etc. Annealing of thin films reduces the defects and
increases crystallite size along with recrystallization process. Kale et al. [58]
deposited the CdSe thin films by aqueous alkaline medium at room temperature
grows with nanocrystalline phase with band gap 2.3 eV and electrical resistivity of
the order of 106 X cm. Air annealing was found to increase crystallinity of the
CdSe films along with recrystallization process that changed nanocrystalline to
metastable cubic to stable hexagonal phase (673 K) at higher annealing temper-
ature. The crystallite size of the particles was increases as a result of increasing the
annealing temperature. Consequently, the electrical resistivity was decreased and
CdSe films showed ‘red shift’ of 0.6 eV. Figure 6.10 shows plot of CdSe
crystallite size versus annealing temperature of CdSe thin films. Tabulation of
crystallite size, band gap ‘Eg’, electrical resistivity and activation energy of
as-deposited and annealed CdSe thin films can be seen in Table 6.2.
Fig. 6.10 Plot of CdSe

crystallite size versus
annealing temperature of
CdSe thin films, reprinted
Lokhande [58]
6.5 Size Effect in Optical Properties of Nanostructured Films 203
Table 6.2 Tabulation of crystallite size, band gap ‘Eg’, electrical resistivity and activation
energy of as-deposited and annealed CdSe thin films, reprinted with kind permission from
Lokhande [58]
Thin films Crystallite Band Electrical Activation energy (eV)
size (Å) gap ‘Eg’ (eV) resistivity ðX:cmÞ
HR LR
As-deposited 40 2.3 3.25 9 105 0.86 0.34
373K 60 2.0 9.58 9 104 0.79 0.31
473K 80 1.8 5.38 9 104 0.72 0.27
573K 120 1.8 8.23 9 103 0.69 0.18
673K 180 1.7 1.17 9 103 0.65 0.16
HR high temperature region and LR low temperature region
Du et al. [59] prepared nano-copper films by DC magnetron sputtering. Their

reflectivity and transmittivity to electromagnetic wave in infrared region were
measured with Fourier Transformation Infrared Spectrometer (FTIR), by which
their complex optical constant and permittivity were obtained. The results show
that the complex optical constant and permittivity of nano-copper films depend
upon the film thickness. This dependence is correlated with microstructure tran-
sition during the film growth.
Nano-sized metal films have been of considerable interest both from funda-
mental point of view and for potential applications in photonics and electronics
devices based on their unique properties which are generally very different from
bulk materials. For example, it has been shown that electrical conductivity, r, of
ultrathin metal film decreases apparently with its decreasing thickness. Strong
interaction between metal films and electromagnetic wave occurs when the film
thickness decreases to nanometer scale. Meanwhile, electromagnetic compatibility
(EMC) of overall quality of nanostructured materials, devices and systems
becomes a more and more serious question with decreasing size and increasing
working frequency of electronic systems. In those cases, a precise knowledge on
the complex optical constant and complex permittivity of ultra-thin metal films, for
a thickness range from a few nanometers up to opaque layer, is very important.
Copper as a kind of metal with high conductivity, electromagnetic perfor-
mances of its films have been widely studied for the application in Integrated
Circuit (IC) and microelectronics devices as interconnection parts, in semimirrors
as UV radiation filters and as telescope mirror layers. Du et al. [59] deposited
nano-copper films by magnetron sputtering method. Since the complex optical
constant and the complex permittivity are not directly measurable quantities, they
are calculated with reflectivity and transmittivity of copper films to electromag-
netic wave. At the same time, the thickness dependence of nano-copper films on
complex optical constant and permittivity are analyzed.
Du et al. [59] measured the reflectivity and transmittivity of nano-copper films
to electromagnetic wave in infrared region, by which their complex optical con-
stant and permittivity, both the real and the imaginary parts are calculated. All
these parameters are essentially dependent on the film thickness. This dependence
should be considered in application of nano-copper film. The dependence of

electromagnetic parameters on the characteristic size provides new possibilities for
designing high performance electromagnetic functional materials and devices. The
evolution of the film microstructure plays an important role in the size effect of
nano-copper film on complex permittivity. Figure 6.11 shows dependence of
reflectivity (a), transmittivity (b) of nano-copper films on thickness in infrared
region. Figure 6.12 also shows dependence of complex optical constant real and
imaginary parts of nano-copper films on thickness in infrared region.
Tang et al. [60] reviewed studies on ultraviolet stimulated emission and lasing
observed at room temperature from nano-structured ZnO thin films. The nano-
structured ZnO thin films were grown on sapphire substrates using Laser-Molec-
ular-Beam-Epitaxy (L-MBE). The thin film was consisted of regularly arrayed
hexagonal nano-crystallite columns, whose facets form natural micro-cavities.
These nano-crystallites confine the centre-of-mass motion of excitons. As a result
of the quantum size effect, the oscillation strength of the excitons is largely
Fig. 6.11 Dependence of

reflectivity (a), transmittivity
(b) of nano-copper films on
thickness in infrared region,
reprinted with kind
permission from Du [59]
Fig. 6.12 Dependence of

complex optical constant real
part (a), imaginary part (b) of
nano-copper films on
thickness in infrared region,
reprinted with kind
permission from Du [59]
enhanced, which is favored to the radiate recombination of exciton at room

temperature. Excited using the frequency-tripled output of a YAG laser, the nano-
structured ZnO thin film showed strong ultraviolet lasing at room temperature with
a threshold as low as 24 kW/cm2. At a moderate pumping intensity, the room
temperature stimulated emission is associated with an exciton-exciton collision
process. At higher pumping density, the excitons are dissociated, and the ultra-
violet stimulated emission is dominated by an electron–hole plasma recombination
process. Because of the large enhancement of oscillator strength of the excitons,
the optical gain of the stimulated emission measured at room temperature reaches
as high as 320 cm-1, which is an order higher than that observed in bulk ZnO
crystals. In comparison with the electron–hole plasma stimulated emission in most
of commercial semiconductor lasers, the excitonic stimulated emission can be
realized at relatively low external pumping density. The observation of excitonic
lasing effect at room temperature might be valuable in realization of practical
ultraviolet semiconductor laser devices.
Compact short-wavelength semiconductor laser diodes (SLDs) present vast

possibilities in many high-technology applications. For example, in the area of
optical storage, the storage density is limited by the size of the diffraction spot
which is proportional to the square of the laser wavelength. Hence, the availability
of short-wavelength SLD means much greater density of data can be stored on a
disc. Towards this end, InGaAlP-based yellow SLDs had been developed with
wavelength as short as 650 nm. Since this achievement, there was no report of
shorter wavelength SLDs until 1990, when the first demonstration of green–blue
lasing actions in ZnSe-based heterostructures was reported, followed soon by the
successful operation of ZnSe-based laser diode in 1991. However, practical short-
wavelength SLDs are still not available because the lifetime problem. Recently,
room temperature (RT) ultraviolet (UV) stimulated emissions and laser emissions
have been reported in metal nitride systems as a result of the breakthrough in the
growth of high-quality GaN-based heterostructures and successful development of
p-type doping.
ZnO, as an oxide, is superior over nitrides and selenides in thermal stability as
well as in resistance to chemical attack and oxidation. Its RT band gap is 3.37 eV
which is suitable for fabricating UV optoelectronic devices. Its large exciton
binding energy (60 meV) should in principle favour efficient RT excitonic emis-
sion. Because of the current difficulty in heavy p-type doping, research works have
been carried out for study on the properties of stimulated emissions using electron
beam pumping and optical pumping for bulk ZnO crystal at cryogenic tempera-
tures. Few works have been reported on the UV stimulated emission at room
temperature in bulk ZnO crystal, but no emission spectra were given.
Tang et al. [60] reviewed their progress on ZnO nano-crystal ultraviolet laser
research. The nano-crystallite thin films grown by the laser molecular beam
epitaxy (L-MBE) consist of self-assembled, ordered arrays of hexagonal nano-
crystallites. They described the structure and formation mechanism of the hex-
agonally shaped nano-crystals. The facets of the close-packed and ordered
hexagonal nanocrystallites form natural lasing cavities. The optical gain is shown
to be of excitonic nature and has a very large value that is dependent on the size
of the nano-crystallites. The peak gain value is as high as 320 cm-1 for a 55 nm
thick film, an order of magnitude larger than the largest known value for bulk
ZnO. The large gain is attributed to the modification of the spontaneous emission
created by the dielectric photonic structure of these films. The observations
reported demonstrated that ZnO may be a viable material for short-wavelength
optoelectronics application. Figure 6.13 shows lasing threshold as a function of
film thickness.
Bilotsky et al. [61] studied the size dependence of electron-lattice energy
exchange in nanoparticles. Both surface and bulk energy exchange parameters are
examined and it is demonstrated that the bulk energy exchange has non-monotonic
oscillations versus size of the particles. It has been found that the amplitude of
such oscillations increases with decreasing a particle size until the critical size
reaches Lc. These bulk interaction related oscillations disappear for the particles
less than Lc, and only the surface energy exchange remains as the energy flow
Fig. 6.13 Lasing threshold

as a function of film
thickness. An excitation with
a size of 500 lm 9 30 lm
stripe was used, reprinted
Tang [60]
between electrons and phonons subsystems. It has been shown that there exists an
interval of particles sizes with total energy exchange of few orders less than in
massive bulk metals. This condition is crucial for existence of hot electrons in
stationary conditions in metal nanoparticles, metal island films and thin films as
have been observed experimentally.
Hot electrons in metal nanoparticles have been discovered experimentally, or
more specifically, the lighting of gold nano-islands film on a dielectric was
observed when a BIAS voltage was applied to the film. Electrical current flow
resulted radiated light along the system of tunnel-connected island metal films
(IMF). Later a new phenomenon has been observed—electron emission and non-
linear current–voltage characteristics in IMFs altogether with lighting. These
observations were made with applied voltage bias of *10–30 V but the appli-
cation of the same voltage to continuous (thick) films or bulk metallic samples did
not produce above-mentioned phenomena.
These phenomena were explained by a hot electrons concept. It should be
noticed that hot electrons were observed in stationary condition in IMFs gold
samples only but they did not appear in continuous films or bulk metal. However,
hot electrons can be also obtained in IMFs by irradiation of a laser beam. Par-
ticularly, the irradiation with a pulsed CO2 laser (s * 0.2–1.0 ls) has been used.
The duration of the pulse is much larger than all relaxation processes times in
IMFs. The same phenomena (such as lighting and electrons emission in voltage
applied experiments) have been observed in laser irradiation experiments.
Therefore, the hot electrons appeared in quasi-stationary conditions in these
experiments as well.
Bilotsky et al. [61] studied the total electron–phonon energy exchange in
small metal particles which size is less than free path of electron–phonon col-
lisions. This expression contains bulk and surface terms. The bulk contribution
oscillates as the function of the particle size. It is important that the long wave
acoustics phonons generated by the hot electrons can be in non-equilibrium state
with others phonons. Thus, the use of electron–phonon collisions integral
Fig. 6.14 Electron-phonon

energy exchange constants
g(x), g0(x) versus x, reprinted
Bilotsky [61]
approach with Plank distribution function of phonons could be incorrect. As it

has been mentioned above, the hot electrons have been observed in stationary
conditions only in IMFs. Nevertheless, there is one common electron–phonon
energy exchange feature for both IMFs and thin metal films. Microelectronic
devices electric conductivity with such as thin conductors may be quite sensitive
to a film thickness. Figure 6.14 shows electron–phonon energy exchange con-
stants g(x), g0(x) versus x.
6.6 Optical Coatings: Using Ultraviolet Light Block Layers
For a long time, removing and destruction of different substructures and substrates,
such as polymer wooden sub-layers under ultraviolet light, was an important
problem for construction and application of these pieces in different poor climates.
During recent years researchers were able to solve this problem using nano-
materials, particularly ones for nano-coating. It the past different materials were
used, which did not enjoy decent quality and had defects during efficient
absorption of ultraviolet light. Among disadvantages of traditional methods one
can mention decrease of substance transparency and deactivation of ultraviolet
resistant coating before end of piece life.
Through new method, nano-coating of surface is performed with pure and
impure ZnO2 and CuO nano-particles. Nanodur is one of important companies at
this field. Using new coating leads to sufficient absorption of ultraviolet light.
Compared with traditional ones, these coatings are of longer lifetime. Other
advantages of these coatings are their higher resistance against cracking and
abrasion, apparent transparency, and lack of deformation and color change. One of
most important advantages of anti-ultraviolet nano-coating it their permanent
6.6 Optical Coatings: Using Ultraviolet Light Block Layers 209
activity, in contrary with organic materials which deactivate after a while. These
coatings can be applied to optimize most of pieces [62–74].
6.7 Surface Improvement for Making Fog and Vapor

Resistant Layers
Researchers succeed to produce a fog and vapor resistant nano-metric surface

through improving plastic and poly-carbonate surfaces. At this method a new
formulation (Clarity Fog Eliminator) was applied to prevent development of fog
and vapor on surface. These products can be used in lightproof, face protector, and
common or sport eyeglasses. As well as mentioned applications, this product is
even applicable in refrigerator environments.
6.8 Production of Pieces with Nano-Coating
Nanofilm Company is to produce products which use nano-coating technology. In

most of these products coated part serves as main piece part and is considered
among most important applications of nano-coating. One of applied coatings is
one which repels water, snow, ice and other similar pollutions from the glass’s
surface. It is expected to use these glasses in automobile industry. Among other
applications of these coatings one can name other cases such as eyeglasses.
Another fabricated coating is steam resistant nano-coating for sport and military
utilities, optical pieces, and customary, safety, and laser glasses. These pieces can
be applied in car windscreen, bath mirrors, and etc. Another type of fabricated
nano-coat is anti-reflection one, which can be appropriately used in interior mirror
of cars and cosmetic cases. The coat prevents glaring reflection of the light.
6.9 Self-Cleaning Glasses
Self-cleaning glasses is addressed to glasses with photo-catalyst metallic oxide

(especially titanium oxide) coatings, which its surfaces have hydrophobic prop-
erties. Due to sunlight or any source of ultraviolet light on activated surfaces these
nano-coatings get activated and develop catalyst properties. Because of oxidizing
feature of glass surface coating, any artifact is broken on the surface and converted
to inorganic aqua-soluble material. Raining or water spraying on surface destructs
surface of contaminator particles and causes to their collapse, for their hydro-
phobic property [75–84].
6.10 Medical and Hygienic Applications
6.10.1 Inorganic Materials Nano-Coating for Medical

Applications
Chemists at UCLA University have invented a new unique nano-coating for

inorganic materials, which is capable to produce them similar to proteins. Using
this method one can apply these particles as a measuring tool for detecting
intercellular activities. Using these products can be followed by significant
achievements in pharmacy and detecting tools. During this method nano-metric
coating particles and quantum wires by fiber amino-acids with short loops (pep-
tides) are used. Through this kind of coating living cell authorize entering and
exiting of particles, due to their similarity with proteins. These inorganic materials
can even be poisonous. The method makes it possible to perform some investi-
gations in living cells at molecular scale, so this is one of most important appli-
cations of nano-technology in biology and medicine.
The method enables us to produce nano-coating on the surface of semi-con-
ductor particles and import them as electronic measuring tools. Among their
important applications one can name their fluorescence light reflection. During this
method different particles can be imported to the living cells and be stimulated by
blue light. Any of these particles have their own particular fluorescence response.
Using different proteins coating with different fluorescence colors on nano-particles
make it possible to use them as biological label. Researchers mention peptide nano-
coating method as a link between organic and inorganic materials. Also, they
consider their application as a method to produce intelligent drugs.
6.10.2 Using Nano-Particle Masks
After onset of SARS, using anti-bacterium masks was of a great interest. Hence,
efforts for fabrication of bacterium and tiny particles filter have been accelerated.
One of interested fields of this part is nano-coating. Traditional coatings are able
to stop bacterium to enter in living cells; in the other word the entrap bacteria on
their coating. However, due to bacteria and other dangerous particles accumula-
tion in masks they should be replaced as often as possible. To deal with this
problem, using nano-coating was of a great interest among researchers. In these
filters TiO2 nano-particles coating or polluted nano-particles of silver are used.
The main advantage of these filters is that they eliminate dangerous bacteria and
organic particles; then applied filter has no need to be replaced and can be used
for a long time. Applying such filters has been focused to prevent bacterium and
virus entrance. As a considerable share of these materials fabrication leads to
using nano-coating with nano-materials, there predicted to be a satisfactory
market.
6.10 Medical and Hygienic Applications 211
6.10.3 Application of Hydroxyapatite Nano-Coating to Design

