Ashok Thesis Final

Surface Property Modification of Copper
By Nanocomposite Coating

A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE

REQUIREMENTS FOR THE DEGREE OF

Master of Technology
In
Metallurgical and Materials Engineering

Submitted by
Ashok Akarapu
Roll No. 209MM1232

Department of Metallurgical & Materials Engineering
National Institute of Technology
Rourkela
2010-2011

Surface Property Modification of Copper
By Nanocomposite Coating

A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE

REQUIREMENTS FOR THE DEGREE OF

Master of Technology
In
Metallurgical and Materials Engineering

Submitted by
Ashok Akarapu
Roll No. 209MM1232
Under the supervision of
Prof. A. Basu and Prof. S.K. Pratihar

Department of Metallurgical & Materials Engineering
National Institute of Technology
Rourkela
2010-2011

National Institute Of Technology
Rourkela

CERTIFICATE

This is to certify that the thesis entitled, Surface Property Modification of Copper by
Nanocomposite Coating, submitted by Ashok Akarapu in partial fulfillment of the requirements
for the award of Master of Technology Degree in Metallurgical and Materials Engineering
Department at the National Institute of Technology, Rourkela is an authentic work carried out by
him under our supervision and guidance.
To the best of our knowledge, the matter embodied in the thesis has not been submitted to any other
University/ Institute for the award of any degree or diploma.

Prof. A. Basu Prof. S.K. Pratihar
Dept. Metallurgical & Materials Engineering Dept. Ceramic Engineering
National Institute of Technology National Institute of Technology
Rourkela-769008. Rourkela-769008.
Date: Date:
i

ACKNOWLEDGEMENT

With deep regards and profound respect, I avail this opportunity to express my deep sense of
gratitude and indebtedness to Prof. A. Basu, Department of Metallurgical and Materials
Engineering and Prof. S.K. Pratihar, Department of Ceramic Engineering NIT Rourkela, for
their inspiring guidance, constructive criticism and valuable suggestion throughout in this
research work. It would have not been possible for me to bring out this thesis without their help
and constant encouragement.

I am sincerely thankful to Dr B. B. Verma, Professor and Head of Metallurgical and Materials
Engineering Department for providing me necessary facility for my work. I express my sincere
thanks to Prof. B. C. Ray and Prof M. Kumar, the M.Tech Project co-ordinators of Metallurgical
& Materials Engineering department and also Prof. Archana Mallik Electro metallurgy lab in
charge for providing me the necessary facilities for my work. I express my sincere gratitude to
Prof S. K. Pratihar, department of Ceramic Engineering, NIT Rourkela for giving me opportunity
of using Nano Zetasizer. I also express my sincere gratitude to Prof K. K. Ray, department of
Metallurgical & Materials Engineering, IIT Kharagpur for allowing me to use Mircrohardness
machine for my work. I also express my sincere gratitude to Prof D. Behera, department of
Physics NIT Rourkela, given opportunity for measuring Electrical Resistivity of my samples.

I am highly grateful to lab Members of Department of Metallurgical and Materials Engineering,
NIT Rourkela, especially Mr. Heymbram, Mr. R. Pattanaik, Mr. U.K. Sahu for their help during
the execution of experiments.

Special thanks to my family members always encouraging me to higher studies, all department
members specially Mr. Tanti, Lab assistant of Electro Metallurgy lab and all my friends of
department of Metallurgical and Materials Engineering for being so supportive and helpful in
every possible way.

Date: Ashok Akarapu
ii

LIST OF FIGURES
Figure 2.1: Electrodeposition setup for Copper from Copper sulfate solution.
Figure 2.2: pH versus zeta potential illustrating the Isoelectric point.
Figure 2.3: Schematic of Electrocodeposition process.
Figure 2.4: Mechanism of Particle codeposition into a metal deposit.
Figure 2.5: Schematic of Adhesive wear mechanism.
Figure 2.6: Schematic of Abrasive wear mechanism.
Figure 2.7: Schematic of Erosive wear mechanism.
Figure 2.8: Schematic of Surface Fatigue wear mechanism.
Figure 3.1: Nanozeta sizer (Model: Nano ZS, Malvern instrument).
Figure 3.2: JEOL JSM-6480LV Scanning Electron Microscopy.
Figure 3.3: LECO LM700 Microhardness tester.
Figure 3.4: DUCOM TR-208-M1 Ball on plate wear tester.
Figure 4.1: Particle size distribution of (a) TiO
2
powder (b) Al
2
O
3
powder.
Figure 4.2: pH Vs Zeta potential for isoelectric point determination of (a) TiO
2
(b) Al
2
O
3

powder in water.
Figure 4.3: XRD peaks of (a) Raw TiO
2
powder (b) Raw Al
2
O
3
powder.
Figure 4.4: Comparable XRD pattern of Cu-TiO
2
coatings (a) 10 g/l TiO
2
(b) 30 g/l TiO
2
in the
bath along with substrate (pure Cu) XRD pattern.
Figure 4.5: Enlarged XRD pattern of Cu-TiO
2
coating at TiO
2
10 g/l, current density 8 A/dm
2
.
Figure 4.6: Comparable XRD pattern of Cu-Al
2
O
3
coatings (a) 10 g/l Al
2
O
3
(b) 30 g/l Al
2
O
3
in
the bath along with XRD pattern of substrate (pure Cu).
iii

Figure 4.7: EDS of (a) Cu-TiO
2
deposited at 10 g/l TiO
2
, 5 A/dm
2
(b) Cu-Al
2
O
3
deposited at 30
g/l Al
2
O
3
, 11 A/dm
2
, Spot EDS on surface of (c) Cu-TiO
2
(d) Cu-Al
2
O
3
composite coatings.
Figure 4.8: Surface morphology of electrodeposited Cu-TiO
2
coatings (a) & (b) TiO
2
10 g/l in
bath, current density 5, 11 A/dm
2
, (c) & (d) TiO
2
30 g/l in bath current density 5, 11 A/dm
2
.
Figure 4.9: Surface morphology of electrodeposited Cu-Al
2
O
3
coatings (e) & (f) Al
2
O
3
10 g/l in
2
(g) & (h) Al
2
O
3
30 g/l in bath, current density 5, 11 A/dm
2
.
Figure 4.10: Effect of TiO
2
/Al
2
O
3
concentration in bath on co deposited wt% of (a) TiO
2
(in
terms of Ti) (b) Al
2
O
3
(in terms of Al) in composite coatings at current densities 5, 8, 11 and 14
A/dm
2
.
Figure 4.11: Effect of current density on microhardness of (a) Cu-TiO
2
(b) Cu-Al
2
O
3
coatings at
current densities 5, 8, 11 and 14A/dm
2
.
Figure 4.12: Comparable wear plots between wear depth and sliding distance of Cu- 10 g/l
TiO
2
, Cu-30 g/l TiO
2
and without TiO
2
coatings (a) at 11 A/dm
2
(b) at 14 A/dm
2
current
densities.
Al
2
O
3
, Cu- 30 g/l Al
2
O
3
and Cu without Al
2
O
3
2
(b) 14 A/dm
2
.
Figure 4.14: SEM micrographs of wear track of (a) substrate (pure Cu) (b) Pure copper (without
ceramic oxide) at 11 A/dm
2
( c ) Cu- 10 g/l TiO
2
at 11 A/dm
2
current density and (d), (e) & (f)
SEM micrographs of same wear tracks at higher magnification.