Prosthesis
IMC (Infromat Company) produces some prosthesis with nano-structured

n-Hydroxyapatite HA coatings which serve as marker layer with electrophoretic
method at common temperatures. In comparison with conventional pieces, newly
made ones are of more compatibility with human body and are much cheaper.
Coating according mentioned method and through nano-structures, compared with
common coating methods, is of so many advantages such as enhancement of
pieces strength, bonds stability, and resistance against corrosion. To examine
features of this kind of coating there have been performed various tests to assess
hardness of these pieces. One of these tests was for evaluation of coated Ti6Al4V
pieces hardness, which reveals up to 3 times increase in cohesion and strength of
surface coating. That mentioned coating is very dense and hard and exhibits a high
resistance against corrosion in human body.
One of existed problems at this method is lack of adjustment thermal for
expansion coefficient of titanium/HAP. This inequality against thermal expansion
coefficient leads to development of stresses in the piece. Another existed problem
during application of these pieces is development of an oxide, with low resistance
against corrosion, at interface of titanium and nano-structure coating.
To solve the problem, IMC has used a glass coating, compatible with human
body. Using this coating at interface of nano-structured coating and titanium the
problem of incompatibility of thermal expansion coefficient can be easily
removed. Besides, using similar coatings it is possible to prevent development of
instable oxide at the interface.
Using nono-structural coating of nano-hydroxyapatite lifetime of pieces has
been dramatically increased. There are different methods for making above-
mentioned nano-structured coating, such as plasma aerosol, chemical deposition,
and electrophoretic. It seems that electrophoretic coating method has higher
compatibilities for different applications.
6.10.4 Using Nanocomposite Coating for Food Packaging
The food is offered in different packages, in terms of the food kind and required
time. In some food the product should maintain its original and natural shape. One
of important points in this field is paying attention on purchasers needs. Consumer
is interested to buy fresh food with least of necessary changes during extra pro-
cesses for increase of food preservation. Since its initiation time, food packaging
industry has been subjected to many changes, based on demands of consumers,
such as improvement of preservation, food health, and food compatibility with
environment. Responding to these needs, there have been various researches in
field of packaging quality and use of new intelligent materials.
Todays, technological achievements in food packaging industry have enabled us

to apply intelligent packaging in order to change conditions and data delivery from
food situation. This package is called active packaging. One applied method, is use
of nano-composite coating to coat plastic layers. Over the time, food releases gasses
and moisture in their packages. In some packaging gas and moisture absorbent are
used, which leads to healthiness and preservation of the food. Some intelligent
coatings show leakage or increase of temperature. Nowadays, there are some
attempts to promote packaging quality through coating of food packages using anti-
microbial coatings. Till now, use of these coatings has not been of much interest.
Regarding available technologies use of these coatings is not economic yet.
However, some active companies in this field hope to produces low cost surfaces
with decent anti-bacterial property—using nano-coating technology—to coat food
products. Another application of nano-coating is production of biosensors, attached
to packages in coating form. Biosensors can offer information about quality of
packaged materials, their state of healthiness, and etc. [85–91]
6.10.5 Antipollution Materials in Shipping Industry
Recently, nano-materials are used in shipping industry as an antipollution and

deodorant agent. Nano-particles are remained in network of antipollution coating
and release their ions over the time, which causes antipollution traits. Todays, use
of Sn-tributyl, once broadly used, is stopped and there is a need for other substitute
materials. Lifetime of materials such as copper oxide and other similar materials is
not efficient for this application, though nano-materials used for this application
seems to be suitable. Polluted Copper oxide or zinc oxide nano-particles can be
efficiently replaced at coating formulation of shipping industry. Researchers have
shown that these materials exhibit a loner lifetime for antimicrobial applications.
6.10.6 Nano-Coating Use Against SARS Virus
Recently, SARS virus is proposed as one of main dangers and there have been so
many concerns about its epidemic issue. To deal with this virus, researchers of
nano-material field have achieved nano-coating, which is a good weapon to stop
this virus activity. These nano-materials include titanium oxide coated with Ag
nano-particles. Researches have shown that release of Ag ions during a long time
to stop activities of these viruses. These coatings with inappropriate ratio of
constituents can cause serious damages to human body. There are some other
researches performed by TN Nanovation. GmbH, which produce a nano-powder,
called Nanozid, which is added as additive to the color, in order to coat diurnal
appliances and tools such as beds and other staffs used in hospitals. These coatings,
as well as the similar ones, can be used in food beverage industry.
6.10 Medical and Hygienic Applications 213
6.10.7 Application of Ag Nanoparticles as Antibacterial Coating
German researchers at Institute for New Materials (INM) have created antibac-
terial surfaces with Ag nanoparticles. Adding a little amount of these materials to
coating make it possible to obtain a big deal of these nano-materials. These
materials can release a considerable deal of Ag ions, which is also able to elim-
inate other pollutions. Different nano-coatings for antipollution goals are available
in the market; however produced compound in this research institute is of a unique
application variety. The coating can be applied in all surfaces which can poten-
tially be harmful for health. Among these materials one can name hospitals,
offices, public places and even houses. These coatings are used on all touchable
surfaces, even metallic, plastic, or glass ones. They can also be useful in appli-
ances with public uses [92–100].
6.10.8 Using TiO2 Nano-Particles to Decrease Environmental

Contaminations
Contaminated materials, especially those caused by oil pollutions, due to trans-

portation process or other similar accidents are among most important sources for
environmental contaminations. Another case of pollution is one induced by
uncontrolled release of industrial wastewater. There are different methods to
decrease pollutions caused by organic materials, e.g. using catalysts for degrada-
tion of organic molecules to harmless ones. Among most important catalysts one
can name TiO2 particles. These particles are coated on efficient substrates and
exposed to ultraviolet light in particular pools. Energy gap of this semi-conductor
is about 3 eV. Due to radiation of ultraviolet light, there develops an oxidizing
property in electron, produced cavity, and the material. Due to oxidization, they
are degraded to some harmless materials, such as H2O, CO2, and other inorganic
materials. Some experiments suggest that a wastewater polluted with oil organic
materials can be completely degraded after 7 days. To improve efficiency of these
nano-particles there also is a use of TiO2 polluted with Fe and Er. Due to pollution
energy gap significantly decreases and oxidization process happens under radiation
with longer wavelength.
6.11 Electrical and Electronic Applications
6.11.1 Production of Transparent Conductor Coatings

by Carbon Nano-Tubes
With respect to broad applications of transparent conductor coatings there have

been developed different materials and methods to produce these coatings.
Among most commonplace methods one can name using ITO coatings.
Regarding achievements in nano-technology, another method is application of
carbonic nano-particles and nano-tubes. In case of broad using these materials
for transparent conductor coating, there would be a dramatic growth in appli-
cation of these coatings. One of famous companies in this field is Eikos which
uses carbon nano-tubes to product conductor coatings. For industrial applica-
tions, produced layers must be of high transparency, suitable conductivity, low
price, decent printability, and flexibility and resistance against environmental
agents. Carbon nano-tubes have efficient electrical and thermal conductivity,
equal to those of diamonds. Regarding their low weights (1/6 of steel’s) this
tubes have considerable hardness. Todays, vaporization of polluted zinc oxide
with InSnO2 in vacuum tube is applied as a standard industrial coating. The thin
film of this material has efficient light transparency and excellent conductivity.
Thin films of ITO are not suitable to coat polymeric surfaces; also conductivity
of pieces considerably decreases through its bending and other types of
deformation.
Metallic nano-particles have fairly high price and very low transparency and
then are not convenient for painting. According to mentioned points produced
transparence conductive coating with carbon nano-tubes is completely efficient,
compared with the other mentioned methods. They only setback of this method is
its lower, but enough, conductivity. For different coatings, depending on type and
application of the coating, different materials are used. Among these materials one
can mention atomic nano-clusters such as quantum particles, inorganic and
molecular particles, nano-tubes with quantum wires, and nano-composites. The
other important used compounds for coating are:
• Silicide, carbide, nitride, and oxide
• Boride, selenaride, fluoride, and various types of sulfides
• Halide, alloys, intermetallic materials, metals
• And organic polymers
6.11.2 Application of Nano-Coating on Solar Cells
Since nano-coating can be applied to improve quality of existed products and

produce of new materials, some companies, e.g. Nanogate have used these
coatings to promote available systems. This company, which has previously
developed sport facilities with nano-coating, attempts to improve some of its
other products. One of its study fields is antipollution coating of solar cells.
Coatings surface of solar cells with antipollution and snow resistant coatings, a
bigger deal of solar energy can be absorbed and solar cells show a significant
efficiency [101–107].
6.11 Electrical and Electronic Applications 215
6.11.3 Nano-Coating of Nickel Particles by Oxides
Ceramic multilayer capacitor is a piece with broad use in electronic. Using these
capacitors in smaller volumes and materials such as BaTiO3, it is possible to
achieve higher capacities. For economizing these capacitors there was an effort to
alternate Pd/Ag electrodes with those made of metals such as Ni. These particles
problem is their oxidation with increase of temperature, happening in concentrated
circuits with many capacitors. One solution for this phenomenon is using oxide
coating with stable oxides. BaTiO3 is rather desirable for this goal. Unless coating
with this material is performed in nano thickness, it is probable dielectric prop-
erties of the layer be changes. For this aim, method of TiCl hydrolyzing in
butanone is applied. Using this method it is predicted to obtain low price high
efficiency capacitor in small volumes.
6.11.4 Using Polarizer Nano-Layers to Produce LCD

Monitors
Todays, a big share of monitors is devoted to LCDs. For their many advantages,
compared with CRT monitors, their application is dramatically increase. These
monitors include two groups: Active Matrix and Passive Matrix monitors. About
30% of monitors’ price is for their polarizer part. Nowadays, a type of 200 lm
layers is used to produce Active LCDs. Optiva Company is determined to use self-
organizer nano-structures which are capable of being coated with (Thin Crystal
Film) TCF method. These layers should be of equal cohesion and homogeneity in
any surface. In case of using this method there will be monitors with high reso-
lution, broader sight angle, and lower prices.
6.11.5 Produce of Electrically Conductive Transparence

Nano-Coatings
Eikos and FLEXcom Companies are determined to cooperatively produce elec-

trically conductive transparence layers with carbon nano-tubes. Defense Ministry
of the United State has devoted 1 million dollars to development of this tech-
nology. The layers can be used in solar cells, flat monitors, organic photonic
diodes, intelligent windows, and etc. Compared with traditional ITO (Indium Tin
Oxide) methods, this technology is cheaper and more trustable, with less volume
and higher efficiency. Regarding present applications for ITO it seems there will
be a good market for this new product.
6.11.6 Increase of Data Storing Capacity with Magnetic

Nano-Layers
Thanks to nano-layers, researchers have achieved higher density of storing in thin

layers. In this method thin magnetic contained nano-layers are used and storing
capacity has reached to 12 Gb/in2; however the bigger figures are also achievable.
Researchers believe that the nano-particle contained layers, as well as having an
enhancement in their efficiency and homogeneity, will completely dominate
present products.
6.12 Lubricating and the Other Applications
Using nano-technology and Self-Organizing polymers and nano-particles, Nanogate

Coating Systems Gmbh has achieved production of very high quality oils for sport
applications such as ski. Using this lubricators is easier that previous ones; also they
are more compatible with variant climates and increase speed and maneuverability in
slopes. The layers are also compatible with different types of snow.
6.13 Ag-Polluted SnO2 Particles
Recently, Nanophute Technology group announced produce of Ag-polluted SnO2

particles. These nano-particles diameter is about 30 nm and contain 3 weight
percent of Ag. The nanoparticles are currently used in semi-industrial scale.
Ag-polluted SnO2 nano-particles are used for many aims such as industrial anti-
microbial applications of wood protection, additives for plastic, and for electrically
conductive coating.
6.14 Development of Nano-Coating for Surface Lubrication
Nano-coated surfaces have shown an acceptable potential for lubrication. For this
aim, nano-metric coating of materials such as Al2O3/TiO2, WC/Co, and Cr2O3/
TiO2 have been widely focused. Another applied material is Yttria-stablized-
Zinconia. Today, many companies and institutes dependent to nano-particles
coating and production, decided to apply available technologies for nano-coating.
For example, one of widely used methods in coating industry is thermal spray. Use
of this method for nano-coating is accompanied with some difficulties. It has been
tried to eliminate the problems. Defense centers such as Navy Force of United
States have extensively invested in this field of nano-coating research and
6.14 Development of Nano-Coating for Surface Lubrication 217
development. For this aim there is a comprehensive cooperation between academic

and industrial centers [108–121].
6.15 Size Dependency in Nanocomposite Layers
Hard silica/epoxy nanocomposite layers were prepared by spinning method on the

surface of AA6082 aluminum alloy with addition of CdTe quantum dots as the
second phase in hard nanocomposite coating with different ratios in respect to
main phase (silica nanoparticulates). Electrical conductivity tests have been done
on the coatings for investigation of the possible enhanced or inverse effects of
addition QDs on properties of hard nanocomposite. The effects of some effective
factors have been investigated and it has been shown that by adding QD nano-
particulates the electrical conductivity of layers is completely controllable without
adverse effect on wear resistance. Figure 6.15 shows the effect of different rotating
speeds on the electrical conductivity of obtained layers. Density of different
nanoparticulates will decrease significantly by increasing rotating speed. By
increasing rotating speed, nanoparticulates will distribute far from each other. By
increasing rotating speed, electrical resistivity completely obey a linear relation
with respect to rotating speed.
Electrical resistivity acts to some what different from previous relations how-
ever it remains also completely predictable. Its plot (Fig. 6.16) can be divided into
three sections. First section is a completely slight linear increase follows by a
severe linear increase in second section and the third section is like the first one. It
is worthwhile mentioning here that due to difference in trends which observed in
this plot these sets of experiments have been done three times and reproducibility
of the results has been proved. It can be said that due to the effective share of QD
nanoparticulates in electrical conductivity of obtained layers, the amount of them
and bridging among them will cause the rapid increase in second section of the
curve. After reaching a special level for presence of QD nanoparticulates and
increasing their joining, the electrical conductivity will increase again with a slight
slope, as it can be seen in third section of the curve.
Fig. 6.15 Effect of rotating

speed on electrical resistivity
of different silica/epoxy
nanocomposite layers [122]
Fig. 6.16 Effect of SiO2/QD

ratio on electrical resistivity
of different obtained layers
[122]
References
1. Feng, J.L., Yue, C.Y., Chian, K.S.: Development and characterization of bismaleimides
containing aliphatic chain for microelectronics application. E-Polymers 1–11 (2006)
2. Goodman, J.: Microelectronics lessons apply to fuel cell development. Fuel Cells Bull.
2003, 10–12 (2003)
3. Kang, S.K.: Development of lead (Pb)-free interconnection materials for microelectronics.
Metals Mater. Int. 5, 545–549 (1999)
4. Siemroth, P., Schülke, T.: Copper metallization in microelectronics using filtered vacuum
arc deposition—principles and technological development. Surf. Coat. Technol. 133–134,
106–113 (2000)
5. Symko, O.G., Abdel-Rahman, E., Kwon, Y.S., Emmi, M., Behunin, R.: Design and
development of high-frequency thermoacoustic engines for thermal management in
microelectronics. Microelectron. J. 35, 185–191 (2004)
6. Zhang, H.Y., Pinjala, D., Joshi, Y.K., Wong, T.N., Toh, K.C.: Development and
characterization of thermal enhancement structures for single-phase liquid cooling in
microelectronics systems. Heat Transf. Eng. 28, 997–1007 (2007)
7. Lakatos, A., Erdelyi, G., Langer, G.A., Daroczi, L., Vad, K., Csik, A., Dudas, A., Beke,
D.L.: Investigations of diffusion kinetics in Si/Ta/Cu/W and Si/Co/Ta systems by secondary
neutral mass spectrometry. Vacuum 84, 953–957 (2010)
8. Cojocaru-Mirédin, O., Perrin-Pellegrino, C., Mangelinck, D., Blavette, D.: Boron
redistribution during reactive diffusion in Ni-Si contacts. Microelectron. Eng. 87, 271–
273 (2010)
9. Tam, P.L., Jelvestam, U., Nyborg, L.: Corrosion behaviour of amorphous Ni-Si thin films on
AISI 304L stainless steel. Mater. High Temp. 26, 177–186 (2009)
10. Schaefer, A., Zielasek, V., Schmidt, T., Sandell, A., Schowalter, M., Seifarth, O., Walle,
L.E., Schulz, C., Wollschäger, J., Schroeder, T., Rosenauer, A., Falta, J., Bäumer, M.:
Growth of praseodymium oxide on Si(111) under oxygen-deficient conditions. Phys. Rev.
B. Condensed Matter Mater. Phys. 80, 045414-0-13 (2009)
11. Cojocaru-Mirēdin, O., Cadel, E., Blavette, D., Mangelinck, D., Hoummada, K., Genevois,
C., Deconihout, B.: Atomic-scale redistribution of Pt during reactive diffusion in Ni (5%
Pt)-Si contacts. Ultramicroscopy 109, 797–801 (2009)
12. Chirkin, A.D., Lavrenko, V.O., Talash, V.M.: High-temperature and electrochemical
oxidation of transition metal silicides. Powder Metall. Metal Ceram. 48, 330–345 (2009)
13. Hähnel, A., Pippel, E., Woltersdorf, J.: Control of Ni/SiC reactions by germanium, studied
on the atomic scale. Scripta Mater. 60, 858–861 (2009)
14. Agarwal, G., Sharma, P., Jain, A., Lal, C., Kabiraj, D., Jain, I.P.: Ion beam induced mixing
at Co/Si interface. Vacuum 83, 397–400 (2008)
References 219
15. Ohno, T., Numakura, K., Itoh, H., Suzuki, H., Matsuda, T.: Control of the quantum size
effect of TiO2-SiO2 hybrid particles. Mater. Lett. 63, 1737–1739 (2009)
16. Chu, M.M., Chou, J.H.: Advances in selective wet etching for nanoscale NiPt salicide
fabrication. Jpn. J. Appl. Phys. 49, 06GG161–06GG165 (2010)
17. Ghai, D., Mohanty, S.P., Kougianos, E.: A variability tolerant system-on-chip ready nano-
CMOS analogue-to-digital converter. Int. J. Electron. 97, 421–440 (2010)
18. Raoult, J., Pascal, F., Leyris, C.: I-V and low frequency noise characterization of poly and
amorphous silicon Ti- and Co-salicide resistors. Thin Solid Films 518, 2497–2500 (2010)
19. Guangxin, D., Lingdou, C., Zhongli, L.: Design for an IO block array in a tile-based FPGA.
J. Semicond. 30, 085008-1-6 (2009)
20. Zimmermann, S., Zhao, Q.T., Höhnemann, H., Wiemer, M., Kaufmann, C., Mantl, S.,
Dudek, V., Gessner, T.: Roughness improvement of the CoSi2/Si-interface for an
application as buried silicide. Microelectron. Eng. 84, 2537–2541 (2007)
21. Hwang, K.J., Oh, J.H., Sung, N.K., Ryu, D.Y., Sa, S.H., Park, K.J., Lee, J.K., Lee, J.G.,
Park, S.H., Goo, T.G., Lee, H.D.: Characterization and improvement of reverse leakage
current of shallow silicided junction for Sub-100 nm CMOS technology utilizing N2 PAI.
J. Korean Phys. Soc. 49, S795–S799 (2006)
22. Erbetta, D., Lazzari, C.M., Brambilla, M., Marangon, T.: Impact of an As implant before
CoSi2 formation on the sheet resistance and junction breakdown voltage. Microelectron.
Eng. 83, 2258–2263 (2006)
23. Zimmermann, S., Zhao, Q.T., Höhnemann, H., Wiemer, M., Kaufmann, C., Mantl, S.,
Dudek, V., Gessner, T.: Different approaches to integrate patterned buried CoSi2 layers in
SOI substrates. Microelectron. Eng. 83, 2112–2116 (2006)
24. Tan, S.Y.: Dopant enhanced in nickel silicide formation for high-k dielectric applications.
J. Mater. Sci. Mater. Electron. 21, 1195–1201 (2010)
25. Li, Z., Gordon, R.G., Li, H., Shenai, D.V., Lavoie, C.: Formation of nickel silicide from
direct-liquid-injection chemical-vapor-deposited nickel nitride films. J. Electrochem. Soc.
157, H679–H683 (2010)
26. Chen, X., Zhao, A., Shao, Z., Li, C., Williams, C.T., Liang, C.: Synthesis and catalytic
properties for phenylacetylene hydrogenation of silicide modified nickel catalysts. J. Phys.
Chem. C 114, 16525–16533 (2010)
27. Verleysen, E., Bender, H., Richard, O., Schryvers, D., Vandervorst, W.: Characterization of
nickel silicides using EELS-based methods. J. Microsc. 240, 75–82 (2010)
28. Vassilevski, K., Nikitina, I.P., Horsfall, A.B., Wright, N.G., Johnson, C.M.: Growth of few
layers graphene on silicon carbide from nickel silicide supersaturated with carbon. In:
Materials Science Forum, p. 589. (2010)
29. Vassilevski, K., Nikitina, I.P., Horsfall, A.B., Wright, N.G., Johnson, C.M.: 6 kV, 10.5
mOhm cm2 nickel silicide Schottky diodes on commercial 4H-SiC epitaxial wafers. In:
Materials Science Forum, pp. 897–900. (2010)
30. Bhaskaran, M., Sriram, S., Holland, A.S.: Interfacial resistive properties of nickel silicide
thin films to doped silicon. J. Electrochem. Soc. 157, H842–H846 (2010)
31. Chen, H.Y., Lin, C.Y., Huang, C.C., Chien, C.H.: The effect of pulsed laser annealing on the
nickel silicide formation. Microelectron. Eng. 87, 2540–2543 (2010)
32. Kobayashi, K., Watanabe, H., Maekawa, K., Kashihara, K., Yamaguchi, T., Asai, K.,
Hirose, Y.: Oxygen distribution in nickel silicide films analyzed by time-of-flight secondary
ion mass spectrometry. Micron 41, 412–415 (2010)
33. Song, O., Kim, K., Choi, Y.: Nano-thick nickel silicide and polycrystalline silicon on glass
substrate with low temperature catalytic CVD. J. Korean Inst. Metals Mater. 48, 660–666
(2010)
34. Utlu, G., Artunç, N., Budak, S., Tari, S.: Structural and electrical characterization of the
nickel silicide films formed at 850C by rapid thermal annealing of the Ni/Si(1 0 0) films.
Appl. Surf. Sci. 256, 5069–5075 (2010)
35. De Keyser, K., Van Bockstael, C., Van Meirhaeghe, R.L., Detavernier, C., Verleysen, E.,
Bender, H., Vandervorst, W., Jordan-Sweet, J., Lavoie, C.: Phase formation and thermal
stability of ultrathin nickel-silicides on Si(100). Appl. Phys. Lett. 96, 173503-1-3 (2010)
36. Verleysen, E., Bender, H., Schryvers, D., Vandervorst, W.: Chemical analysis of nickel
silicides with high spatial resolution by combined EDS, EELS and ELNES. J. Phys.: Conf.
Series 209, 1–4 (2010)
37. Tsui, B.Y., Lee, C.M.: Thermal stability of nickel silicide and shallow junction electrical
characteristics with carbon ion implantation. Jpn. J. Appl. Phys. 49, 04DA04-1-6 (2010)
38. Tan, O.K., Zhu, W., Yan, Q., Kong, L.B.: Size effect and gas sensing characteristics of
nanocrystalline xSnO2-(1-x)a-Fe2O3 ethanol sensors. Sens. Actuators B Chem. 65, 361–
365 (2000)
39. Yoon, J.H.: Synthesis and charge storage properties of double-layered NiSi nanocrystals.
J. Nanopart. Res. 12, 2387–2391 (2010)
40. Yoo, J.H., Sohn, H., Ko, D.H., Cho, M.H.: Enhancement of thermal stability in Ni silicides
on Epi-Si1-x Cx by Pt addition. J. Electrochem. Soc. 157, H837–H841 (2010)
41. Lee, S.W., Huang, S.H., Cheng, S.L., Chen, P.S., Wu, W.W.: Ni silicide formation on
epitaxial Si1-YCy/(001) layers. Thin Solid Films 518, 7394–7397 (2010)
42. Alptekin, E., Ozturk, M.C.: NixPt1-xSi/n-Si contacts with sub-0.1 eV effective Schottky
barrier heights obtained by sulfur segregation. Microelectron. Eng. 87, 2358–2360 (2010)
43. Whang, S.J., Joo, M.S., Seo, B.M., Chang, K.E., Kim, W.K., Jung, T.W., Kim, G.H., Lim,
J.Y., Kim, K.Y., Hong, K., Park, S.K.: Thermally stable NiSi gate electrode with TiN barrier
metal for high-density NAND flash memory devices. Jpn. J. Appl. Phys. 49, 04DA17-1-4
(2010)
44. Imbert, B., Pantel, R., Zoll, S., Gregoire, M., Beneyton, R., Medico, S.D., Thomas, O.:
Nickel silicide encroachment formation and characterization. Microelectron. Eng. 87, 245–
248 (2010)
45. Lee, S.W., Huang, S.S., Hsu, H.C., Nieh, C.W., Tsai, W.C., Lo, C.P., Lai, C.H., Tsai, P.Y.,
Wang, M.Y., Wu, C.M., Lei, M.D.: C redistribution during Ni silicide formation on Si1-y
Cy epitaxial layers. J. Electrochem. Soc. 157, H297–H300 (2010)
46. Lee, J.B., Jeong, S.Y., Park, B.J., Choi, C.J., Hong, K., Whang, S.J., Seong, T.Y.: Improved
electrical and thermal properties of nickel silicides by using a NiCo interlayer. Superlattices
Microstruct. 47, 259–265 (2010)
47. Tsui, B.Y., Hsieh, C.M., Hung, Y.R., Yang, Y., Shen, R., Cheng, S., Lin, T.: Improvement
of the thermal stability of NiSi by germanium Ion implantation. J. Electrochem. Soc. 157,
H137–H143 (2010)
48. Wang, C.C., Lin, H.H., Chen, M.C.: Thermal stability of Cu/NiSi-contacted p+n shallow
junction. Jpn. J. Appl. Phys., Part 1: Regular Papers and Short Notes and Review Papers 43,
5997–6000 (2004)
49. Wang, R.N., He, Y., Feng, J.Y.: Explanation of the enhancement of NiSi thermal stability
according to TFD equations and Miedema’s model. Nucl. Instrum. Methods Phys. Res. Sect.
B Beam Interact. Mater. Atoms 222, 462–468 (2004)
50. Zhao, F.F., Zheng, J.Z., Shen, Z.X., Osipowicz, T., Gao, W.Z., Chan, L.H.: Thermal
stability study of NiSi and NiSi2 thin films. Microelectron. Eng. 71, 104–111 (2004)
51. Wang, R.N., Feng, J.Y.: Comparison of the thermal stabilities of NiSi films in Ni/Si, Ni/Pd/
Si and Ni/Pt/Si systems. J. Phys. Condensed Matter 15, 1935–1942 (2003)
52. Wang, R.N., Feng, J.Y., Huang, Y.: Mechanism about improvement of NiSi thermal
stability for Ni/Pt/Si(1 1 1) bi-layered system. Appl. Surf. Sci. 207, 139–143 (2003)
53. Wong, A.S.W., Chi, D.Z., Loomans, M., Ma, D., Lai, M.Y., Tjiu, W.C., Chua, S.J., Lim,
C.W., Greene, J.E.: F-enhanced morphological and thermal stability of NiSi films on BF+2-
implanted Si(001). Appl. Phys. Lett. 81, 5138–5140 (2002)
54. Liu, J.F., Feng, J.Y., Zhu, J.: Comparison of the thermal stability of NiSi films in Ni/Pt/
(111)Si and Ni/Pt/(100)Si systems. J. Appl. Phys. 90, 745–749 (2001)
55. Liu, J.F., Chen, H.B., Feng, J.Y.: Enhanced thermal stability of NiSi films on Si(1 1 1)
substrates by a thin Pt interlayer. J. Cryst. Growth 220, 488–493 (2000)
References 221
56. Liu, J.F., Chen, H.B., Feng, J.Y., Zhu, J.: Improvement of the thermal stability of NiSi films
by using a thin Pt interlayer. Appl. Phys. Lett. 77, 2177–2179 (2000)
57. Mangelinck, D., Dai, J.Y., Pan, J.S., Lahiri, S.K.: Enhancement of thermal stability of NiSi
films on (100)Si and (111)Si by Pt addition. Appl. Phys. Lett. 75, 1736–1738 (1999)
58. Kale, R.B., Lokhande, C.D.: Influence of air annealing on the structural, optical and
electrical properties of chemically deposited CdSe nano-crystallites. Appl. Surf. Sci. 223,
343–351 (2004)
59. Du, H., Lee, S.W., Gong, J., Sun, C., Wen, L.S.: Size effect of nano-copper films on
complex optical constant and permittivity in infrared region. Mater. Lett. 58, 1117–1120
(2004)
60. Tang, Z.K., Kawasaki, M., Ohtomo, A., Koinuma, H., Segawa, Y.: Self-assembled ZnO
nano-crystals and exciton lasing at room temperature. J. Cryst. Growth 287, 169–179 (2006)
61. Bilotsky, Y., Tomchuk, P.M.: Peculiarity of electron-phonon energy exchange in metal
nanoparticles and thin films. Surf. Sci. 602, 383–390 (2008)
62. Grandusky, J.R., Gibb, S.R., Mendrick, M.C., Schowalter, L.J.: Properties of mid-ultraviolet
light emitting diodes fabricated from pseudomorphic layers on bulk aluminum nitride
substrates. Appl. Phys. Express 3, 072103-1-3 (2010)
63. Hirayama, H., Tsukada, Y., Maeda, T., Kamata, N.: Marked enhancement in the efficiency
of deep-ultraviolet AlGaN light-emitting diodes by using a multiquantum-barrier electron
blocking layer. Appl. Phys. Express 3, 031002-1-3 (2010)
64. Lee, K.B., Parbrook, P.J., Wang, T., Bai, J., Ranalli, F., Airey, R.J., Hill, G.: Effect of the
AlGaN electron blocking layer thickness on the performance of AlGaN-based ultraviolet
light-emitting diodes. J. Cryst. Growth 311, 2857–2859 (2009)
65. Takeuchi, M., Maegawa, T., Shimizu, H., Ooishi, S., Ohtsuka, T., Aoyagi, Y.: AlN/AlGaN
short-period superlattice sacrificial layers in laser lift-off for vertical-type AlGaN-based
deep ultraviolet light emitting diodes. Appl. Phys. Lett. 94, 061117-1-3 (2009)
66. An, S.J., Yi, G.C.: Near ultraviolet light emitting diode composed of n-GaN/ZnO coaxial
nanorod heterostructures on a p-GaN layer. Appl. Phys. Lett. 91, 123109-1-3 (2007)
67. Huang, G.S., Kuo, H.C., Lo, M.H., Lu, T.C., Tsai, J.Y., Wang, S.C.: Improvement of
efficiency and ESD characteristics of ultraviolet light-emitting diodes by inserting AlGaN
and SiN buffer layers. J. Cryst. Growth 305, 55–58 (2007)
68. Georgieva, J., Armyanov, S., Valova, E., Poulios, I., Sotiropoulos, S.: Enhanced
photocatalytic activity of electrosynthesised tungsten trioxide-titanium dioxide bi-layer
coatings under ultraviolet and visible light illumination. Electrochem. Commun. 9, 365–370
(2007)
69. Ichikawa, M., Kobayashi, K., Koyama, T., Taniguchi, Y.: Intense and efficient ultraviolet
electroluminescence from organic light-emitting devices with fluorinated copper
phthalocyanine as hole injection layer. Thin Solid Films 515, 3932–3935 (2007)
70. Sakai, N., Prasad, G.K., Ebina, Y., Takada, K., Sasaki, T.: Layer-by-layer assembled TiO2
nanoparticle/PEDOT-PSS composite films for switching of electric conductivity in response
to ultraviolet and visible light. Chem. Mater. 18, 3596–3598 (2006)
71. Kyono, T., Hirayama, H., Akita, K., Nakamura, T., Adachi, M., Ando, K.: Influence of
residual oxygen impurity in quaternary InAlGaN multiple-quantum-well active layers on
emission efficiency of ultraviolet light-emitting diodes on GaN substrates. J. Appl. Phys. 99,
114509-1-7 (2006)
72. Izaki, M., Shinagawa, T., Takahashi, H.: Room temperature ultraviolet light emitting ZnO
layer prepared by low-temperature electrodeposition. J. Phys. D Appl. Phys. 39, 1481–1484
(2006)
73. Kwon, M.K., Park, I.K., Baek, S.H., Kim, J.Y., Park, S.J.: Si delta doping in a GaN barrier
layer of InGaN/GaN multiquantum well for an efficient ultraviolet light-emitting diode.
J. Appl. Phys. 97, 1–3 (2005)
74. Liu, Y.H., Li, H.D., Ao, J.P., Lee, Y.B., Wang, T., Sakai, S.: Influence of undoped GaN
layer thickness to the performance of AlGaN/GaN-based ultraviolet light-emitting diodes.
J. Cryst. Growth 268, 30–34 (2004)
75. Bu, I.Y.Y., Oei, S.P.: Hydrophobic vertically aligned carbon nanotubes on Corning glass for
self cleaning applications. Appl. Surf. Sci. 256, 6699–6704 (2010)
76. Katsumata, K., Okazaki, S., Cordonier, C.E., Shichi, T., Sasaki, T., Fujishima, A.:
Preparation and characterization of self-cleaning glass for vehicle with niobia nanosheets.
ACS Appl. Mater. Interfaces 2, 1236–1241 (2010)
77. Peruchon, L., Puzenat, E., Herrmann, J.M., Guillard, C.: Photocatalytic efficiencies of self-
cleaning glasses. Influence of physical factors. Photochem. Photobio. Sci. 8, 1040–1046
(2009)
78. Kasanen, J., Suvanto, M., Pakkanen, T.T.: Self-cleaning, titanium dioxide based, multilayer
coating fabricated on polymer and glass surfaces. J. Appl. Polym. Sci. 111, 2597–2606
(2009)
79. Medina-Valtierra, J., Frausto-Reyes, C., Ramirez-Ortiz, J., Camarillo-Martínez, G.: Self-
cleaning test of doped TiO2-coated glass plates under solar exposure. Ind. Eng. Chem. Res.
48, 598–606 (2009)
80. Peruchon, L., Puzenat, E., Girard-Egrot, A., Blum, L., Herrmann, J.M., Guillard, C.:
Characterization of self-cleaning glasses using Langmuir-Blodgett technique to control
thickness of stearic acid multilayers. Importance of spectral emission to define standard test.
J. Photochem. Photobiol. A Chem. 197, 170–176 (2008)
81. Zhao, X., Zhao, Q., Yu, J., Liu, B.: Development of multifunctional photoactive self-
cleaning glasses. J. Non-Cryst. Solids 354, 1424–1430 (2008)
82. Daiko, Y., Yajima, H., Kasuga, T.: Preparation of porous titanium phosphate glass-ceramics
for NH3 gas adsorption with self-cleaning ability. J. Eur. Ceram. Soc. 28, 267–270 (2008)
83. Medina-Valtierra, J., Campos-Revna, S.J., Frausto-Reyes, C., Calixto, S., Ramírez-Ortíz, J.:
Self-cleaning test of doped anatase-coated glass plates. Int. J. Chem. React. Eng. 5, A101-1-
4 (2007)
84. Mellott, N.P., Durucan, C., Pantano, C.G., Guglielmi, M.: Commercial and laboratory
prepared titanium dioxide thin films for self-cleaning glasses: photocatalytic performance
and chemical durability. Thin Solid Films 502, 112–120 (2006)
85. Sanchez-Garcia, M.D., Hilliou, L., Lagaron, J.M.: Nanobiocomposites of Carrageenan,
Zein, and Mica of interest in food packaging and coating applications. J. Agric. Food Chem.
58, 6884–6894 (2010)
86. Azeredo, H.M.C., Mattoso, L.H.C., Avena-Bustillos, R.J., Filho, G.C., Munford, M.L.,
Wood, D., McHugh, T.H.: Nanocellulose reinforced chitosan composite films as affected by
nanofiller loading and plasticizer content. J. Food Sci. 75, N1–N7 (2010)
87. Jaworek, A.: Electrostatic micro- and nanoencapsulation and electroemulsification: a brief
review. J. Microencapsul. 25, 443–468 (2008)
88. Kuo, Y.C., Lee, J.W., Wang, C.J., Chang, Y.J.: The effect of Cu content on the
microstructures, mechanical and antibacterial properties of Cr-Cu-N nanocomposite
coatings deposited by pulsed DC reactive magnetron sputtering. Surf. Coat. Technol.
202, 854–860 (2007)
89. Arshak, K., Adley, C., Moore, E., Cunniffe, C., Campion, M., Harris, J.: Characterisation of
polymer nanocomposite sensors for quantification of bacterial cultures. Sens. Actuators B
Chem. 126, 226–231 (2007)
90. Avella, M., Bruno, G., Errico, M.E., Gentile, G., Piciocchi, N., Sorrentino, A., Volpe, M.G.:
Innovative packaging for minimally processed fruits. Packag. Technol. Sci. 20, 325–335
(2007)
91. Brody, A.L.: Food packaging technology. Food Technol. 57, 52–54 (2003)
92. Cao, X., Tang, M., Liu, F., Nie, Y., Zhao, C.: Immobilization of silver nanoparticles onto
sulfonated polyethersulfone membranes as antibacterial materials. Colloids Surf.
B Biointerfaces 81, 555–562 (2010)
93. Seo, Y.I., Hong, K.H., Kim, D.G., Kim, Y.D.: Ag/Al(OH)3 mesoporous nanocomposite film
as antibacterial agent. Colloids Surf. B Biointerfaces 81, 369–373 (2010)
References 223
94. Dastjerdi, R., Montazer, M., Shahsavan, S.: A novel technique for producing durable
multifunctional textiles using nanocomposite coating. Colloids Surf. B Biointerfaces 81,
32–41 (2010)
95. Kim, S., Chung, H., Kwon, J.H., Yoon, H.G., Kim, W.: Facile synthesis of silver chloride
nanocubes and their derivatives. Bull. Korean Chem. Soc. 31, 2918–2922 (2010)
96. Moazami, A., Montazer, M., Rashidi, A., Rahimi, M.K.: Antibacterial properties of raw and
degummed silk with nanosilver in various conditions. J. Appl. Polym. Sci. 118, 253–258
(2010)
97. Pallavicini, P., Taglietti, A., Dacarro, G., Antonio Diaz-Fernandez, Y., Galli, M., Grisoli, P.,
Patrini, M., Santucci De Magistris, G., Zanoni, R.: Self-assembled monolayers of silver
nanoparticles firmly grafted on glass surfaces: low Ag+ release for an efficient antibacterial
activity. J. Colloid Interface Sci. 350, 110–116 (2010)
98. Lin, W.C., Chen, C.N., Tseng, T.T., Wei, M.H., Hsieh, J.H., Tseng, W.J.: Micellar layer-by-
layer synthesis of TiO2/Ag hybrid particles for bactericidal and photocatalytic activities.
J. Eur. Ceram. Soc. 30, 2849–2857 (2010)
99. Basri, H., Ismail, A.F., Aziz, M., Nagai, K., Matsuura, T., Abdullah, M.S., Ng, B.C.: Silver-
filled polyethersulfone membranes for antibacterial applications—effect of PVP and TAP
addition on silver dispersion. Desalination 261, 264–271 (2010)
100. Jin, X., Li, M., Wang, J., Marambio-Jones, C., Peng, F., Huang, X., Damoiseaux, R., Hoek,
E.M.V.: High-throughput screening of silver nanoparticle stability and bacterial inactivation
in aquatic media: influence of specific ions. Environ. Sci. Technol. 44, 7321–7328 (2010)
101. Hong, J.T., Seo, H., Lee, D.G., Jang, J.J., An, T.P., Kim, H.J.: A nano-porous TiO2 thin film
coating method for dye sensitized solar cells (DSSCs) using electrostatic spraying with dye
solution. J. Electrost. 68, 205–211 (2010)
102. Grinis, L., Kotlyar, S., Rühie, S., Grinblat, J., Zaban, A.: Conformal nano-sized inorganic
coatings on mesoporous TiO2 films for low-temperature dye-sensitized solar cell
fabrication. Adv. Funct. Mater. 20, 282–288 (2010)
103. Fan, S.Q., Li, C.J., Yang, G.J., Gao, J.C., Zhang, L.Z., Li, C.X., Wang, Y.Y.: Room-
temperature deposition of nano-TiO2 coating by vacuum cold spraying using TiCl4-
agglomerated nano-TiO2 powder for flexible dye-sensitized solar cell. In: Key Engineering
Materials, pp. 742–745. (2008)
104. Fan, S.Q., Li, C.J., Yang, G.J., Zhang, L.Z., Gao, J.C., Xi, Y.X.: Fabrication of nano-TiO2
coating for dye-sensitized solar cell by vacuum cold spraying at room temperature.
105. Fan, S.Q., Li, C.J., Li, C.X., Liu, G.J., Yang, G.J., Zhang, L.Z.: Preliminary study of
performance of dye-sensitized solar cell of nano-TiO2 coating deposited by vacuum cold
spraying. Mater. Trans. 47, 1703–1709 (2006)
106. Von Sonntag, J., Getzmann, M., Braun, A., Mehnert, R.: Nano-composite synthesis
with a TORUSMILL for the scratch resistant coating of flexible solar cells
[Nanokompositsynthese mit einer TORUSMILL für die Kratz-festbeschichtung flexibler
Solarzellen]. 38, 16–17 (2005)
107. Nakato, K., Takabayashi, S., Imanishi, A., Murakoshi, K., Nakato, Y.: Stabilization of n-Si
electrodes by surface alkylation and metal nano-dot coating for use in efficient
photoelectrochemical solar cells. Sol. Energy Mater. Sol. Cells 83, 323–330 (2004)
108. Liew, W.Y.H.: Low-speed milling of stainless steel with TiAlN single-layer and TiAlN/
AlCrN nano-multilayer coated carbide tools under different lubrication conditions. Wear
269, 617–631 (2010)
109. Zhang, Y.: A survey of boundary lubrication effect in elastohydrodynamic lubrication.
J. Comput. Theor. Nanosci. 7, 1496–1500 (2010)
110. Puértolas, J.A., Martíez-Nogués, V., Martíez-Morlanes, M.J., Mariscal, M.D., Medel, F.J.,
Ópez-Santos, C., Yubero, F.: Improved wear performance of ultra high molecular weight
polyethylene coated with hydrogenated diamond like carbon. Wear 269, 458–465 (2010)
111. Abdul Samad, M., Sinha, S.K.: Nanocomposite UHMWPE-CNT polymer coatings for
boundary lubrication on aluminium substrates. Tribology Lett. 38, 301–311 (2010)
112. Pham, D.C., Na, K., Yang, S., Kim, J., Yoon, E.S.: Nanotribological properties of silicon
nano-pillars coated by a Z-DOL lubricating film. J. Mech. Sci. Technol. 24, 59–65 (2010)
113. Koshy, R.A., Graham, M.E., Marks, L.D.: Temperature activated self-lubrication in CrN/
Mo2N nanolayer coatings. Surf. Coat. Technol. 204, 1359–1365 (2010)
114. Mulligan, C.P., Blanchet, T.A., Gall, D.: CrN-Ag nanocomposite coatings: tribology at
room temperature and during a temperature ramp. Surf. Coat. Technol. 204, 1388–1394
(2010)
115. Zhang, Q., Xiao, F., Guo, H., Li, C., Gao, L., Guo, X., Han, W., Bondarev, A.B.: Warm
negative incremental forming of magnesium alloy AZ31 Sheet: new lubricating method.
J. Mater. Process. Technol. 210, 323–329 (2010)
116. Levashov, E.A., Zamulaeva, E.I., Pogozhev, Y.S., Kurbatkina, V.V.: Nanoparticle
dispersion strengthened WC-C based coatings on Ti-alloy produced by sequential
chemical reaction assisted pulsed electrospark deposition. Plasma Process. Polym. 6,
S102–S106 (2009)
117. Hope, P.: Developing an electrophoretically depositable self-lubricating nanocomposite
paint process for a short recoil semi-automatic handgun application. In: Key Engineering
Materials, pp. 157–163. (2009)
118. Bobzin, K., Bagcivan, N., Immich, P., Warnke, C., Klocke, F., Zeppenfeld, C., Mattfeld, P.:
Advancement of a nanolaminated TiHfN/CrN PVD tool coating by a nano-structured CrN
top layer in interaction with a biodegradable lubricant for green metal forming. Surf. Coat.
Technol. 203, 3184–3188 (2009)
119. Dasch, J.M., Ang, C.C., Wong, C.A., Waldo, R.A., Chester, D., Cheng, Y.T., Powell, B.R.,
Weiner, A.M., Konca, E.: The effect of free-machining elements on dry machining of B319
aluminum alloy. J. Mater. Process. Technol. 209, 4638–4644 (2009)
120. Nie, C., Liu, X., Watanabe, H.: The lubrication properties of diamond-like carbon coatings
in engine oil. In: Materials Science Forum, pp. 652–657. (2009)
121. Kang, J.J., Wang, C.B., Wang, H.D., Xu, B.S., Liu, J.J., Li, G.L.: Characterization and
tribological properties of composite 3Cr13/FeS layer. Surf. Coat. Technol. 203, 1927–1932
(2009)
122. Aliov, M.K., Sabur, A.R.: Formation of a novel hard binary sio2/quantum dot
nanocomposite with predictable electrical conductivity. Mod. Phys. Lett. B 24, 89–96
(2010)
Chapter 7
Conclusions
Based on the discussions in different chapters of the book, these conclusions and
suggestions were extracted:
1. The scale of nano (in nanotechnology) is usually from 1 to 100 nm (usually
less than 10 nm). Application of nanotechnology rooted in basic elements.
Each one has specific characteristics which creates remarkable attributes in
various fields. Application of Nanoparticle in producing simple medicine and
bandages with no need to renewal, diagnosing early cancer cells and analyzing
environment pollutants are the examples of nanotechnology.
2. Nanomaterials are the new materials that their basic construction has formed
by nanometric scale engineering. On such scale the specific or completely
different material indicates the possibility to create more accurate new
materials and devices with vast capacities. The scale of nanomaterials should
be classified from 1 to 100 nm which means clusters or (Atomic) nuclear
pellet with no less than 100 nm, fibers less than 100 nm in diameter and films
thickness less than 100 nm. In this range nanomaterials show specific prop-
erties which they did not show for bigger dimensions such as micrometers and
bigger. This effects which have came from size of nanomaterials are known as
‘‘size effect’’. Size effect can be seen in different properties of nanomaterials.
For example, the hard agglomeration of the primary particles was successfully
suppressed to obtain TiO2–SiO2 nano-hybrid particles with controlled chem-
ical modification of titanium alkoxide. The quantum size effect of nano-hybrid
particles was confirmed by the band gap energy shift, using ultraviolet–visible
spectroscopy (UV–vis).
3. Nanoparticles have new qualities in them which it’s specified features are
covers size, distribution, shape, phase and etc. Nanoparticles can be con-
structed from a wide range of materials generally metallic oxide ceramics,
metals, silicates and non-oxide ceramics. The scientists hope to use nano-
particles in fabrication of ideal materials with desired mechanical, electrical,
magnetic or optical characteristics and progress their capacities. In the case
that this prospect occurs, it will affect positive impact on environment and low