iv

LIST OF TABLES
Table 3.1: Composition of Copper sulfate bath solution for Cu-TiO
2
/ Cu- Al
2
O
3
and pure
copper coatings.
Table 3.2: Deposition parameters of Cu-TiO
2
/ Cu-Al
2
O
3
and Pure Copper coatings.
Table 4.1: Relative Texture Coefficient (RTC
(hkl)
) of Cu- TiO
2
composite coatings at 10, 30 g/l
TiO
2
and current densities 5, 8, 11, 14 A/dm
2
.
(hkl)
) of Cu-Al
2
O
3
Al
2
O
3
2
.
(hkl)
) of unreinforced Copper coatings at Current
densities 5, 8, 11 and 14 A/dm
2
.
Table 4.4: Co-deposited TiO
2
(in terms of Ti), Al
2
O
3
(in terms of Al) wt% in Cu-TiO
2
& Cu-
Al
2
O
3
composite coatings at 10 g/l, 30 g/l in bath and Current densities 5, 8, 11 and 14 A/dm
2
.

v

Abstract
Copper has high electrical and thermal conductivities, good corrosion resistance at ambient
temperature, excellent malleability/workability and reproducibility, apart from these it is cheap
and abundantly available metal other than good conducting metals like Silver. But has poor
mechanical properties such as hardness and wear resistance. Some applications like Contacts in
electrical switches necessitate the improvements in the mechanical properties without much loss
of electrical and thermal conductivities. Bulk modification / alloying have been tried but
limitations in alloying and adversely decrease in its electrical and thermal conductivities has
been reported. Another way to improve its mechanical properties is with Surface modification by
developing composite coating on its surface. In the present work we employed Electrodeposition
process to develop a composite coating with Cu matrix and Ceramic oxide particles TiO
2

(particle size ~202 nm), Al
2
O
3
(particle size ~287 nm) as reinforcements. The coatings were
developed with 10 g/l, 30 g/l and 0 g/l (unreinforced) concentrations in bath, at four different
current densities (5, 8, 11, 14 A/dm
2
) with using copper sulfate bath in order to study the effect
of Current density and particle concentration in bath, on structure and properties of the coatings
developed. The crystallite size was averagely 50-65 nm and a strong (220) texture was obtained
in composite coatings and unreinforced Cu coatings determined from the XRD data. The
composition and surface morphology of coatings were studied by using EDS and SEM. Hardness
and Wear resistance of the coatings were determined by using microhardness tester and ball on
plate wear tester, improved hardness and wear resistance of composite coatings were observed
compared to the unreinforced copper coatings.

Keywords: Electrodeposition, Electrocodeposition, TiO
2
, Al
2
O
3
, copper, texture, microhardness,
wear.

CONTENTS

Title Page No
ACKNOWLEDGEMENT i
LIST OF FIGURES ii
LIST OF TABLES iv
ABSTRACT v
CHAPTER 1
INTRODUCTION
1.1 Introduction 1
1.2 Objectives and Scope of the present study 2
1.3 Scope of the thesis 3
CHAPTER 2
LITERATURE REVIEW
2.1 Strengthening of Copper 4
2.1.1 Bulk modification 4
2.2 Surface Engineering 6
2.2.1 Various Coating techniques 6
2.3 Electrodeposition 8
2.3.1 Advantages of Electrodeposition 9
2.3.2 Applications of Electrodeposition 10
2.3.3 Electrodeposition as synthesis of Nanostructured materials 11
2.4 Pulsed Electrodeposition 12
2.5 Electrophoretic deposition 13
2.5.1 Factors influencing EPD 14
2.5.2 Zeta potential and its importance 14

2.6 Electrocodeposition 15
2.6.1 Mechanisms in Electrochemical Codeposition 17
2.6.2 Effect of deposition parameters on ECD 19
2.6.3 Different baths used for copper electroplating 21
2.7 Brief literature reviews of Cu-TiO
2
and Cu-Al
2
O
3
systems 21
2.7.1 Cu-TiO
2
Literature 21
2.7.2 Cu-Al
2
O
3
Literature 22
2.8 Wear and Various wear mechanisms 23
CHAPTER 3
EXPERIMENTAL
3.1 Sample preparation 27
3.2 Plating bath solution preparation 27
3.3 Particle size analysis 28
3.4 X-ray diffraction studies 29
3.5 Microstructural studies 30
3.5.1 Scanning Electron Microscope studies 30
3.6 Surface Mechanical property studies 31
3.6.1 Microhardness measurement 31
3.6.2 Wear behavior of the coatings 31
CHAPTER 4
RESULTS AND DISCUSSIONS
4.1 Particle size 33
4.2 Zeta potential measurement 34
4.3 XRD analysis 35
4.4 Microstructural characterization 41
4.4.1 EDS Analysis 41
4.4.2 SEM studies 43

4.5 Effect of TiO
2
&Al
2
O
3
concentration in bath 45
4.6 Surface Mechanical Properties 46
4.6.1 Microhardness study 46
4.6.2 Wear study 48
4.7 Brief comparisons of TiO
2
and Al
2
O
3
systems 52
CHAPTER 5
CONCLUSIONS
5.1 Conclusions 53
5.2 Scope of future work 54
CHAPTER 6
REFERENCES
6.1 References 55

Chapter 1
Introduction
Introduction
Objectives and Scope of the Present study
Scope of the thesis