226 7 Conclusions
budget achievements such as the influence of nanotechnology on medical

systems.
4. High volumes of nanoparticles can be applied in detergents, cosmetics, pes-
ticides, environmental modification, catalysts, lubricants, sealants, adhesives
and coatings fields. The coatings obtained by nanoparticles are remarkable
category in current and future applications. By these coatings, a profound
level of material properties can be used such as scratch resistance, optical
features (transparency or adjusted reflection) and also self cleaning properties.
5. Scientists apply the thin films by using different materials with thicknesses
less than 100 nm to benefit the size effect in nanostructured films. The basic
advantage of thin films as any other coating is that it can transfer material
properties to the surface so it is possible to use materials with their basic
characteristics. The substrate material and thin film create a system with
different enhanced properties. Nanotechnology creates instrument for control
of three key parameters for thin films: (a) Chemical composition (crystalline
structure in nanometer range), (b) Thickness and (c) surface geometry
(including thin films patterns on nanoscale).
6. The most prominent size effects of nanostructured films are as (a) Optical
properties (including optical entrapment, transparency, opaque, florescence …)
(b) Mechanical properties (including resistance to abrasion and wear, stiff-
ness …) (c) Electronic properties (including potential energy, binding
energy …) (d) Chemical properties (including water repellence, anti fog …)
(e) Magnetic properties (such as saving data ability) (f) Thermal properties
(such as application of thin film in multiple layers as an obstacle to prevent
expansion of atomic vibration.)
7. Different processes applied for production of thin nanostructured films. Some
of them are: chemical vapor deposition (CVD), physical vapor deposition
(PVD), thermal evaporation, magnetron sputtering and laser pulsed deposi-
tion. Controlling on nanoscale is an important issue to classify these methods.
8. Sol–gel method is an effective method to produce nanomaterials. The aim of
sol–gel method is to perform chemical process in low temperature for pro-
ducing objects, films, fibers, particles or composites with suitable form and
surface. Traditional production processes of ceramics leads to fabrication of
materials which has micro-structures with dimensions in 1–100 micrometers.
Sol–gel process can change this limitation to dimensions in 1–100 nm and in
molecular level. These materials usually have uniform chemical and physical
properties. Sol is constant suspension from rigid Colloid ingredient or polymer
which placed in one liquid. These particles can be crystalline or amorphous.
Sols are diffused chloride particle in ointment on 1–100 nm dimension which
due to it’s miniscule size and constant moving they stay floating. Gel is rigid
network connected with pores under micrometer dimension and polymer
chains with approximately more than one micrometer length. In Colloid gel
the network is created by amalgamation of Colloid particle while the polymer
gel has a under structure in other words polymer unites creates gel. In most
Sol–gel systems creation of gel occurs by covalence combination and gel is
7 Conclusions 227
not reversible which means it can not turn into Sol position again. If the gel
has combination other than covalence it can be reverse.
9. The use of acid catalysts or alkali can have impact on hydrolysis and con-
densation speed so it can alter the final product. By giving their H+ the acids
increase the Alco oxide speed in the Hydrolysis reaction. But by reducing the
pH the Condensation reaction reduces as well. Adding alkali can either
increase or decrease Hydrolysis which depends on types of Alco oxide but the
speed of Condensation increase without considering the kind of material and
therefore the density of chains will enhance. Gels that created by Acid cata-
lysts have longer time to transform into jelly condition and have less density
that face much contraction while Gels that created by catalysts alkali will have
less contraction in the process of drying due to it’s high density.
10. Self lay out created under proper condition by molecule and atomic design
which occurs in chemical and physical process. It leads to self organization of
atoms and molecules in suitable location with proper construction. The layout
of thin films (mostly in single layers) and on sub layer surfaces which simplify
molecules growth and organization. According to scientists the method is one
the rare down to up methods which pass its infancy and considering many
coatings before entering the industrial phase the basic science should develop.
Also there is a vast confinement in the materials that can be utilized in self
layout construction still there is large area to be discovered. The idea of
multiple layers with same action adds another aspect to the issue. One of the
technical problems insisted by many specialist is molecule activity which
becomes polymerize easily under effect of moisture and create blocks on the
surface and reduce the film reaction. The fact that chemical formulation and
surface pattern of self layout layers are suitable for specific sub layer and leads
to progress in specific usage which also become very expensive. The patterned
sub layers that direct the de coring process or effect growth of thin films is an
obstacle which will be appear by start of industrialized process.
11. Plasma polymerization use source of plasma to exit gas, the eviction has the
necessary energy to activate or analysis gas and liquid monomer which usu-
ally include vinyl group so the polymerization process starts. The plasma
polymerization method profits from AC/RF/MW/DC and pulse methods, the
method leads to steady thin polymer films with extensive width connections
and heat resistance. By choosing certain kind of monomer and energy density
for each monomer the chemical form and structure of thin film can be alter in
a wide range. The speed of plasma polymer precipitation is identified by the
following parameters: geometry system, primary monomer reaction, the pace
of monomer circuit, gas pressure, conjoined frequency, signal and finally the
sub layer temperature.
12. Annealing is a heating treatment which has an altered material in it’s structure
which leads to change in it’s features like constancy and steadiness. This
process includes two phases: slow heating and cooling. The heating treatment
usually leads to alteration in crystal structures of atoms. This alteration
includes crystal defects removal which ends by basic changes in primary
228 7 Conclusions
features like electric aspect of material. The main processes are gas annealing
and vacuum annealing. The vacuum annealing will cause adhesive improve-
ment, solidity stretchiness and electric treatment and material pit. Although
annealing is developed process but it still needs growth in mechanism and
structure control and morphology. Understanding the effect of annealing on
thin film features especially thin polymer films has significant importance.
13. Nowadays, nanotechnology is rapidly developing and promoting the quality of
many products. Industries are making efforts to use these created opportunity
to enhance their products efficiency and quality, as well as decreasing their
products’ price. With no doubt, the future belongs to those companies and
industries which invest in this area and extensively apply it. As this is a fairly
new emerging technology, it may enable many industries of our country to
invest in this field and realization using this technology’s outcomes and
advantages. Nano-structured coating is one of most effective broadly used
applications of nano-technology. In most cases, nano-structured coatings
characteristics have a significant improvement in comparison with traditional
ones. Some of these characteristics are: increase of hardness, wear strength,
abrasion, decadence, environmental pollutions, and etc.
14. During production, packaging, and finally preparing in markets, all applied
products needed form require coating. Coatings are used to enhance resistance
against different environmental agents such as various types of corrosion,
create new compatibility in surfaces (e.g., in optical layers), increase hardness,
and improve some physical features such as magnetic and electrical ones.
Practice of coating to deal with corrosion, by its own, is enough to highlight
importance of using coatings. In many developed countries damages induced
from corrosion is from 3.5 to 5 percent of gross product. Regarding to
importance and broad applications of coating, applied methods in this field are
permanently developing and the latest technology is applied in this field.
15. Coating is among main parts of surface engineering. Surface engineering is an
important technology and competition of various industries depends on
sponsoring of this part for them. Besides, as it will be discussed, coating is an
economically vital issue. Considering this, in many countries surface engi-
neering share in key industry sectors is defined and some of future questions
and different predictions are answered. Discussed topics are similar for many
countries. Then, regarding available reports in this field, upcoming develop-
ments of surface engineering markets and plans in England are studied. In
1995, England market for surface engineering exceeded 10 billion pounds,
where 4.5 billion pounds of these figure was expended on coating for
improvement and enhancement of surface properties and resistance against
corrosion. This figure has caused a 95.5 billion pounds value effect on
amounts of different products.
16. Thermal spraying involves particles quick surface melting and freezing.
Thermal spraying nano-composites are of higher abrasive resistance in com-
parison with micro-coatings. For their high hardness, thermal stability, cos-
metic appearance, and chemical neutrality, transitional metal nitride coatings
7 Conclusions 229
are of a great interest among researchers. In normal circumstances, these