1

CHAPTER 1
INTRODUCTION
1.1 Introduction
Copper (Cu) is environment friendly and abundantly available material that possesses a unique
combination of low electrical resistivity (16.78x10
9
m) and high thermal conductivity (394
Wm
-1
K
-1
), excellent malleability/workability, attractive colour, reasonably good corrosion
resistance at ambient temperature [1] and recyclability, apart from these it is cheaper than the
other conducting metals. Due to these excellent combination of properties Cu and its alloys are
most widely used engineering materials for conduction of electricity (electrical conductors,
wires, contacts, plugs) and heat (heat exchangers, linings, radiators, electrodes). However, poor
mechanical property often necessitates strengthening without adversely affecting its
electrical/thermal conductivity. Some applications like electrical contacts require mainly good
surface mechanical properties like hardness, wear resistance due to frequent rubbing action
during switching. Bulk modification/alloying decreases thermal and electrical conductivity and
along with electrical conductivity, thermal conductivity is also important so that the contacts can
quickly release the heat accumulated due to resistance heating and rubbing action during
switching. In such components Surface Engineering approach is wise one as it does not
adversely affect bulk properties like electrical and thermal conductivities compared to bulk
modification. The wide variety of surface coating techniques available are Physical vapor
deposition, Chemical vapor deposition, Thermal spraying, Electrodeposition, Electroless
deposition, Diffusion coatings, and Laser based techniques (Laser Cladding, etc.).
Metal matrix nanocomposites containing dispersed second-phase particulates have various
special properties such as dispersion hardening, self-lubricity, high temperature inertness, good
wear and corrosion resistance, and chemical and biological compatibility [27].
Electrocodeposition has several advantages in developing Metal matrix composite coatings
among other coating processes such as, uniform depositions on complexly shaped substrates, low
cost, good reproducibility and the reduction of waste [8]. Electrocodeposition process has been
in use successfully to develop such nanocomposite coatings from the past decades. The second
phase can be hard oxide (Al
2
O
3
, TiO
2
, SiO
2
) [7] or carbides particles (SiC, WC) [7], etc.,
2

embedded in metals like Cu, Ni, Cr, Co and various alloys. The applications of these coatings
include wear and abrasion resistant surfaces, lubrication, high hardness tools, dispersion-
strengthened alloys, and for protection against oxidation and hot corrosion [7, 9 -11].
The quality of the deposits influenced by wide number of variables which include current
density, particle characteristics, bath composition, hydrodynamics and the particle-bath
interaction. The amount of embedded second phase particles plays an important role in
improving the surface mechanical properties by refining the grain size of the matrix and also by
dispersion strengthening mechanism. Several parameters affect the embedded vol.% of second
phase particles, among which current density, particle concentration in the bath, and pH of the
solution are important variables. Current density plays an important role in controlling the
deposition rate which will in turn affect the concentration of incorporated particles in the
coatings.
In the present work parallel plate electrodeposition process employed to improve the surface
mechanical properties of copper without adversely effecting its electrical and thermal
conductivities, by developing a layer of nanocomposite coating consisting of copper matrix and
ultrafine ceramic oxide particles (TiO
2
, Al
2
O
3
) on surface of copper. And to determine the
optimized current density and particle concentration in the bath with the coating results achieved.
1.2 Objectives and Scope of the Present study
The aim of the present work is to improve the surface mechanical properties of Cu by electro
codeposition of Cu with dispersed second phase ultra fine particles like TiO
2
, Al
2
O
3
individually
the objectives of the work as summarized below:
1. To determine the particle size and Zeta potential (for isoelectric point) of the ceramic oxide
powders (TiO
2
, Al
2
O
3
) procured from Inframat Advanced Materials, Formington, USA by using
Malvern Zetasizer nano series Nano- ZS model instrument.
2. Electro codeposition of Cu with dispersed second phase ultra fine particles TiO
2
, Al
2
O
3

individually such that to develop Cu-TiO
2
and Cu-Al
2
O
3
nanocomposite coatings uniformly on
the surface of the Copper substrate.
3

3. Characterizations of The coatings developed
Phase identification, texture analysis and Chemical analysis (XRD, EDS).
Microstructure and Morphology (SEM, FESEM).
Surface mechanical properties (Hardness, Wear).
4. Optimization of the process.
5. Correlation with process parameters.
1.3 Scope of the Thesis
The organization of the rest of the thesis is as follows: Different strengthening mechanisms of
Cu, brief explanation about electrodeposition process with advantages over other coating
techniques, applications and about electro codeposition, effect of different parameters on the
properties of electro codeposited coatings, their applications and brief literature reviews on Cu-
TiO
2
and Cu- Al
2
O
3
composite coatings were provided in chapter 2. A detailed experimental
study and about different characterizations techniques were provided in chapter 3. In chapter 4 a
discussion about the results obtained from the characterizations of the powders (TiO
2
, Al
2
O
3
)
along with the mechanical property study of different co deposited samples were provided. In
chapter 5 a summary of main findings and conclusions of the present work were reported.
References were provided in chapter 6.

Chapter2
Literature Review

Strengthening Mechanisms of Copper
Surface Engineering
Electrodeposition
Pulsed Electrodeposition
Electrophoreticdeposition
Electrocodeposition
Brief Literature Reviews on Cu Nanocomposites
Wear and Various Wear Mechanisms

4

CHAPTER 2
LITERATURE REVIEW

2.1 Strengthening Mechanisms of Copper
2.1.1 Bulk modification
Copper have poor mechanical properties, usually the strength of the copper can be enhanced
based on solid solution (substitutional/interstitial), precipitation (coherent/semi-coherent) and/or
dispersion (externally added phases) strengthening mechanisms [12].
(a) Solid solution Strengthening / Alloying
Solid solution strengthening / alloying is the common process to improve the hardness and to
strengthen the pure copper. When Small amounts of an alloying element added to molten copper
will completely dissolve and form a homogeneous microstructure (a single phase). The common
alloying elements used for copper are Zn, Sn, Be, Cr, Ag, Au, Ni, Al, As, Fe, etc., When tin
added to copper the alloy formed is known as bronze the resulting alloy is stronger and harder
than either of the pure metals. When Zn added to pure copper the alloy is known as Brass. Tin is
more effective in strengthening copper than zinc, but is also more expensive and has a greater
detrimental effect on the electrical and thermal conductivities than zinc. Aluminum (forming
alloys known as aluminum bronzes), Manganese, Nickel, and Silicon can also be added to
strengthen the copper.
(b) Precipitation hardening / Dispersion Strengthening
Precipitation hardening/ Dispersion Strengthening is another strengthening mechanism of
copper. Both of the processes involves hindering or pinning of the dislocation motion in matrix
phase and strengthens the matrix phase. Precipitation process involves quenching a
supersaturated solid solution from an elevated temperature, then reheating to a lower temperature
(aging) to allow the excess solute to precipitate out and form a second phase. This process is
often used for copper alloys containing beryllium, chromium, nickel, or zirconium.
5

In Dispersion strengthening mechanism the strength of copper can be increased by finely
dispersing small, hard and inert particles in copper matrix. The dispersed second phase particles
again act as obstacles for dislocation motion same as in Precipitation hardening. They are not as
effective in increasing the strength of materials compared to precipitates since their size is
commonly larger than 10 nm and they are generally incoherent with the matrix. The main
advantage, however, is that these foreign particles generally neither dissolve at high temperatures
nor grow in size, as is known for precipitates. Thus, dispersion hardened materials maintain their
strength even at high temperatures.
(c) Grain size Strengthening
The strength of the materials can also be increased by increasing the grain boundary surface area
or decreasing the existing grain sizes to nanometers. The mechanism involved in increasing
strength is that the small grain sizes acts as obstacles to the dislocation motion and thus increase
in strength. According to the Hall-Petch relation the strength is inversely proportional to the
square of the average grain diameter. (i.e.,
y
=
0
+ k d
-1/2
) where
y
is the yield stress,
0
is
friction stress, k is the locking parameter, and d is grain diameter.
However, bulk modification approach is widely investigated for improvement of mechanical
properties of Cu and thereby improving the life of the Cu contacts. But bulk modification has
restrictions on solubility limit, also adversely affecting the electrical and thermal conductivities.
For example bulk alloying with Zn, Si, Sn and Al, though is effective in improving mechanical
strength by solid solution strengthening but proves counterproductive by decreasing the mean
free path of electrons and thereby increasing electrical resistivity [13]. On the other hand, Cr and
Be are the only alloying elements that enhances mechanical strength of Cu without adversely
affecting its electrical/thermal conductivity [14]. However, both Cr and Be have restricted solid
solubility in Cu (e.g. 0.89 at. % Cr in Cu at 1000 C) and Be is toxic, breathing of Cu-Be dust, as
formed when machining or welding may cause serious lung damage [15].
Another way to improve the mechanical properties of Cu and hence copper contacts is by
modifying the surface of the Cu contacts with hard coatings by using Surface Engineering
Techniques without adversely affecting the bulk properties such as electrical and thermal
conductivities of the contacts which are necessary for the contact applications.
6

2.2 Surface Engineering
Surface engineering is defined as branch of science that deals with the different techniques to
achieve desired surface properties and their behavior in service for engineering components.
Surface engineering techniques are being used in the automotive, aerospace, missile, power,
electronic, biomedical, textile, petroleum, petrochemical, chemical, steel, power, cement,
machine tools, and construction industries [16]. Surface engineering techniques can be used to
develop a wide range of functional properties, including physical, chemical, electrical, electronic,
magnetic, mechanical, wear-resistant and corrosion-resistant properties at the required substrate
surfaces. Almost all types of materials, including metals, ceramics, polymers, and composites
can be coated on similar or dissimilar materials.
Surface treatments that cause microstructure changes in the bulk material include heating and
cooling/quenching through induction, flame, laser, and electron beam techniques, or mechanical
treatments (one example is cold working). Surface treatments that alter the chemistry of a surface
include carburizing, nitriding, nitrocarburizing, carbonitriding, boronizing, siliconizing,
chromizing and aluminizing. Hard facing is another form of surface treatment, where the bulk
materials surface is given a protective layer of another material having more superior properties
than those of the bulk material. Each method of hard facing, examples of which are coating
deposition, cladding or welding, causes particular physical and chemical effects on the bulk
material, some beneficial, some detrimental [17]. The wide variety of Surface coating techniques
available are Thermochemical coatings (carburizing, nitriding etc.), Spray Coatings (thermal
spray coatings, Flame spray, Plasma spray coatings etc.), Electrodeposition,
Electrolessdeposition, Physical Vapor deposition ( Sputtering, Ion Plating, Ion Implantation etc.),
Chemical Vapor deposition (Plasma Enhanced chemical vapor deposition etc.) and Laser
Cladding, etc.,
2.2.1 Various Coating Techniques
(a) Electroplating
Electroplating is often also called "electrodeposition", a short version of electrolytic deposition,
Its a process using electrical current to reduce cations of a desired material from a solution and
coat that material as a thin film onto a conductive substrate surface.
7

(b) Electroless plating
Electroless plating processes involves no external current to reduce the metal cations into metal
atoms. Metal coatings in this process are produced by chemical reduction with electrons supplied
by a reducing agent (R.A.) present in the solution. The process was reported by Brenner and
Riddell [18] in 1946 for nickel and cobalt coatings and has been using extension to electroless
plating of copper, gold, palladium, platinum, silver and a variety of alloys involving one or more
of these metals.

(c) Physical Vapor Deposition
Physical vapor deposition (PVD) includes a broad class of vacuum coating processes in which
the material is physically removed from a source by evaporation or sputtering, transported
through a vacuum and condensed as a film on the surfaces of appropriately placed parts or
substrates. The thickness of the deposits can vary from angstroms to millimeters. PVD coatings
are generally used to improve hardness, wear resistance and oxidation resistance. Thus such
coatings use in wide range of applications such as Aerospace, Automotive, Medical / Surgical,
Cutting Tools, etc., As this process is carried out in a vacuum chamber, the size limitation of the
work piece is the drawback of this process. In addition the process is effectively line of sight so
deep holes, bores and undercuts cannot easily be coated. And also high capital cost, slower
deposition rate are the drawbacks of the PVD process.
(d) Chemical Vapor Deposition
This process involves meeting of one or more volatile precursor gases in the reaction chamber at
the heated surface (substrate), and they react or decompose forming a solid phase which and are
deposited onto the substrate surface.
The main steps that occur in the CVD process can be summarized as:
Transport of reacting gaseous species to the surface.
Adsorption of the species on the surface.
Heterogeneous surface reaction catalyzed by the surface.
Surface diffusion of the species to growth sites.
8