coatings are produced through chemical vapor deposition (CVD) and physical
vapor deposition (PVD), although their nano-structural coatings can be
obtained using ion beam. Mentioned nano-coatings are of a great hardness.
This increase in hardness of multi-layers and multi-grids (two-layers) are more
intense. Spraying of transition metal nitride nano-particles in an amorphous
nitride matrix gives a rise to development of grains with dimensions lower
than one nanometer, which makes them efficient for uses such as enhancement
of abrasive resistance in copper cutting tools.
17. Oxide ceramics such as alumina, chromia, titania, and zirconia, are widely
used as surface coating materials for improvement of abrasive resistance,
wearing, and cavity. Coatings made from zirconia are used for cylinder head
and piston crown at internal combustion engines to improve thermal effi-
ciency, output force, and fuel efficiency. These coatings involve cavities
which are characteristics of plasma-sprayed coatings. Nano-crystalline zir-
conia coatings show lower porosity (8%) in comparison with micro-crystalline
coating (12%). Fine co-axis grains are cooled because of homogenous ger-
mination of mentioned melt, while columnar grains growth is due to hetero-
geneous germination in boundaries, where there is a higher cooling gradient.
For efficient melting of nano-zirconia source at plasma jet, boundaries are very
thin and their interface is fairly narrow.
18. In recent years, hydroxyapatite (HAP) has been introduced as a porous layer
on metallic substrates to provide easier in-growth of bony tissues. The size
effect on these kinds of coating that were fabricated by microplasma spray has
been studied. The metallic substrate from a surgical grade, biocompatible
austenitic stainless steel was used. The choice was done in accordance to
better corrosion resistance properties, mechanical properties and lower cost of
SS316L than those of the conventional Ti6Al4V alloy. Phase pure and
flowable HAP granule from conventional wet chemical route were prepared.
HAP coatings of thickness near 200 lm were prepared by microplasma
spraying on SS316L substrates. It was assumed that higher scatter of data at
lower load could be linked to stochastic nature of interaction between the
indenter that penetrated a very shallow depth and the flaws that scale with the
size/depth of the indentation and which possessed a highly statistical size
distribution in the surface and in the close vicinity of sub-surface region. At
higher load, it was suggested that due to a larger indentation zone of influence,
an averaging out effect of indenter-flaw interaction predominated to affect a
reduction in data scatter. At a low load of 10 mN, the coating demonstrated a
hardness value of about 5 GPa at a depth of about 170 nm which dropped by
60%, e.g., near 2 GPa at a depth of about 3 microns for a higher load of
1,000 mN. These data recommended the presence of a strong indentation size
effect in the nano-hardness behaviour of the coatings.
19. Production of hard coatings with transitional metal nitrides, through IBAD
method is an extensive study area. These nitrides include titanium nitride,
chromium nitride, vanadium nitride, zirconium nitride, and aluminum nitride.
230 7 Conclusions
Also, their obtained coatings have different mechanical and chemical prop-
erties. For example, titanium nitride has a structure similar to that of NaCl, but
titanium nitride have more hardness, higher chemical stability, and efficient
cohesion to matrix, which makes it most famous coating for cutting tools.
Titanium nitride is oxidized at temperatures higher than 500C. This causes
development of pure titanium oxide, attached to titanium nitride, which leads
to reduce of abrasive resistance of titanium nitride coatings. Due to devel-
opment of a passive and compacted oxide layer, chromium nitride indicates a
higher resistance against oxidization in comparison with chromium oxide,
which limits next oxidization. Aluminum nitride is among substances which
can be applied at higher temperatures, where nitrogen and aluminum atoms
are bonded with strong covalent bonds. Once, this coating is subjected to high
temperatures, aluminum move to surface and compose aluminum oxide layer,
which is an extremely efficient barrier to prevent later oxidization reactions.
20. At industrial applications there is an increasing demand for coatings having
higher resistance against oxidation, higher hardness, and longer life than those
of single layer coatings. To supply industrial needs for development of
improved coatings, there has been many efforts to design and produce super
consolidated coatings. Some researchers proposed notion of designing solids
with strong coatings, using two alternative layers with high and low elastic
constants. Each layer’s thickness must be in nano range and there must be no
dislocation source between layers. If dislocations could be created in the zone
of materials with lower modulus, they must be overcome to the noticeable
stress diffused from the phase with higher modulus, before creep phenomenon
(along the layers). Thus they must prohibit the creep along the layers. Such
multilayer coatings are called super-lattice and their two layers can be
metallic, carbide, and nitride. A multilayer includes different piled materials
on atomic scale. During multilayer coatings designing both related structural
and constitutional factors must be considered. These factors are: Grain size,
layers individual thickness, combination module, the number materials
interfaces (assuming the last layer is resistant against abrasion).
21. Applied ceramic micro- and nanoparticles mostly include aluminum oxide,
carbide, chromium oxide, titanium oxide, molybdenum oxide, tungsten car-
bide, and etc. Besides, polymeric particles such as polyethylene and polytet-
rafluoroethylene are used to decrease friction ratio and achieve a nonstick
composite surface. According to performed studies, fine-grained Ni–SiC
composite has a smoother surface and there is stronger bond between SiC and
Ni. Once SiC particles are bigger than 0.1 lm, usually there develops an oxide
layer on SiC particles which have a weak bond with nickel matrix, which leads
to development of cavities and cracks in grains boundary. On the other hand,
interface of a very fine SiC and mixed Ni is free of any defect. In the same
volumetric fraction very fine particles are more abundant, which prevent
grains growth at higher temperatures. However, investigations show a
decrease in particles size leads to decrease of simultaneous deposition of the
particles.
7 Conclusions 231
22. These coatings have typical structure of nc–MnN/a–Si3N4, where c and n are,
respectively, crystalline and amorphous phases and Mn stands for transitional
metals such as Ti, W, V, and Zr. In nano-composite coatings, transitional
metal-nitride phase is hard enough to bear exerted load while, on the other
hand, amorphous nitride provides flexibility of the structure. Based on com-
puter simulations plastic deformation in nano-crystalline materials, where
particle size is less than 10 nm, can be corresponded with particle boundary.
Here, grains boundaries slip—which is controlled by diffusion of grain
boundary—may be responsible for plastic deformation in nano-crystalline
materials. Slip is caused by atomic movements and stress induced from 3D free
migration; in the other words, once nano-crystalline materials are extremely
tiny indicate soft behaviors. Hence, an increase of hardness is required locking
in grains slip boundaries. Indeed, this is the reason for increase of hardness in
nc–MnN/a–Si3N4 system, for nano-composite coatings of nc–TiN/a–Si3N4 and
nc–W2N/a–Si3N4, where particles’ size decreases up to 4 nm. It was declared
that these developed nano-composite coatings by CVD method, will reach to
diamond hardness (70–80 MPa), where grain size is about 2 nm.
23. Al based composites with aluminum borate whiskers—which are created
using high pressure casting—indicate a comparable strength and modulus with
those of aluminum composites with SiC or silicon nitride whiskers. However,
they have a lower thermal expansion and higher abrasive resistance. Besides,
another priority of these whiskers is their very low costs in comparison with
those of SiC—1/20 of SiC whiskers. Hence, aluminum borate whisker is of
great qualifications for expansion of aluminum based composite applications.
Also, based on existed theoretical and empirical studies, it was revealed that
aluminum borate whisker is unstable in Al alloys, and the reaction occurs in
their interface. To control reaction in interface, nitriding process of these
whiskers, based on thermodynamic calculations, was suggested. To reach a
continuous and homogenous phase nitrided nano-coating must be used. Phase
analysis implies presence of BN and alumina on nitrided surface. Nitrided
nano-coating with thickness of 40–60 nm isolates the whisker from sur-
rounding matrix and aluminum/coating interface will be free reaction
productions.
24. Titanium oxide is of abundant usage in gas sensors and photo-catalysts. For
example, it is used in gas sensors to detect explosion released gases such as
natural gas and hydrogen. Due to their crystalline structure, surface area, their
cavity types (in terms of opening and closure), and their size distribution,
photo-catalysts are used for segregation of air pollutants and organic con-
taminator in waters. It has been currently shown that TiO2 nano-coatings are
of a greater sensation compared with that of micro-structure ones. The easiest
and simplest way to achieve a nano-coating with thermal spray method is
using raw materials with nano-size. However, directly adding such nano-
powders during spray process is difficult. Moreover, plasma or gas flame leads
to melting and removing its initial structure. Therefore, it was achieved that
better characteristics through simultaneous spray of the other substance which
232 7 Conclusions
prevents development of TiO2 powder in the furnace. Thus particles of

metallic Al, which are of a lower temperature and higher reactivity in com-
parison with TiO2, are added to Al/TiO2 composite powders to enhance
spraying efficiency. Al particles have significant role to create homogenous
sediment. They lead to reach to unique characteristics of nano-structures,
maintaining nanometric structure during spraying process.
25. It is found that development of nano-size dual metallic phases in alumina can
noticeably enhance its thermal and mechanical characteristics. Metallic phase
exhibits higher thermal conductivity and resistance against thermal shock in
comparison with alumina ceramic. Also, metallic phase can increase ceramic’s
ductility as metallic particles deform plastically. In performed operations on
metallic/alumina nano-composites, metals such as Cr, Ni, Fe, W, titanium
carbide were used, which leads to 2–3 times increase of ductility. Second phase
has been added through mechanical combining of alumina and metallic pow-
ders, and their under-pressure sintering of graphite crucibles. The main problem
of mechanical combination method is to find out how to reach to second phase’s
fine dispersion and favorite thermal expansion difference between alumina and
metal. Thus, a chemical coating method was used for preparation of ceramic/
metallic nano-composites, which has variant advantages compared with
mechanical combination method. The obtained powder in this method is more
homogenous and of a higher cohesion between metal and ceramic. Preparing
nano-composite coating of Al2O3/Al wet chemical coating method was applied.
Aluminum nano-particles are solved in appropriate solution, then Al2O3 is
added, and finally considered composite is deposited in the solution. Through
occurred reactions, there develops a thick Al(OH)3 layer on aluminum particles’
surface which, after calcification, is converted to alpha alumina nano-particles
(with grain sizes of 10–20 nm) and distributed Al particles. The advantage of
Al2O3/Al composite is development of a thin transition layer between Al and
Al2O3, which is able to improve their bond.
26. Although tri-valence chromium ions, and particularly hexa-valence ones, are
very poisonous, chromium plated coatings are widely used to enhance surface
abrasive resistance. Another problem of plated chromium coatings is their
decrease in thermal mobility with increase of temperature, so hardness and
abrasive resistance of plated layers reduces. Hereabout there have been many
studies in surface engineering to find a suitable substitute for this coating,
leading to promising results. First choice is tungsten carbide or tungsten-
carbide/cobalt. As it previously mentioned nano-crystalline materials show
unusual chemical, physical, and mechanical properties, in comparison with
amorphous ones. This is caused due to nano-crystalline materials’ noticeable
decrease in grain size and volumetric ratio of grain’s boundary, and triple
connections. Here, a decrease in tungsten carbide grain size up to 70 nm in
tungsten-carbide/Co composite leads to a two-time increase in abrasive
resistant.
27. Electrochemistry is an advanced technology in production of nano-particles.
Before studying use of different electrochemical methods for nano-coatings
7 Conclusions 233
production, first it should be defined that how colloidal chemical state leads to
creation of nano-particles. This leads to better understanding of electro-
chemistry concept and its effect on nano-coatings. In colloid science, nano-
particles mostly obtained from surfactant contained saturated solutions. The
first rule of organic ligands is inactivation of surface and development in
suspending state. This preparation technique of nano-particles is called
engaged sedimentation. Similar methods for development of nano-particles on
conductive matrix have dramatically advanced in electrochemistry. It has been
proved that adding surface intermediates can lead to deposition of nano-par-
ticles during plating. Additives prevent particles growth and maintain parti-
cles’ size to be approximately constant. A more common method is creating
changes in plating parameters, e.g., voltage or current. However, there is
another two-step method including a high extra voltage in a short time for
germination of metallic particles on surface and then slow growth of particles
in a lower extra voltage. Low extra voltage results in minimum change (about
7%) in particle size. this stops diffusion of mixed layers and decrease in
growth rate. particles shape produced by engaged electro-deposition depends
on applied matrix and extra voltage. Metals such as Au, Ag, Ni, and polymeric
nano-particles with spherical geometry on graphite matrixes, are created by
this method.
28. The results of hardness measurement for plated Ni–P whiskers at room tem-
perature were reported. Same results were obtained for Pd and Cu produced
from neutral gas evaporation method. An increase in grain size is accompa-
nied with considerable decrease of hardness in range of lower than 20 nm.
These observed reductions of hardness are not corresponded with Hall–Petch
behavior. Recently, performed investigations on tensional strength of Ni
nano-crystal at room temperature have shown a behavior similar to that of
determined with hardness. It is found that grain boundary diffusion in creep
phenomenon is not an efficient factor to determine mechanical behavior of Pd
and nano-crystalline Cu at room temperature. Start point for hardness decrease,
i.e., deviation from Hall–Petch behavior, occurs once triple lines occupy a high
ratio of sample volume. This phenomenon is generally in accordance with
softening effect of triple lines. Through electrochemical grinding of wires to
sizes lower than grains average size, triple connections can be displaced in fine
structures. At all cases this transition, increase of strength, and decrease of
malleability is shown from co-axis state to columnar one.
29. In general, corrosion resistance of nano-crystalline materials in aqueous
solutions is of great importance in an extensive area for future applications.
There performed few studies in this area. Both improved and disadvantageous
results for development of nano-crystalline in corrosion process have been
recorded for corrosion behavior of nano-crystalline produced by amorphous
materials crystallization. Obtained results are highly influenced by weak
characteristics of crystallized amorphous materials. In the other words, during
last few years, there have been considerable advancements in perception of
fine structures effect on corrosion properties for materials produced by
234 7 Conclusions
electrodeposition process. Nano-crystalline specimens show the same active-