Nucleation and growth of the film.
Desorption of gaseous reaction products and transport of reaction products away from the
surface [19, 20].
CVD is a more complex method of forming thin films and coatings than PVD. CVD exhibits
several advantages such as the capability of producing highly pure and dense films or fine
particles at reasonably high deposition rates, and the capability of coating complex-shaped
components uniformly due to its non-line-of-sight nature. CVD is a versatile technique that can
be used to process metallic, ceramic compound and semiconducting thin films, some of these
include Elements, metals and alloys, carbides, nitrides, borides, oxides, etc., Depending on the
sources used for the activation of chemical reactions, the deposition process can be categorized
into thermally activated, laser-assisted and plasma-assisted CVD. The greatest problem with this
technique is the associated high temperature.
(e) Thermal Spray Coatings
Thermal spray processes haven been in using to form hard coatings on selected component
surface. The process involves heating of the material to be coated in a gaseous medium and
projected at high velocity as molten droplets onto a substrate surface. Upon impacting the
substrate surface, the droplets become flattened, transfer the heat to the cold substrate and
solidify rapidly to form the splats. Powders, rod and wires can be used as feedstock materials.
Several processing routes can be employed depending on the materials and desired coating
performances. These include plasma spraying, high velocity oxyfuel (HVOF) spraying,
detonation flame spraying, and flame spraying. Metals, polymers and ceramics are the most
widely used coating materials. Typical coating thickness obtainable with this process are 50-300
m. Out of all the coating techniques Electrodeposition is the oldest and widely using technique
to produce thin films the reasons were explained in detail in the coming section.
2.3 Electrodeposition
Electrodeposition is also called "electroplating", a short version of electrolytic deposition. Its a
process using electrical current to reduce cations of a desired material from a solution and coat
that material as a thin film onto a conductive substrate surface.
9

Electrodeposition is a versatile technique in making coatings, bulk products in micro to nano
dimensions. Electrolyte in the electroplating process is used as precursor for the material to be
developed and the material on which the material is to be deposited is termed as a cathode. If
coating is the objective of the processing, then the substrate material itself is used as a cathode.
Bath composition, temperature, pH, type of power supply, current density are the key parameters
which influences the deposition process and hence the properties of the deposited materials. The
Figure 2.1 shows a simple electroplating system for copper deposition from copper sulfate
solution.

Figure 2.1: Electrodeposition setup for Copper from Copper sulfate solution.

Materials processed via electrodeposition are pure Ni, Ni-based nanocomposites, copper, Cu-
based nanocomposites, layered CuNi nanocomposites, pure cobalt, CoNi alloys, WC-based
coatings, TiO
2
Ni nanocomposite coatings [2, 21] etc.

2.3.1 Advantages of Electrodeposition
Electrodeposition has several advantages over the conventional and latest deposition processes
summarized as
Low cost and industrial applicability, as it involves little modification of existing
electroplating technologies.
The process parameters can be easily tailored to get the desired microstructure.
10

Simple operation, as the electro deposition parameters can be easily tailored to meet the
required crystal grain size, microstructure and chemistry of products.
Versatility, as the process can produce a wide variety of pore free materials and coatings.
High production rates, even nano crystalline deposits can be formed on a cathode surface
during plating by properly controlling the electro deposition parameters, e.g. bath
composition, current density, temperature, pH, etc.,
Process can also be operated at room temperature and pressure.
Ability to produce compositions unattainable by other techniques.
No post deposition treatment.
Metals, alloys and polymers can be deposited by using this process. The metals have been
deposited are Ni, Cu, Cr, Co, Au, Zn, Pd etc., and alloys such as Co-Cu, Ni-Co, Ni-Cu,
Cu-Al, etc. Multilayer deposition can also be done by this process.
2.3.2 Applications of Electrodeposition
Since its invention in 1805 by Italian chemist, Luigi Brugnatelli, electroplating has become an
extensively used industry coating technology. Its applications are as given below [2, 4].
1. Decoration: Coating a more expensive metal onto a base metal surface in order to improve the
appearance. Applications are jewellery, furniture fittings, builders hardware and tableware.
2. Protection: Corrosion-resistant coatings such as chromium plating of automobile parts and
domestic appliances, zinc and cadmium plating of nuts, screws and electrical components. Wear-
resistant coatings such as nickel or chromium plating of bearing surfaces and worn shafts.
3. Electroforming: Manufacture of sieves, screens, dry shaver heads, record stampers, moulds,
and dies.
4. Enhancement: coatings with improved electrical and thermal conductivity, solderability,
reflectivity etc.
5. The magnetic and electrical properties make electrodeposited nanomaterials attractive as soft
magnets for high-efficiency transformers, power supplies and motor applications.
11

6. The exceptional catalytic properties make them strong contenders for different applications
such as electrodes for hydrogen evolution and fuel cells.

2.3.3 Electrodeposition as synthesis of Nanostructured materials
Nanostructured materials are those in which the main structural dimensions vary at the
nanometer scale; typical dimensions are smaller than 100 nm. From the synthesis point of view
electrodeposition is one of the oldest methods used to produce nanostructured materials for many
years. The synthesis of nanostructured materials with grain size control during the
electrodeposition process can be considered a distinct form of grain boundary engineering in
which the grain boundary content (types and quantities of grain boundaries) of a material are
controlled during material processing to achieve certain physical, chemical and mechanical
properties [22]. The final result is thus a bulk interfacial material, as originally defined by Gleiter
[23] which does not require any further processing of precursor powder material. In this respect,
electrodeposited nanocrystals are quite different from other nanostructures which are based on
consolidated particles. Potentially there are a very large number of pure metals, alloys,
composites, and ceramics which can be electrodeposited with grain sizes less than 100 nm. These
materials can be deposited as thin films (1 to 100 m) or in bulk form (several mm thick). The
co-deposition of ceramic materials with metals and polymers has created opportunities for the
preparation of novel hybrid nanomaterials and nanostructures that cannot be obtained by other
methods.
Fundamentally, electrodeposition process yields grain sizes in the nanocrystalline range when
the electrodeposition variables (example bath composition, pH, temperature, current density,
etc.) are chosen such that nucleation of new grains is favored rather than the growth of existing
grains. In practice, this can be achieved by using high deposition rates, formation of appropriate
complexes in the bath, addition of suitable surface active elements (Surfactant) to reduce surface
diffusion of ad-atoms, etc., The two key mechanisms that have been identified as the major rate
determining steps for nanocrystal formation are charge transfer at the electrode surface and
surface diffusion of adions on the crystal surface [24]. The diffusion of adions on the surface is
controlled by inhibition, for example, it is achieved by adsorption of foreign species such as
grain refiners on the growing surface. The effectiveness of the grain refiners depending upon
surface adsorption characteristics, compatibility with the electrolyte and temperature stability.
12