inactive-trance-passive behavior; and differences are between passive current
density and open circuit potential. Nano-crystalline specimens indicate more
intense current in passive zone, implying higher corrosion rate. This current
density is mostly because of more grain boundaries and triple connections in
nano-crystalline samples, creating electrochemically active spots. This density
difference in current density decreases for higher potentials. At this potential
difference, final dissolve rate overcome to structurally control dissolve rate,
existed at low potentials. Another obvious difference in polarization result, in
varying potential of nano-crystalline and multi-crystalline samples, is open
circuit potential. It seems that positive transition of open circuit potential for
nano-crystalline samples is due to catalyst properties of hydrogen releasing
reaction.
30. Thermal stability of nano-crystals is of a great importance in high temperature
applications. For electro-deposited nano-crystals thermal stability is examined
through TEM and an indirect method, involving determination of thermal
stability using harness measurements as a function of annealing time. For
synthetic growth of grains there are some preventing factors for grain
boundary movements leading to their thermal stability. There is a slowing dual
force in nano-crystals due to triple connections. It can be easily shown that
grain growth for fined multi-crystal materials is controlled by inherent
movement of triple connections. For thermal stability of nano-structures, extra
distributions of triple connections lead to preferred dissolve in these spots.
Such a dissolve was observed in nano-crystals in triple connections using
TEM method. Ni stability with grain sizes of 10 and 20 nm was investigated,
using TEM. Degradation temperature for these materials is 353 K. This lack of
stability is due to unusual germination after annealing.
31. As it is expected from Hall-Petch assumptions, there are different practical
applications for nano-crystals based on existed criteria for development of
resistant coatings. Preferential mechanical properties of electro-deposited
nano-structures are among their most important industrial applications.
Electroplating process is applied for in situ maintenance of nuclear steam
generator tubes. This process is successfully applied in aqueous reactors in US
and Canada and registered as a standard method for repairing pressure tube.
Through this application, Ni with grain size of 100 nm, is created on interior
walls of steam generator tubes to perform a complete structural maintenance
in places where primary homogeneity of tube structure is mitigated. High
strength and convenient malleability of these 100 nm grains result in appli-
cation of a thin plate (0.5–1 mm) which minimizes fluid current and heat
transition in steam generator. Recent geometrical models and empirical
achievements have shown that nano-structural materials can have a high
resistance against creep and inter-granular cracking.
32. The various types of nanostructured materials enjoy two joint and common
specifications: (1) Atomic areas (granules or phases) have been restricted in
space smaller than micron scale. (2) High volume fraction of atoms exists in
7 Conclusions 235
interface areas. Nanostructured materials can be observed in dimensionless, one

dimensional, two dimensional and three dimensional forms. Atom nucleate or
atom sprouts have been recognized as dimensionless nanostructures. Nanorods
and similar nanostructures such as nano-whiskers can be considered as one
dimensional nanostructures while separate or isolated layers or multi-layers,
grown in one or two directions, are known as two-dimensional nanostructures.
In addition, nano-crystalline or nano-phases are considered as three-dimen-
sional (3D) nanostructures and regarded as highly-used nanostructures in metal
systems. The significance of nanometer scale is originated from the fact that
some of properties undertake remarkable amounts at this dimension range.
Since properties of a solid material is first controlled by density and atom
co-ordination number, nano feature of sizes of granules in crystalline materials,
despite chemical composition in nano-crystalline and microcrystalline state,
causes that properties like specific heat, thermal capacity, thermal extension
coefficient, magnetic properties and mechanical properties in nano-crystalline
state are considered completely different from microcrystalline state.
33. Materials with nanometer (nano-crystalline) structure are away from equi-
librium state. The factors, which affect on additional free energy of these
materials, have been recognized. High density of interface and sever changes
of chemical composition and stress gradient are the cases which can be
effective in abnormal thermodynamic changes of these materials. The origin
of these impacts has been recognized theoretically and experimental tests have
proven these cases as well. The nano-crystalline structure can be considered as
compound form, comprised of small crystalline areas with long-range order
and with various crystallography orientations and inter-connected lattice of
inter-grain areas, lacking any full crystalline order.
34. With regard to phase balance in microscopic structure, energy interface does
not play a significant role and only Gibbs free energy of whole object is
important. With regard to materials with microscopic structure, thermody-
namics of interface can be ignored. Of course, some common cases are
controlled and monitored through interface energy. For example, it can be
referred to the phenomenon of growth of grain. For nanostructured materials,
conducting thermodynamics studies merely on whole object is not sufficient
due to very high density of interface. And following interface thermodynamics
should be taken into consideration.
35. Free energy of a phase in a multi-crystalline material has higher amount than
materials with mono-crystalline state. Such additional amount is related to the
existence of inner-structure imperfections. High amount of grain boundary
constitutes major part of these imperfections. The amount of grain boundary
can be measured with regard to a nanostructured material. The total area,
which a grain boundary is occupied, is in compatible with d-1 in which d is
diameter of granule. The contact area of grain boundary has separate structure
that can affect on degree of free energy. Total length of these contact areas is
proportional to d-2. Contact area of these connections with grain vertices
affect on free energy. The population of these areas is proportional to d-3.
236 7 Conclusions
36. Coating has variant applications, such as protecting coatings against corrosion,
scratch, stain, denting, bending, foliation, or making water proof and acid
resistant coatings. Coating is used in every aspect of life from coating on
glass, wood, plastic, paper, fibers, or similar foliations, to coating in heavy
industries and special applications (e.g., military applications). Also, coatings
have a key role as protector against climatic conditions such as rain, snow,
solar ultraviolet beam, or chemical pollutions. Regarding abundant applica-
tions of coating in variant tools, researchers have always been trying to pro-
mote coating quality and lower its costs in academy and industry. Todays,
advancements in technology have significantly increased coating quality.
Recently, Coating through nano-materials has reached to practical scale and
some famous supplier companies of industrial panels and automobiles use this
coating in their products.
37. Active points are probably considered as the most significant obstacle in
nucleation kinetics. Regarding the unique properties of a specific electro-
chemical system, active points are appeared or disappeared completely dif-
ferent on surface of electrode. The main reason of the issue is related to
different chemical and electrochemical reactions like adsorption and separa-
tion of organic and non-organic ions or molecules, direct oxidation or
reduction of electrode surface which is occurred previously or concurrent with
process of formation of nucleation on electrode surface. That is to say that
assumption of a neutral electrode is considered as a completely optimistic
approach. A theoretical model has been proposed for formation of nucleus
thanks to time-dependency of number of active points on electrode surface.
38. Non-dimensional distribution of constant nucleation rate (critical nucleus)
around a semi-spherical nucleus inside the area was observed which over-
potential and concentration have been decreased. If various semi-spherical
nucleuses are formed on electrode surface, the local areas around nucleuses,
which nucleation rate has been decreased in there, are developed and are
overlapped each other gradually. That is to say that a general theoretical
model, indicating overall nucleation rate, should be considered with taking
into account effects of interaction of nucleuses on each other.
39. Existing ions in solution are primarily encircled by other species such as
molecules, ions, especially water molecules. When these ions are encircled by
water molecules, geometrical structure of water molecules plays a key role in
subsequent processes. The 104.45 angle formed between two hydrogen-
oxygen bonds, existing in water molecule, is as a result of strong bipolar
forces inside it. Electrostatic gravity between metal cations with positive
charge and water molecules results in hydration of existing ions or in other
words, covering metal ions by water molecules. The hydration process metal
ions are shown in which for comparison, display of an anion is also shown.
Generally speaking, taking two major points into consideration is of para-
mount significance.
40. There are numerous separate stages during transfer of metal ion from inside of
whole solution to creation of metal lattice on cathode surface. Each of these
7 Conclusions 237
stages can be a controller of velocity. The first stage at this route is transfer or
movement of the desired ions from whole solution to the vicinity of cathode.
Metallic ions, which exist either in hydrated or complex forms, first move
towards cathode in solution. This stage is usually carried out by convection
flows inside solution. Migration of ions under effect of potential gradient
between anode and cathode can play a key role in ionic transfer, but com-
paratively play a partial and meager role in material transfer resulted from
convection inside the solution. Transferred ions reach external part of pene-
tration layer and pass from penetration layer as a result of existing concen-
tration gradient. At this stage, solution convection does not play a key role in
transfer of ions. When these ions pass from diffusion layer and electrical dual
layer (Helmholtz Layer), they reach to cathode surface and are turned into
pure metal ions. Pure metal ions are turned into adatoms through combining
with electrons on cathode surface, adatoms start moving on surface with the
aim of being adsorbed in active areas as well as forming a very strong
chemical bond. At this stage, metal atoms are operated and distributed
appropriately, aimed at creating a crystal lattice. This stage includes nucle-
ation and coating growth stages. Controlling stages of reactions velocity
should be reduced or omitted in order to increase velocity of reactions on
cathode surface. When velocity controlling stage is under control of material
transfer, increase of over-potential will accelerate reaction.
41. Pulse Electrochemical Deposition process has been paid more attention in
recent years. Some researchers have reported reduction of porosity value of
gold cover by pulse current. The theory related to pulse plating (electroplat-
ing) is simple. The cathode layer is kept rich with metal ions and impurities
are decreased as much as possible. During on-pulse time (Ton), when current is
connected, metal ions are reduced on cathode. When current is disconnected
(off-pulse time), any type of concentration gradient, appeared during on-pulse
time (Ton), will be eradicated and there is possibility of separation of gas
bubbles and impurities which have been adsorbed on cathode and this process
is repeated once again. In pulsed electrochemical deposition method, related
parameters can be changed in wide scale independently. In electrochemical
deposition method with DC current, current density is the only changeable
parameter. Consequently, creation of various situations faces more restriction.
There are impurities which have been adsorbed on cathode and then this
process is repeated once again. In electrochemical deposition method with
pulse current, related parameters is changeable in a wide range independently.
In electrochemical deposition method with direct current, current density is
the sole changeable parameter and consequently, creation of various situations
faces more restriction. In terms of production methods, it can be stated that
electrochemical coating method is regarded as one of the oldest methods for
imposing nanostructured coatings.
42. As a general principle, it should be said that plastic deformation of a nano-
structure coating strictly depends on its grain size. Various tests in environ-
ment temperature have shown that with decreasing grain size beyond certain
238 7 Conclusions
limit, Hall–Petch equation doesn’t apply and contrary to expectation, material

will become softer. It has been observed that this affair occurs when amount of
triple junctions shows remarkable growth. Some other mechanical properties
of these coatings can be justified with studying behavior of this material and
considering the triple junctions. Reduction of granule size has remarkable
effect on improvement of resistance against erosion in nanostructure and
composite materials. Of course, most research activities have been made on
double-phase and/or composite nanostructures and not appropriate research
activities have been made with relation to pure nano-crystalline metals.
Research activities made on frictional behavior of multilayer nano-coats show
that their behaviors have been more affected with chemical composition of
materials and their nano-microstructure has not any effect on their frictional
behavior. Erosion behavior, under high stresses, is severely affected with
chemical composition of materials and their nano-microstructure has not any
remarkable affect on their frictional behavior. Study of erosion behavior under
low and average loading condition in nano-materials shows that because of
higher stiffness, erosion resistance of these materials is more than that of
materials with large size. With regard to creep in nanostructured materials,
since grain boundary’s slip is regarded as one of the mechanisms of creep,
creep rate in nanostructured materials is more than microcrystal materials.
43. In spite of this fact that corrosive properties of nanostructured coating is of
paramount significance, very few research activities have been made in this
regard. Nano-crystalline materials provide new approach for improvement of
properties, without any change in chemical composition. Small size of grain
and high volumetric fraction of grain boundary can cause different corrosion
behavior with respect to multi-crystalline materials. Effect of reduction of
grain size on increase of resistance against local corrosion of stainless steel
has been reported.
44. During recent years, successful coexistence of very minute particles, like
metallic powders, silicon carbide, oxides, diamonds and polymers, has been
reported with metallic or alloy field and their accordance structures and
properties have been studied by various researchers. Not only structure and
properties of nanocomposite coatings depends on density, size, distribution
and nature of improved particles nature, but also it depends on type of used
solution, current density plating parameters, temperature, and degree of pH,
etc. Nanocomposite plating includes revival of metallic ions from suspension
electrolyte and insoluble powders like oxides (SiO2, TiO2, Al2O3), carbides
(SiC), nitrides (Si3N4), polymers (PTFE, Polytetrafluoroethylene). This
activity will result in entering very minute particle to the growing metallic or
alloy substrate. High superficial energy and inclination of nanoparticle to
agglomeration in high conductor metallic electrolyte will bar congruousness
of distribution of particles.
45. Due to the application of nickel as protective coating, nickel nanocomposite
coatings, containing ceramic nanoparticle with high hardness and resistance to
erosion, have been taken into consideration seriously. Hardness and resistance
7 Conclusions 239
of deposited coatings of nickel nanocomposite strictly depends on degree of

ceramic particles extant in nickel background. Al2O3, WC, MoS2, TiO2,
Cr2O3, ZrO2 and diamond are of ceramic powders which have been used in
manufacturing of nanocomposites with nickel background. Up to the present
time, more research activities have been made on nanocomposite coatings of
Ni/Al2O3 and Ni/SiC.
46. Participation of alumina nanoparticle will improve hardness and resistance of
coating against friction remarkably. Final tension will boost traction and
tension of submit in comparison with nickel, depending on degree of partic-
ipation of particles in coating, partly twofold or more than two fold. Resis-
tance against friction is boosted upon increase of density of alumina in
coating. At any rate, ductility of nickel-alumina nanocomposite coatings is
less than sole nickel. Annealing of nanocomposite in high temperature will
increase ductility but will reduce their strength. Resistant against corrosion of
nickel is improved with alumina nanoparticle. Increase of hardness is made
based on preventing grains from growing and according to Hall-Petch law.
47. In systems with simple counting ions, zeta potential is regarded as a criterion
for gradient of electrical potential, when surface potential is fixed. The pH,
which its zeta potential is equal to zero, is called Iso Electric Point. To enrich
loading of hydrated surface by OH– and H3O+, increase or decrease of pH
from Iso Electric Point will first boost absolute fraction of zeta potential. Iso-
electric point for alumina is pH = 9 i.e., alumina particles will have negative
superficial load in the electrolyte with pH more than 9. In the same direction,
alumina particles will have positive superficial load at the pH with less than 9.
Consequently, alumina nanoparticle can be seeped simultaneously with nickel
for formation of composite layers without needing to specific additives.
Because, pH of all composite plating solutions of nickel is smaller than IEP
for alumina and alumina particles at these baths have positive superficial load.
But, alumina nanoparticles are agglomerated easily in electrochemical elec-
trolyte due to their high superficial energy and this activity will cause weak
mechanical properties in nanocomposite coatings, for, it prevents particles
from being distributed equally. After carrying out operations, physical dis-
tribution of nanoparticles at electrolyte solution by mixing and ultrasonic
operation and/or through distribution of chemical dispersants in electrolyte is
a mandatory activity. The more volumetric percentage of alumina nanopar-
ticles can be boosted in Ni/Al2O3 nanocomposite coating the more provided
hardness of nanocomposite coat can be expected. Hence, this activity requires
getting familiarity with effective parameters in simultaneous electrical depo-
sition process of alumina and nickel.
48. Some researchers analyzed ultra-thin elastic films of nano-scale thickness with
an arbitrary geometry and edge boundary conditions. An analytical model is
proposed to study the size-dependent mechanical response of the film based on
continuum surface elasticity. By using the transfer-matrix method along with
an asymptotic expansion technique of small parameter, closed-form solutions
for the mechanical field in the film is presented in terms of the displacements
240 7 Conclusions
on the mid-plane. The asymptotic expansion terminates after a few terms and
exact solutions are obtained. The mid-plane displacements are governed by
three two-dimensional equations, and the associated edge boundary conditions
can be prescribed on average. Solving the two-dimensional boundary value
problem yields the three-dimensional response of the film. The solution is
exact throughout the interior of the film with the exception of a thin boundary
layer having an order of thickness as the film in accordance with the Saint–
Venant’s principle.
49. The effect of the material micro-structural interfaces increases as the surface-
to-volume ratio increases. Researchers showed that interfacial effects have a
profound impact on the scale-dependent yield strength and strain hardening of
micro/nano-systems even under uniform stressing. This is achieved by
adopting a higher-order gradient-dependent plasticity theory that enforces
microscopic boundary conditions at interfaces and free surfaces. Those non-
standard boundary conditions relate a micro-traction stress to the interfacial
energy at the interface. In addition to the non-local yield condition for the
material’s bulk, a microscopic yield condition for the interface is presented,
which determines the stress at which the interface begins to deform plastically
and harden. Hence, two material length scales are incorporated: one for the
bulk and the other for the interface. Different expressions for the interfacial
energy are investigated. The effect of the interfacial yield strength and
interfacial hardening are studied by analytically solving a one-dimensional
Hall-Petch-type size effect problem. It is found that when assuming compliant
interfaces the interface properties control both the material’s global yield
strength and rates of strain hardening such that the interfacial strength controls
the global yield strength whereas the interfacial hardening controls both the
global yield strength and strain hardening rates. On the other hand, when
assuming a stiff interface, the bulk length scale controls both the global yield
strength and strain hardening rates. Moreover, it is found that in order to
correctly predict the increase in the yield strength with decreasing size, the
interfacial length scale should scale the magnitude of both the interfacial yield
strength and interfacial hardening.
50. Tensile and fatigue tests of ultra-thin copper films were conducted using a
micro-force testing system by some researchers. Fatigue strength as a function
of film thickness was measured under the constant total strain range control at
a frequency of 10 Hz. The experimental results exhibit that both yield strength
and fatigue lifetime are dependent on film thickness. Fatigue damage behavior
in the 100 nm thick Cu films with nanometer-sized grains is different from
that in the micrometer-thick copper films with large grains observed before.
Fatigue of thin metal films is a key issue for the long-term service of micro-
devices. Previous investigations of fatigue of thin metal foils show a tendency
of the improved fatigue strength with decreasing foil thickness. Especially,
several studies on thin metal films, such as thin Ag films and Cu films, have
demonstrated that fatigue properties of these metal films are significantly
different from those of the bulk materials. When the film thickness approaches
7 Conclusions 241
200 nm, interface-induced fatigue damage becomes more prevalent. In these