For example saccharin [25], coumarin, and formic acid [26] have all been successfully applied to
achieve grain refinement down to the nanocrystalline range for nickel electrodeposits. The
second important factor in nanocrystal formation during electro crystallization is overpotential
[27, 28]. At lower potential and high surface diffusion rates the grain growth is favored, on the
other hand, high over potentials and low diffusion rates promote the formation of new nuclei.
The electrochemical processing have been used for the synthesis of nanocrystalline pure metals
(e.g., Ni, Co, Pd and Cu), binary alloys (e.g., Ni-P, Ni-Fe, Zn-Ni, Pd-Fe and Co-W), and ternary
alloys (e.g., Ni-Fe-Cr). Even multilayered structures or compositionally modulated alloys (e.g.,
Cu-Pb, Cu-Ni, Ag-Pd, Ni-P), metal matrix composites (e.g., Ni-SiC), ceramics (e.g., ZrO
2
), and
ceramic nanocomposites (e.g., Tl
a
Pb
b
O
c
) [4, 22, 29-30] have been successfully produced by
electrodeposition methods. DC electroplating, pulsed-current electrodeposition, as well as
codeposition processes to produce nano-composite materials are the types of electrodeposition
techniques have been used to produce nanostructured materials.
2.4 Pulsed Electrodeposition
Electrodeposition is the traditional method of DC electroplating. This has been modified by the
use of current interruption or even current reversal termed as pulsed electro deposition. In DC
plating, only the current or potential can be varied [31]. However, in pulse plating it is possible
to vary parameters independently, the current density, pulse frequency and the duty cycle which
is the ratio of pulse on time to the sum of on time and off time. The properties can be improved
because it is possible to obtain coherent, non dendritic deposits at much higher current densities
than with the straight direct currents [31-32]. The accompanying higher over potentials results in
higher nucleation rates thus results in finer grain size. Because of foreign substances may be
either adsorbed or not when the current is off during pulse plating [33-34] the mechanical
properties, the structure and texture can be different from those observed with conventional
deposition. The important parameters of EPD process include conditions of both the
electrochemical bath and the substrate. The conditions of the electrolyte bath are bath
composition, temperature, current density at the cathode, and transport behavior and those of
substrate (cathode) are crystallography and surface topography.
A major limitation of the electrodeposits produced by direct current is porosity and rough
deposits [35]. Pulse plating improves the deposit properties viz., porosity, ductility, hardness,
13

electrical conductivity, plating thickness distribution, finer grain size. Numerous NC metals and
alloys including Ni, Co, Cu, Zn and NiFe [31-34] have been produced by pulse
electrodeposition and reported to have unique properties in contrast to their coarse-grained (CG)
counterparts.
2.5 Electrophoretic deposition
Electrophoretic deposition is the process of depositing charged powder particles dispersed or
suspended in the liquid medium on the conductive substrate of opposite charge by the application
of DC Electricfield. Compared to other advanced shaping techniques, the EPD process is
versatile since it can be modified easily for a specific application. For example, deposition can be
made on flat, cylindrical or any other shaped substrate with only minor change in electrode
design and positioning. Also has advantages of short formation time, needs simple apparatus,
little restriction of the shape of substrates. The basic difference between an electrophoretic
deposition process (EPD) and an electrolytic deposition process (ELD) is that the former is based
on the suspension of particles in a solvent whereas the later is based on solution of salts, i.e.,
ionic species [36].
The electrophoretic deposition (EPD) technique has a wide range of novel applications in the
processing of advanced ceramic materials and coatings, such as in the fabrication of wear
resistant and anti-oxidant ceramic coatings, fabrication of functional films for advanced
microelectronic devices and solid oxide fuel cells as well as in the development of novel
composites or bioactive coatings for medical implants, there has been increased interest for its
application in nanoscale assembly for advanced functional materials. And also has been used
successfully for thick film of silica, nanosize zeolite membrane, hydroxyapatite coating on metal
substrate for biomedical applications, luminescent materials, high-Tc superconducting films, gas
diffusion electrodes and sensors, multi-layer composites, glass and ceramic matrix composites by
infiltration of ceramic particles onto fibre fabrics, oxide nanorods, carbon nanotube film,
functionally graded ceramics, layered ceramics, piezoelectric materials [36-42], etc.,

14

2.5.1 Factors influencing EPD
The process being involved the deposition of charged particles from the suspension onto the
conducting substrate (cathode) by the application of electric field. Thus two groups of parameters
determines the characteristics of this process
(1) Parameters those related to the suspension such as Particle size, Dielectric constant of the
liquid, conductivity, stability & viscosity of the suspension and Zeta potential.
(2) Parameters those related to the process including the physical parameters such as the
electrical nature of the electrodes, the electrical conditions (voltage/intensity relationship,
deposition time, etc.), effect of deposition time, applied voltage, concentration of the solid in the
suspension.
2.5.2 Zeta Potential and its importance
Zeta potential is the electrical potential that exists at the interface between the particle surface
and the stationary layer of the fluid attached to the particle; it is the key factor in the
electrophoretic and electrocodeposition procesess. It is a function of surface charge of a particle,
any adsorbed layer at the interface and nature and the composition of the surrounding medium in
which the particle is suspended. It is a very good index of the magnitude of the electrostatic
repulsive interaction between particles. It gives the degree of stability of the suspension.
If all the particles in suspension have a large negative or positive zeta potential then they will
tend to repel each other and there is no tendency to flocculate. However, if the particles have low
zeta potential values then there is no force to prevent the particles coming together and
flocculating. The general dividing line between stable and unstable suspensions is generally
taken at either +30 mV or -30 mV. Particles with zeta potentials more positive than +30 mV or
more negative than -30 mV are normally considered stable.
The most important factor that affects zeta potential is pH of the suspension. Let us suppose that
a particle in suspension with a negative zeta potential. If more alkali is added to this suspension
then the particles will tend to acquire a more negative charge which indicates lower pH value. If
acid is then added to this suspension a point will be reached where the negative charge is
neutralized. Any further addition of acid can cause a buildup of positive charge, indicates the
increase in the pH. Therefore a zeta potential versus pH curve will be positive at low pH and
lower or negative at high pH.
15

The below Figure 2.2 shows the plot between pH versus zeta potential, the point where the curve
passes through zero zeta potential is called the Isoelectric point and is very important from a
practical consideration. It is normally the point where the colloidal system is least stable or the
particle or molecule in the suspension carriers no net charge. In the typical schematic below the
Isoelectric point (I.P) is observed at pH 5.5.

Figure 2.2: pH versus zeta potential illustrating the Isoelectric point.