studies, the film thickness and grain size are usually ranged from several
micrometers to sub-micrometers. However, little is known about fatigue
damage and strength of metal films with nanometer-scale thickness and grain
size.
51. Researchers produced nano-composite materials made of steel alloy, with very
few molecules in their particles which can be used in buildings to increase
strength and other similar cases. There existed a common physical mechanism
which contributes to control alloy hardness. Hardness increase causes mal-
leability, foliating, and tabularization decrease. Using nano-composites in
these alloys it is possible to decrease these shortages to a high extent. This is
caused by an increase in controlling mechanisms for each material property in
nano scales. This method involves creating an alloy in frozen glass structure.
Grinding obtained product make it possible to produce a particular powder
which make bonds with other materials and create a very dense coating during
heating process. Under this conditions particles diameter is about 50 nm. The
process can generate very strong bonds in substances. Available steels are of
strength about 10 percent of those calculated through theoretical methods,
once using this method enables us to reach strengths about 40 to 45 percent of
calculated one. This method also contributes to obtain better corrosion
resistant properties.
52. Nowadays metal silicides are an important component of an electronic part.
The Self-aligned Silicide (SALIIDE) process leads to the formation of a
uniform type of metal silicides formed simultaneously in the regions of gate,
source, and drain; and it is so successful due to its reliability and simplicity.
Therefore, application of metal silicides has been promoted in electronics
industry. The most common silicides used in electronic parts are PtSi, TiSi2,
and CoSi2, although using C54–TiSi2 (phase with less special resistance) and
CoSi2 in smaller parts (less than 0.2 and 0.04 lm respectively) is so difficult.
In future parts we must use silicides layers with very low thickness. The
silicides layer’s thickness was about 20 nm in 2005, and it is expected that it
will be reached to 5.5 nm in the year 2015. Recently NiSi has attracted much
attention and the latest progresses reference to the vast efforts in order to the
application of NiSi in MOS parts in future technologies. NiSi is of great
importance because of its low special resistance, low contact resistance,
potential to form in low thicknesses, and its consistency. Therefore, it is
inevitable to study its specifications.
53. Some researchers described the control of the quantum size effect by controlling
the coating layer thickness in TiO2–SiO2 core-shell hybrid particles obtained by
the liquid phase deposition (LPD) method. The quantum size effect of the
obtained nano-hybrid particles was estimated by the band gap energy shift,
using ultraviolet-visible spectroscopy (UV–vis). As a result, we successfully
controlled the degree of the quantum size effect by controlling the coating layer
thickness in core-shell TiO2–SiO2 hybrid particles. They concluded the
successful preparation of core-shell type TiO2–SiO2 hybrid particles by LPD.
242 7 Conclusions
The coating layer thickness and the crystallite size were controlled by con-
trolling the [Ti]/[Si]. In the case of the [Ti]/[Si] ratio of over 0.1, silica particles
were completely coated by titania. The degree of the blue shift of the band gap
energy by the quantum size effect for the obtained particles was approximately
0.13 eV larger than that of the pure titania, because of the existence of the Ti–
O–Si bond. If the Ti–O–Si bond effect was removed, the blue shift of the band
gap energy for core-shell type TiO2–SiO2 particles was nearly the same value as
that of the reported values for the pure titania. From these results, the quantum
size effect was successfully controlled by controlling the coating layer thickness
of core-shell type TiO2–SiO2 hybrid particles.
54. The formation of self-aligned silicide happens after the formation of source/
drain. Therefore, the temperature formation of silicide must be low enough to
keep the joint thin in under 100 nm CMOS technologies. NiSi has the lowest
formation temperature among all the silicides, and the thermal stability
interval is 350–750C. For TiSi2, the thermal stability interval is very limited.
Contact resistance of TiSi2 is high before 800C, due to the presence of C49
crystal phase. Between 850 and 950C it decreases due to the formation of phase
with formation of C54. Above the 950C, due to the accumulation of surface
resistance, it increases. In the other words, the contact resistance of NiSi gets
stable and minimized between 350 and 750C. The increase of resistance above
750C is due to the fusion of phase from NiSi to NiSi2. Therefore, NiSi is
thermally suitable for the technologies under 100 nm. In the other words, it
must be kept in mind that the temperatures of processes after the formation of
silicide must not exceed 750C.
55. Some researchers prepared non-equilibrium nanocrystalline xSnO2–(1 - x)
a-Fe2O3 powders by using the mechanical alloying technique. The thick film
screen printing technology is then employed to fabricate these ethanol gas
sensors. The gas sensing characteristics are also measured. New structural
model for these non-equilibrium nanocrystalline xSnO2–(1- x)a-Fe2O3
materials explains both the lattice expansion of these high energy mechani-
cally alloyed powders as well as the charge neutrality in terms of additional
oxygen dangling bonds at the nano-sized particle surfaces. It is those enor-
mous oxygen-dangling bonds at the particle surfaces that give rise to the high
gas sensitivity. The sensors are found to be 32.5 times more selective to the
ethanol gas compared to CO and H2 gases. They have illustrated a promising
method of using mechanical alloying in the preparation of nano-sized a-Fe2O3
materials for gas sensing applications. In particular, the sensor has shown
good ethanol gas sensitivity values of as high as 845 at 1,000 ppm in air. The
sensor is selective to ethanol gas over carbon monoxide and hydrogen gases.
The gas sensitivity is also found to be very stable. These excellent experi-
mental results can be explained by the fact that such mechanical alloying
materials have nano-sized particle grains and exhibit enormous oxygen dan-
gling bonds at their particle surfaces.
56. Some researchers fabricated cadmium selenide nano-crystallites onto amor-
phous glass substrate from an aqueous alkaline medium, using chemical bath
7 Conclusions 243
deposition method at room temperature. The samples are annealed in air for
4 h at various temperatures and characterized by structural, optical and
electrical properties. After annealing metastable nanocrystalline cubic phase
transformed into stable polycrystalline hexagonal phase. Depending upon
temperature, decease upto 0.6 eV and 103 X cm were observed in the Eg, and
electrical resistivity, respectively. These changes have been attributed to the
increase in the grain size of the CdSe crystallites. They report on the room
temperature chemical deposition of CdSe thin films from an aqueous alkaline
medium. In order to get good quality CdSe thin films, the preparative
parameters such as concentration of cadmium, deposition time and pH were
optimized. Freshly deposited thin films may contain many defects such as
voids, pinholes, etc. Annealing of thin films reduces the defects and increases
crystallite size along with recrystallization process.
57. Some researchers prepared nano-copper films by DC magnetron sputtering.
Their reflectivity and transmittivity to electromagnetic wave in infrared region
were measured with Fourier Transformation Infrared Spectrometer (FTIR), by
which their complex optical constant and permittivity were obtained. The
results show that the complex optical constant and permittivity of nano-copper
films depend upon the film thickness. This dependence is correlated with
microstructure transition during the film growth. They measured the reflec-
tivity and transmittivity of nano-copper films to electromagnetic wave in
infrared region, by which their complex optical constant and permittivity, both
the real and the imaginary parts are calculated. All these parameters are
essentially dependent on the film thickness. This dependence should be con-
sidered in application of nano-copper film. The dependence of electromag-
netic parameters on the characteristic size provides new possibilities for
designing high performance electromagnetic functional materials and devices.
The evolution of the film microstructure plays an important role in the size
effect of nano-copper film on complex permittivity.
58. Studies on ultraviolet stimulated emission and lasing observed at room
temperature from nano-structured ZnO thin films have been reviewed. The
nano-structured ZnO thin films were grown on sapphire substrates using
Laser-Molecular-Beam-Epitaxy (L-MBE). The thin film was consisted of
regularly arrayed hexagonal nano-crystallite columns, whose facets form
natural micro-cavities. These nano-crystallites confine the centre-of-mass
motion of excitons. As a result of the quantum size effect, the oscillation
strength of the excitons is largely enhanced, which is favored to the radiate
recombination of exciton at room temperature. At a moderate pumping
intensity, the room temperature stimulated emission is associated with an
exciton-exciton collision process. At higher pumping density, the excitons are
dissociated, and the ultraviolet stimulated emission is dominated by an elec-
tron-hole plasma recombination process. Because of the large enhancement of
oscillator strength of the excitons, the optical gain of the stimulated emission
measured at room temperature reaches as high as 320 cm-1, which is an order
higher than that observed in bulk ZnO crystals. In comparison with the
244 7 Conclusions
electron-hole plasma stimulated emission in most of commercial semicon-

ductor lasers, the excitonic stimulated emission can be realized at relatively
low external pumping density. The observation of excitonic lasing effect at
room temperature might be valuable in realization of practical ultraviolet
semiconductor laser devices.
59. Some researchers studied the size dependence of electron-lattice energy
exchange in nanoparticles. Both surface and bulk energy exchange parameters
are examined and it is demonstrated that the bulk energy exchange has non-
monotonic oscillations versus size of the particles. It has been found that the
amplitude of such oscillations increases with decreasing a particle size until
the critical size reaches Lc. These bulk interaction related oscillations disap-
pear for the particles less than Lc, and only the surface energy exchange
remains as the energy flow between electrons and phonons subsystems. It has
been shown that there exists an interval of particles sizes with total energy
exchange of few orders less than in massive bulk metals. This condition is
crucial for existence of hot electrons in stationary conditions in metal nano-
particles, metal island films and thin films as have been observed experi-
mentally. They studied the total electron-phonon energy exchange in small
metal particles which size is less than free path of electron-phonon collisions.
This expression contains bulk and surface terms. The bulk contribution
oscillates as the function of the particle size. It is important that the long wave
acoustics phonons generated by the hot electrons can be in non-equilibrium
state with others phonons. Thus, the use of electron-phonon collisions integral
approach with Plank distribution function of phonons could be incorrect.
60. Todays, technological achievements in food packaging industry have enabled
us to apply intelligent packaging in order to change conditions and data
delivery from food situation. This package is called active packaging. One
applied method, is use of nano-composite coating to coat plastic layers. Over
the time, food releases gasses and moisture in their packages. In some
packaging gas and moisture absorbent are used, which leads to healthiness and
preservation of the food. Some intelligent coatings show leakage or increase
of temperature. Nowadays, there are some attempts to promote packaging
quality through coating of food packages using anti-microbial coatings. Till
now, use of these coatings has not been of much interest. Regarding available
technologies use of these coatings is not economic yet. However, some active
companies in this field hope to produces low cost surfaces with decent anti-
bacterial property—using nano-coating technology—to coat food products.
Another application of nano-coating is production of biosensors, attached to
packages in coating form. Biosensors can offer information about quality of
packaged materials, their state of healthiness, and etc.
Index
A Atomistic simulation, 154

Abrasion, 4–5, 15–16, 31, 33–36, 42, 49, 61, Atoms, 1, 12–13, 15, 34, 55–56, 77, 79, 90–91,
99–101, 103–104, 173, 208, 226, 94–95, 111–112, 114–116, 118,
228, 230 127–128, 135, 197, 199, 200, 220,
Abrasion resistant coating, 61, 101 227, 230, 237
Abrasive resistance, 29–30, 34, 37, 43, 44–45, Automobile industry, 37, 65, 209
47, 60, 63, 228–232 Average current density, 47, 119
Accumulation, 8, 43, 192, 199–200, 242 Average size of nanometric particulates
Adatom, 114, 127, 237 (ASNP), 175
Adhesives, 4, 236
Aero gel, 7, 9
Agglomeration, 2, 9, 50, 80, 113, 152, 164, B
166–167, 169, 178, 201, 225, 235 Band gap energy, 2, 149, 187, 225, 241
Air pollutants, 44, 231 Binding energy, 5, 188
Alco gel, 7 Biocompatibility, 31
Aluminum oxide, 21, 34, 38–39, 230 Bio-stability, 31
Amalgamation, 6, 164, 226 Butler-volmer equation, 131
Amorphous, 6, 30–32, 36, 40–42, 52, 56, 60,
94, 150, 175, 191, 201, 226, 229,
231–233 C
Anatase, 2–3, 149 Cantilever, 38, 72
Anisotropy, 36, 59 Carbon nanotubes, 2, 49–51, 112–113, 121
Annealing, 13, 56, 58, 86, 94, 153, 195, Catalyst, 4, 7–8, 11, 44, 52, 60, 133, 187, 209,
200–202, 227–228, 234, 239, 243 213, 226–227, 231, 234
Anode, 111, 113–114, 126, 129 Catalyst properties, 52, 133, 209, 234
Anti corrosive coating, 5 Catalytic systems, 85
Anti fog, 5, 15, 226 Cathode, 39, 111, 114–115, 119, 125–130,
Anti scratch, 15 162, 166, 168, 170, 236–237
Antibacterial coating, 101, 213 Cathodic over-voltage, 114
Anti-bacterium masks, 210 Celice model, 162
Anti-corrosive properties, 133 Ceramics, 3, 6–7, 9, 30, 61, 66, 68, 85,
Antipollution, 212–214 101–102, 135, 225–226, 229
Antistatic, 92–93 Cerium oxide, 10
Asymptotic analysis, 155 Characterization, 77, 180, 182, 192
Atomic force microscopy (AFM), 166 Charge transfer, 118, 122, 127–128, 131
Atomic nucleation theory, 116 Chemical barriers, 5
Atomic vibration, 5, 226 Chemical collide, 4
245
246 Index
C (cont.) Detergents, 4, 226

Chemical composition, 4, 78–79, 83–84, Dielectric constant, 135–137
92–93, 96, 133–134, 226, Dip coating, 82
235, 238 Dislocation, 35–36, 42, 48–49, 77, 85,
Chemical elements, 4 156–161, 230
Chemical potential, 91–92, 94–95, Dispersant, 80, 153–154, 164–166, 239
113–114, 163 Dispersion hardening, 97
Chemical reaction, 4, 7, 10, 51, 94, 96, 119, Dissolution methods, 4
127, 167, 236 Distribution, 3, 32, 37–38, 43–44, 48–51,
Chemical synthesis, 4 53–54, 58, 79, 89, 92, 112–113,
Chemical vapor deposition (CVD), 4–6, 29, 116, 120–121, 123–125, 133–134,
150, 226, 229 152–156, 164, 167, 169, 171,
Chromium oxide, 34, 230 175–176, 196, 208, 225, 229, 231,
Clusters, 1, 3, 95, 214 234, 236, 238–239, 244
CMOS, 189, 192, 242 Double layer, 112, 124–128, 130–132,
Coercivity, 47 163–166, 169
Coherency, 84 Double-layer structure, 124–125
Cohesion, 30–31, 33–36, 45, 100, 103, 211, Driving force, 79, 84, 91, 95, 111, 114, 134,
215, 230, 232 196, 199
Commercial methods, 4 Drying process, 2, 149, 151
Compact structure, 35 Ductility, 35, 42, 45, 153, 232, 239
Compatibility, 17, 31, 63, 65–66, 97–98, 103, Duty cycle, 37, 50–53, 112–113, 116, 162,
190, 203, 211, 228 170, 175
Complex compound, 127
Compressed metals, 94
Compression, 95, 157 E
Compressive stress, 90 Elastic strain, 90
Concentration over-potential, 127 Elastic stress, 90
Conduction, 5 Elastic tension, 90
Convection phenomena, 112 Elcho oxide orbit, 7
Corrosion current density, 112 Electrical, 3–4, 16–17, 34, 39, 43, 45, 56,
Cosmetics, 4, 226 58–60, 62, 66, 77–78, 82, 85–87,
Creep, 35, 48, 49, 59, 65, 133, 230, 233, 94–96, 99–102, 111–112, 124–128,
234, 238 130–133, 152, 154, 162–163,
Creep rate, 48–49, 238 165–167, 169, 176–177, 201–203,
Crushing, 103 207, 212, 214–217, 224, 228, 237,
Crystalline, 4, 6, 21, 30–31, 34–36, 40–42, 239, 243
44–45, 47–49, 52, 54–60, 71, 75, Electrochemical deposition, 78, 96, 111, 129,
77–81, 83–85, 89, 92–96, 100, 111, 130, 132, 237
114, 128, 131, 133–135, 139, 152, Electrochemical deposition process, 96, 111,
156, 174, 183, 192, 201–202, 226, 129, 237
229, 231–235, 138, 242–243 Electrochemical nucleation, 123
Crystalline nuclei, 111 Electrochemical phase state, 119
Crystalline structure, 4, 44, 55, 58, 77, 79–80, Electrochemical potential
83–85, 92, 174, 231, 235 of electrolyte, 113
Crystallization of glassy phases, 96 Electrochemical properties, 93, 111, 113, 138
Cyclic loading, 160 Electrochemical supersaturation, 114
Electrochemistry, 29, 46, 141, 232, 233
Electro-crystallization, 47, 111, 116
D Electrode surface energy state, 119
Data storing capacity, 216 Electrodeposition, 5, 40, 49–50, 52, 69, 97,
Decomposition, 79, 95, 127 121, 146, 152, 174–175, 178, 234
Densification, 8 Electro-explosion, 4
Density of deposited metal, 39 Electromagnetic compatibility, 203
Index 247
Electron-phonon collision, 206, 244 H