2.6 Electrocodeposition
It is the process of particle incorporation during the electrolytic deposition of metal, which
involves both the processes, elctrodeposition of metal from electrolyte solution and
electrophoretic deposition of the small sized particles from the suspension, the schematic of the
process is as shown in below Figure 2.3
16

Figure 2.3: Schematic of Electrocodeposition process

This process produces composite films consisting of a metallic matrix containing a dispersion of
small particles. The particles of pure metals, ceramics, and organic materials, for example oxide
or carbide particles, such as Al
2
O
3
, SiC, TiO
2
, WC, SiO
2
or diamond, a solid lubricant, such as
PTFE, graphite or MoS
2
, or even liquid-containing microcapsules ranging in size from sub-
micron to 100 m in diameter are used as dispersed second phase particles, and embedded in
electroplated Cu, Ni, Co, Cr, and various alloys. The concentration of particles suspended in
solution have varied from 2 up to 200 g/l producing composites with typically 1 to 10 vol% of
embedded particles [43].
The advantages of electrocodeposition technique over other coating methods are the uniformity
of deposition even for complex shapes, reduction of waste often encountered in dipping or
spraying techniques, low levels of contamination, the ability to produce functionally-gradient
material and to continuously process parts. In addition, this process avoids the problems
associated with high temperature and high pressure processing.
The applications of these electrocodeposited coatings include wear and abrasion resistant
surfaces, lubrication, high hardness tools, dispersion-strengthened alloys, and for protection
against oxidation and hot corrosion [44-46]. And also Electrocodeposition has been used to
produce high surface area cathodes which have been used as electro catalysts for hydrogen
electrodes in industrial water electrolysis [43]. The first application of electrodeposited
composite coating was the Ni/SiC coating used as the wear-resistant improvement in the Wankel
engine by Metzger et al., in 1970 [47]. The metal matrix composites have been synthesized
using Electrocodeposition include Ni-SiC and NiCo/Al
2
O
3
, Ni-TiO
2
, Ni-Co, Ni-Zn, Ni-Fe, Co-
17

W, Co-P, Pd-Ni, Cu-TiO
2
, Cu-Al
2
O
3
, Cu- ZrO
2
, Cu-ZrB
2
, Cu/CNTs, , Cu- WC, Ni-Fe-nano-
Si
3
N
4
, Co-Ni-nano- Al
2
O
3
, Zn-Ni-nano-SiC etc. [43].

2.6.1 Mechanisms in Electrochemical Codeposition
The general mechanism of electrocodeposition was analogous to that of electrophoretic
deposition. In electrophoretic deposition, the following steps involves in the deposition of
particles from the suspension, i) the particles in suspension acquire a surface charge, ii) the
charged particles are transported through the liquid by the application of an electric field
(electrophoresis), iii) the particles are deposited onto the electrode, and iv) the particles adhere to
the electrode surface through vander Waals forces, chemical bonding, or other forces. But the
process mechanism for electrocodeposition differ from the above listed steps only in the last two
steps, in which metal plating takes place simultaneously with particle deposition and metal
encapsulation provides an additional means of particle adherence.
Several theoretical models have been proposed to describe the mechanism of particle entrapment
of electrocodeposition process. All these theories are developed based on the investigations of
micron sized particles. In 1972 Guglielmi [48] proposed the first mechanism on
electrocodeposition of inert particles in the metal matrix, and later this mechanism has been
adopted by various authors. According to this mechanism the process involves a two step
mechanism. The solid particles are surrounded with a cloud of adsorbed ions in the electrolyte
solution, and in the first step, when the particles approach the cathode they become weakly
adsorbed at the cathode surface by Vander Waals forces. In the second step, particles adsorb
strongly on the cathode surface by Coulomb forces and consequently are incorporated into the
growing metal matrix. The model proposed by Guglielmi does not consider mass transfer.
Martin and Williams suggested that electrocodeposition was simply due to the mechanical
entrapment of the particles by the deposited metal. Snaith and Groves [49] supported this
proposition based on their observation that when a codeposited film was mechanically polished
and then etched, the particles which had been incorporated within the metal matrix fell out.
A generally accepted mechanism suggested by Kurozaki [50] includes the transport of solid
particles from the solution to the cathode surface by agitation. This model involves a three step
process according to which, dispersed particles are transported to the Helmholtz's double layer
by mechanical agitation in the first step, and in the second step, particles charged in the high
18

potential gradient are transported to the cathode surface by electrophoresis. In the third step,
particles are adsorbed at the cathode surface by the Coulomb force which exist between particles
and adsorbed anions, and are incorporated by the growing metals.
Figure 2.4 shows the common processes involved in the codeposition of particles into growing
metallic layers. Five consecutive steps during the codeposition process can be identified [51]:

formation of ionic clouds on the particles
convection towards the cathode
diffusion through a hydrodynamic boundary layer
diffusion through a concentration boundary layer and finally
adsorption at the cathode where particles are entrapped within the metal deposit.

Figure 2.4: Mechanism of Particle codeposition into a metal deposit.

19

2.6.2 Effect of deposition parameters on ECD

(a) Bath composition
The composition of the codeposition bath is not only defined by the concentration and type of
electrolyte used for depositing the matrix metal, but also by the particle loading in suspension,
the pH, the temperature, and the additives used. A variety of electrolytes have been used for the
electrocodeposition process to form metal matrix of copper include acid copper sulfate bath,
alkaline pyrophosphate bath. Electrolyte concentrations typically range between 100-600 g/l and
the particle loading in suspension has ranged from 2-200 g/l. The effect of some of the process
variables can also vary for particle-electrolyte combinations and cell configurations.
(b) Particle Loading in Suspension
Particle loading or concentration of particles in the suspension is important factor which affects
the amount of particle concentration in the deposits. At low loadings, codeposition is limited by
the supply of particles to the electrode surfaces (cathode) leads to small amount of particles in
the deposition. As the particle loading increases, supply of particles to the electrode increase so
does the incorporation level in the deposition increases. But at the highest loadings (beyond
which particle settling becomes significant), the increase in incorporation is not proportional to
the increase in loading. For the parallel plate system, the amount of incorporation has been found
to increase with increasing particle loading following a Langmuir-adsorption type isotherm [52].
(c) Bath Agitation
Increase in the bath agitation in the parallel plate electrode setup has been found to increase the
amount of particles codeposited within the electroplated film for the Ni-Al
2
O
3
and Ni-TiO
2

systems [53]. When the agitation is increases, a greater number of particles arrive at the electrode
surface and the amount of particle incorporation in the metal film increases. However, if the
agitation is too intense, the residence time for the particles at the electrode surface is insufficient
and the particles are swept away before they can be incorporated into the growing metal film.
Also, the amount of codeposition has also been observed to decrease in the Cu-SiC and Cu-CrB
2
systems with increasing agitation [54].