Electrostatic sustainability, 165 Hall-petch, 48–49, 59, 132, 156–157,
Entangle bonding energy, 164 233–234, 238–240
Enthalpy, 93–95 Hardness, 15, 17, 29–36, 41–42, 45, 47–52,
Environmental modification, 4, 226 60, 100, 102, 112, 149, 152–154,
Equilibrium state, 77, 83, 91–92, 94, 162–163, 170, 173–175, 211, 214,
113–115, 192, 206 228–233, 238–239, 241
Evaporation, 6, 36, 48, 55, 64, 95, Helmholtz-perrin model, 125
226, 233 High temperature inertness, 97
Exchanged current density, 39 High velocity oxygen fuel spraying, 29
Holmholtz free energy, 92
Homogenous system, 92
F Hybrid sol, 2
Fabrication methods, 6 Hydro gel, 7
Faraday constant, 39, 94, 126 Hydrogen-reduction reaction, 134
Fatigue strength, 171, 240 Hydrogen solubility, 47
Finite element implementation, 160 Hydrogen transition, 54
Florescence, 226 Hydrolysis, 2, 7–8, 10–11, 136, 227
Foliating, 173, 241 Hydrolysis reaction, 2, 7–8, 10–11,
Foliation, 99, 102, 236 136, 227
Food packaging, 16, 211–212, 244 Hydroxyapatite, 31, 144, 211, 229
Free energy, 77, 85, 88–95, 195–196, Hydroxyl groups, 102
199, 235 Hygienic, 16, 210
Friction, 15, 38, 45, 47, 49, 121, 132–133,
150, 153, 162, 170, 174, 230,
238–239 I
Fullerenes, 2 Infrared, 25, 100, 203–205, 243
Functional application, 59 Inhibition efficiency, 78
Functionally graded coating (FGC), 32 Insulation, 5
Integrated circuits, 5, 135, 185
Interface atoms, 55
G Interface curvature, 83
Galvanic potential, 114 Interface free energy, 83, 90
Gamma function, 120 Interface traction, 86
Gas annealing, 13, 228 Interfaces thermodynamics, 85
Gas phase pyrolysis of flame, 4 Inter-level connections, 83
Gas-condensation process, 96 Intra-crystalline spaces, 55
Gasro gel, 7 Intra-granular, 54
Gibbs free energy, 85, 93, 196, 235 Ion exchange, 85
Gibbs-thomson equation, 115 Ionic activity, 114–115
Glasses, 7, 9, 15–16, 61, 64, Ionic conductivity, 55–57
100, 102, 209 Ionic radius, 124–125
Gouy-chapman model, 125–126 Iso electric point, 153, 168–169, 239
Grain boundary, 40, 48–49, 52, 54, 56–58,
78–79, 84, 94–95, 130, 132–135,
153, 159, 161, 232, 238 K
Grain size, 34, 39, 41–42, 45, 47–49, 52, Kinetic, 77–78, 117–120, 124, 197, 236
54–56, 58–60, 89, 94–96, 132–134,
156, 171, 178, 193–194, 201,
230–232, 234, 237–238, 241, 243 L
Granule size, 78, 133, 238 Langmuir absorption isotherm, 39
Grinding, 4, 30, 48, 96, 157, 233, 241 Laser abrasion, 4
Guglielmi, 39, 60, 162–163, 222 Lattice imperfections, 84
Guglielmi model, 39, 162–163 LCD monitors, 62
248 Index
L (cont.) N
Light resistant panels, 61, 101 Nano porous material, 2, 9
Light valves, 5 Nano yarn, 9
Local corrosion, 52, 54, 132, 134, 238 Nano-capsule, 2
Lubricants, 4, 226 Nanocoating, 29, 58
Luminescent properties, 201 Nanocomposite
Nanocomposite coatings, 37, 43–44, 69, 97,
116, 146, 150–152, 174–177, 179,
M 238–239
Magnetic, 3–5, 16–17, 36, 38, 55–56, Nano-crystalline alloys, 84
59, 62, 72, 79, 94, 133, 149, Nanocrystalline coatings, 35
203–204, 216, 225–226, 228, Nano-crystalline nickel, 41, 45
235, 243 Nanofibers, 2
Magnetic nano-layers, 62 Nano-hybrid particles, 2, 149, 187, 225, 241
Magnetron sputtering, 6, 27, 205, 226, 243 Nanometric scale, 1, 83, 116, 175, 225
Malleability, 47–49, 59, 223–224 Nano-nucleuses, 122
Mechanical, 3–5, 13, 30–39, 42–45, 48, 59, 63, Nano-particle masks, 210
69, 70–71, 73, 79, 80, 88, 96, 112, Nanoparticles, 3–4, 16, 40, 61, 97, 121–122,
121, 132–133, 151–157, 171–172, 136, 149–154, 162, 166–167,
174, 190, 192–194, 225–226, 169–170, 177–179, 182, 206–207,
229–230, 232–235, 238–239 213, 216, 225–226, 230, 239, 244
Mechanical alloying, 4, 192–194, 242 Nano-porous materials, 2
Mechanical properties, 5, 31–33, 35, 37, Nano-powders, 29, 30, 44, 85–86
42–43, 45, 48–50, 59, 71, 79, Nanorod, 79, 235
112, 132, 133, 149, 153–154, Nano-scale thickness, 154–155, 225
156–157, 226, 229, 232, Nanostructured coating, 1, 15, 27, 29, 45
234–235, 238–239 Nanostructured films, 6, 201, 226
Medical applications, 16, 61 Nanostructured materials, 2, 78–79, 83–85,
Membranes, 42 93–96, 133, 152, 203, 234–235, 238
Metal capacity, 39 Nanosystems, 1, 157
Metal cation, 10, 124, 127, 236 Nanotechnology, 1, 3–4, 15, 99, 225–226, 228
Metal chalcogenide, 201 Nano-whisker, 79, 235
Metal ion structure, 124 Nano-wires, 2, 29, 46–47, 98, 152, 158
Metal lattice, 126, 136 Nernst equation, 114
Metallic ions, 10, 94, 111–114, 126, 152, Neutral surface, 114
237–238 Neutralization, 84
Micro electromechanical Nickel-alumina nanocomposite
systems (MEMS), 36 coating, 152–153, 166, 239
Micro/nano-systems, 156–157, 161, 240 Non-linear optical properties, 201
Microelectronics, 185, 203 Non-oxide ceramics, 3, 225
Milling, 4, 80, 96, 192–194 Norio taniguchi, 1
Mineral materials, 5, 7 Nuclear pellet, 1
Miniaturization, 185 Nucleation, 77–78, 96, 112, 114–121, 123,
Mole fraction, 92 127–128, 130, 158, 236
Molecular electricity, 2 Nucleus situation, 120
Molecular machinery, 1 Nucleuses, 111–124, 191, 198, 236
Molecules, 1, 12, 25, 39
Monomer, 8, 12, 227
Mosfet, 185, 189 O
Multi-crystalline, 45, 49, 52, 55–56, 78, Off-pulse time, 129–132, 237
84–85, 89, 94–95, 134, Olation, 10
234–235, 238 On-pulse time, 129–131, 237
Multi-layers, 29–30, 35, 65, 79, 174, Opaque, 5, 100, 203, 226
229, 235
Index 249
Optical, 3–5, 13–17, 34, 38, 61, 64, 99, 149, Reflection, 4–5, 61, 99, 209–210, 226
201, 203–205, 207–208, 225–226, Resistance over-potential, 128
228, 243 Response surface methodology, 36–37, 175
Optical entrapment, 5, 226 Reversible work, 90
Optical features, 4 Richard feynman, 1
Organic contaminator, 44 Rotating coating, 5
Organic ligand, 233
Organic thin films, 5
Oxolation, 10 S
Saint-Venant’s principle, 154
Salicide, 189–192
P Salt spray test, 132, 134
Particle growth, 8, 10 Scale of nano, 1, 225
Particle polymerization, 8 Scanning electron microscope (SEM), 3
Permeability, 47, 54–55, 85 Scanning tunneling microscopy
Pesticides, 4 (STM), 111
Phase interface, 93 Scratch resistance, 4, 100, 175, 226
Phase isolation, 92 Scratching, 35, 103
Phase transition, 86, 199 Sealants, 4, 226
Photo-catalysts, 44, 231 Self assembling, 5
Physical properties, 6, 36, 38 Self-cleaning glasses, 16, 209
Physical vapor deposition Self cleaning properties, 4, 101, 226
(PVD), 6, 29, 150 Self-lubricity, 97
Pitting corrosion, 135 Semi-conductor wafers, 5
Plasma arc plating, 11 Semi-spherical nucleus, 122–123, 236
Plasma arc spraying, 11 Sensing characterization, 192
Plasma coating, 12 Separation, 79, 119, 129, 237
Plasma polymer precipitation, 12, 227 Setric forces, 165
Plasma scattering coating, 11 Setric sustainability, 164–165
Plasma spray technology, 66 Silicates, 3, 225
Plasma synthesis, 4 Silicide, 185–186, 189–193, 196, 198, 201,
Polarizer, 16, 62, 215 203, 214, 241–242
Polarizer nano-layers, 215 Silicides specifications, 189
Polyethylene, 38, 64, 230 Silicon nitride (Si3N4), 3
Polytetrafluoroethylene, 38, 152, 238 Size dependency, 29, 36, 171, 175, 217
Porosity value, 129, 237 Size effect, 1–3, 31–32, 56–57, 85, 86, 111,
Porous templates, 46 135, 137, 149, 154–161, 187, 189,
Potential energy, 5, 226 192, 201, 204, 225–226, 240–243
Power generation industry, 65 Size-dependent phenomenon, 154
Pulsed current, 36, 40, 49–51, 53, 112, 116, Sodium benzoate, 78
175, 178 Sodium nitrate, 78
Solar cells, 62, 214–215
Sol-gel, 2, 4–10, 13–14, 30, 80–83, 86, 102,
Q 187, 193
Quantum dots, 2, 176, 217 Solid solubility, 47
Quantum phenomena, 98 Solid state method, 4
Quantum size effect, 2–3, 149, 187, 204, 225, Specific heat, 79, 93–94, 235
241–243 Spin-coating, 80
Spray coating, 5, 17
Stern-graham model, 226
R Stiffness, 5, 132–133, 150, 155, 159, 238
Rate of electrode reactions, 126 Stillinger-weber model, 155
Reductant agents, 111 Strain hardening rate, 156, 159, 240
Reduction, 9, 15 Strain-to-failure, 5
250 Index
S (cont.) Thin films, 2, 4–6, 9, 11–12, 15, 42, 56–57, 84,

Strength, 15, 30, 34, 37, 42, 44–49, 54, 59, 61, 124, 149, 156, 158, 169–171,
104, 132, 149–150, 153, 156–161, 202–204, 206, 208–209, 214,
170, 172–173, 204–205, 210, 228, 226–227, 243–244
231, 233–234, 239–241, 243 Titanium aluminide nitride, 33
Strength enhancement, 173 Titanium boro-nitride, 33
Stress corrosion cracking, 47 Titanium carbo-nitride, 33
Stress gradient, 83, 235 Titanium nitride, 33–36, 229–230
Structural applications, 59, 63 Torsion, 160
Structural disorder, 55–56 Transformator, 59
Super elasticity, 150 Transitional metal nitride
Super hard, 29, 35 coatings, 29, 33, 228
Super-hard coatings, 29 Transparency, 4–5, 226
Super-lattice coating, 36 Transparent conductor coatings, 62, 213
Super rough, 35 Transparent glass, 9
Supersaturated state, 114 Transpassive behavior, 134
Surface elasticity, 154–155, 239 Tungsten carbide, 38, 41, 45, 100,
Surface engineering, 16–18, 60, 63–65, 177–178, 232
228, 232 Turbine fans, 101
Surface geometry, 5, 226 Two dimensional nano-films, 154
Surface stress, 88, 154–155
Surface-to-volume ratio, 158
Surfactant, 43, 46, 164, 167, 233 U
Suspension, 6, 8, 152, 165, 168–169, Ultrasonic bath, 49
226, 238 Ultrasonic energy, 43, 167
Ultra-thin films, 171
Ultraviolet, 2, 14, 99–100, 149, 187,
T 204–206, 208–209, 213, 225,
Tabularization, 173 236, 241–243
Tafel polarization, 112, 116 Ultraviolet beam, 99–100, 236
Taguchi method, 40, 97, 121 Ultraviolet-visible spectroscopy (UV-VIS), 2,
Tensile stress, 88 187, 241
Tertiary nanocomposite, 40, 121–122, 178 Ultraviolet–visible spectrumn, 2, 149
Thermal capacity, 79, 235 Uniaxial tensio, 156–157
Thermal evaporation, 6, 226
Thermal expansion, 44–45, 47, 82–84, 132,
211, 231–232 V
Thermal extension coefficient, 79 Vacancy, 57, 77, 132
Thermal light, 100 Vacuum annealing, 13, 228
Thermal oxidation, 13–14 Vacuum chamber, 6
Thermal scattering coating, 11 Van der waals force, 164
Thermal stability, 29, 41, 47, 58, 187, Vapor resistant layers, 16
190–192, 195–202, 207, 228, Vertex energy, 89
234, 242 Viscosity, 8–9, 168–169
Thermodynamic equilibrium, 113 Volatile organic compounds, 65
Thermodynamics, 83, 85–86, 235 Volumetric percentage, 39, 152, 154, 162,
Thermoelectric tools, 5 167–168, 239
Thickness, 1, 4–5, 8–9, 32, 35–36, 42, 44, 48,
55–60, 80, 83, 98, 126–128,
135–137, 149–150, 154–156, 158, W
170–172, 174, 186–187, 189–192, Water memory, 86
197–208, 225–226, 229–231, Water repellence, 5, 226
239–243 Waveguides, 5
Thin film transistor (TFT), 15 Wavelengths, 4
Index 251
Wear, 5, 15–16, 30, 37, 47, 49, 60–61, 82, 97, Y

103, 121, 173, 174, 176–179, 217, Yield strength, 49, 156–160, 171, 240
226, 228–229 Young modulus, 47, 49, 132
Weibull statistics, 32
Z
X Zeldovich factor, 118
Xerogel, 9 Zero dimensional nanomaterials, 29
X-ray diffraction (XRD), 187 Zeta potential, 9, 153, 168, 239

(Engineering Materials) Mahmood Aliofkhazraei (Auth.) - Nanocoatings - Size Effect in Nanostructured Films-Springer-Verlag Berlin Heidelberg (2011)

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

(Engineering Materials) Mahmood Aliofkhazraei (Auth.) - Nanocoatings - Size Effect in Nanostructured Films-Springer-Verlag Berlin Heidelberg (2011)

Uploaded by

Copyright:

Available Formats

Engineering Materials

For further volumes:

ISSN 1612-1317 e-ISSN 1868-1212

ISBN 978-3-642-17965-5 e-ISBN 978-3-642-17966-2

Springer Heidelberg Dordrecht London New York

Ó Springer-Verlag Berlin Heidelberg 2011

Cover design: deblik, Berlin

Printed on acid-free paper

Springer is part of Springer Science+Business Media (www.springer.com)

February 2011 Mahmood Aliofkhazraei

1 Synthesis, Processing and Application

2 Size Dependency in Nanostructures . . . . . . . . . . . . . . . . . . . . . . . 29

2.2.3 Super Rough and Super Hard

3 Characterization of Nanostructured Coatings . . . . . . . . . . . . . . . . 77

3.16 Abrasion, Scratch, and Corrosion Resistant Coatings . . . . . . .. 99

4 Size Effect in Electrochemical Properties

4.18.3 Electrical Properties . . . . . . . . . . . . . . . . . . . . . . . . . 133

5 Size Effect in Mechanical Properties

6 Size Effect in Physical and Other Properties

6.2.3 Transition from TiSi2 to NiSi . . . . . . . . . . . . . . . ... 191

6.12 Lubricating and the Other Applications . . . . . . . . . . . . . . . . . 216

1.1 What is Nanotechnology?

Nanotechnology is a general term identified by advanced technology in the nano

1.2 The Role of Size Effect in Nanotechnology

M. Aliofkhazraei, Nanocoatings, Engineering Materials, 1

Fig. 1.1 The ultraviolet–

Fig. 1.2 a Scanning electron

1.4 Production of Nanoparticles

Production of nanoparticles is achievable through following solutions:

1.5 Applications of Nanoparticles

High volumes of nanoparticles can be applied in detergents, cosmetics, pesticides,

1.6 Thin Films

1.7 Production and Application of Thin Films

Currently different processes are applied for production of thin nanostructured

1.7.1 Introduction to Sol–gel Method

In fact sol–gel procedure is a mineral network synthesis by chemical reactions

MðORÞm þ H2 O ! MðORÞm1 ðOHÞ þ ROH

2. Micro molecule or polymer sols

1.7.2 Sol–gel Chemical Reaction

1. Hydrolysis: Generated by dissolving salt in water, metal cation shapes water

1.7.3 The Effect of Catalyst Hydrolysis

1.7.4 Electric Precipitation

1.7.5 The Rotate Coating

1.7.6 Scattering Coating

1.7.7 Self Layout

1.7.8 Plasma Polymerization

Most serious obstacles like temporary constancy (thermal, mechanical, optical

Annealing is a heating treatment which has an altered material in it’s structure

1.7.10 Heating Oxidation

The thermal oxidation is method used under high temperature (about

1.8 Applications of Nanostructured Coatings

Nowadays, nanotechnology is rapidly developing and promoting the quality of

some parts the important applications of nano-structured coatings have been

Some of applied nano-particles characteristics, compared with those of traditional

1.9 Coating and Surface Engineering

During production, packaging, and finally preparing in markets, all applied

1.10 Coating Issues and Applications

Coating is among main parts of surface engineering. Surface engineering is an

was expended on coating for improvement and enhancement of surface properties

Nanostructures are some 0, 1, 2 or 3 dimensional materials which are mostly

2.2 Nanocomposites and Their Production Methods

2.2.1 Thermal Spraying Nano-Composites

M. Aliofkhazraei, Nanocoatings, Engineering Materials, 29