20

(d) Surfactant
The codeposition of particles increases with increasing the concentration of surfactant in the
solution, this is due to the modification of the surface charge of the particles in the suspension by
the absorbed molecules or ions, thereby decreasing agglomeration of particles and promoting the
electrophoretic migration of the suspended particles. Thus increases in the amount of particle
concentration in the film with homogenous distribution.
(e) Current Density
Current density plays an important role in controlling the deposition rate which will in turn affect
the concentration of incorporated particles in the coatings. It also influences the thickness of the
composite films, such that as the current density increases the thickness of the coatings increases.
When the current density is increased, the amount of particle incorporation obtained has been
found to increase for the Ni-TiO
2
system with a relatively slow agitation [54], decrease for
natural or synthetic diamond in Ni [55] and for Cr particles codeposited in Ni [55] and to be
unaffected when codepositing alumina in Ni. It also plays a role in the thickness of the deposited
films.
(f) Particle Characteristics
Particles can be characterized by their composition and crystallographic phase, as well as by
their size, density, and shape. The particle composition can have a dramatic impact on the
amount of incorporation obtained for a particular bath composition. For instance three times
more TiO
2
than A1
2
O
3
has reportedly [53] been incorporated into a Ni matrix, under the same
deposition conditions. The particle size also effects on the amount of codeposited particles in the
composite coatings. For example when the particle size in the electrolyte increases then amount
of adsorbed ions on the surface increases, which leads to the increase in the migration velocity of
the particles and also results in a higher columbic force of attraction, leads to increase in the
amount of the particles. But the density of particles in the coating decreases as the particle size in
the electrolyte increases. For example increasing the particle size resulted in an increase in the
amount of incorporation for Ni-A1
2
O
3
, Ni-SiC, Ni-Cr, Cu-P, and Cu-Al
2
O
3
[43]. However, other
researchers found particle size to have a negligible influence on the amount of incorporation for
Ni-A1
2
O
3
and SnNi-SiC [43].

21

2.6.3 Different baths used for Copper Elecetroplating

The most commonly used different plating baths for copper electrodeposition for different
application purpose are Copper Cyanide plating baths, Copper pyrophosphate plating baths, and
copper sulfate plating baths.
Copper cyanide plating baths typically contain 30 g/l (4.0 oz/gal) of copper cyanide and either 59
g/l (7.8 oz/gal) of potassium cyanide or 48 g/l (6.4 oz/gal) of sodium cyanide. Cathode
efficiencies range from 30 to 60 percent. These baths mainly used widely in many plating
operations as a strike.
Copper pyrophosphate plating baths typically contain 53 to 84 g/l (7.0 to 11.2 oz/gal) of copper
pyrophosphate and 200 to 350 g/l (27 to 47 oz/gal) of potassium pyrophosphate. These baths are
used for plating on plastics and printed circuits, requires more control and maintenance of the
plating baths than copper cyanide plating does. However, copper pyrophosphate solutions are
relatively nontoxic.
Copper sulfate plating baths typically contain 195 to 248 g/l (26 to 33 oz/gal) of copper sulfate
and 11 to 75 g/l (1.5 to 10 oz/gal) of sulfuric acid. These types of baths are more economical to
prepare and operate than copper pyrophosphate baths, are used for plating printed circuits,
electronics, rotogravure, and plastics, and for electroforming and decorative uses.

2.7 Brief literature review on Cu-TiO
2
and Cu-Al
2
O
3
systems

2.7.1 Cu-TiO
2
Literature
Catalina et al. prepared Cu- TiO
2
nano composite coating on a copper substrate using electro
codeposition technique from copper sulfate bath. They studied the influence of the concentration
of TiO
2
nano particles as dispersed phase in copper matrix coatings obtained at different current
densities, and also studied the influence of TiO
2
on structure and properties of coatings. They
have taken concentrations of nano-TiO
2
particles (17 nm) as 5, 10 and 50 g/l in electroplating
bath. The surface morphology and composition of layers were studied by optical and scanning
electron microscopy (SEM) and EDX analysis [48].
Ramalingam et al. prepared Cu- TiO
2
nano composite coating on copper substrate using electro
codeposition technique from copper sulfate bath. Aim of their work was how to assess the effect
of nano sized TiO
2
content on the wear and corrosion resistance of the deposited coatings. And
22

how the composition of codeposited TiO
2
nanoparticles in the composite coatings was controlled
by the addition of different concentrations of TiO
2
nano particles in the bath solution. The
surface morphology and composition of the nano composites were examined by scanning
electron microscopy and energy dispersive X-ray spectroscopy analysis [56].
2.7.2 Cu-Al
2
O
3
Literature
Andreas Bund et al. prepared Cu- Al
2
O
3
thin films by using three different types of baths such as
an acidic copper sulfate, a neutral pyrophosphate, and an alkaline sorbitol based bath, with
covering a wide pH range were used. The highest amount of incorporated particles (ca.11 wt%
alumina) was found for the pyrophosphate bath. And they measured the zeta potential of the
particles in dilute solutions of the components of the plating baths. Furthermore, the
microstructure, microhardness and electric conductivity of the layers were characterized [57].
I. Zamblau, et al. prepared Composite coatings of copper incorporating Al
2
O
3
nanoparticles by
using electrodeposition on carbon steel and characterized. By using electrochemical methods
such as open circuit potential (ocp) measurements, polarization curves and electrochemical
impedance spectroscopy, the corrosion behavior of the Al
2
O
3
-copper nanocomposite coatings
was examined [58].
J. R. Roos, et al. prepared Cu-A1
2
0
3
deposits containing either -A1
2
0
3
or -A1
2
0
3
particles in
copper sulphate plating baths to which the addition agents thallium sulfate or aluminum sulfate
were added. In their work they studied the effect of thermo mechanical processing on the
microhardness of copper deposits containing a dispersion of -Al
2
0
3
or -A1
2
0
3
particles in the
bath. The as-deposited microhardness and the effect of annealing on the microhardness and on
the microstructure of cold-rolled and hot-rolled Cu- A1
2
0
3
deposits were investigated in
particular. The effect on mechanical properties of the use of promoting agents for codeposition
was also studied [59].

23

2.8 Wear & Various wear Mechanisms

Wear is defined as the erosion of material from a solid surface by the action of another surface. It
is related to surface interactions and more specifically the removal of material from a surface as a
result of mechanical action. The real area of contact between two solid surfaces compared with
the apparent area of contact is invariably very small, being limited to points of contact between
surface asperities. The load applied to the surfaces will be transferred through these points of
contact and the localized forces can be very large. The material intrinsic surface properties such
as hardness, strength, ductility, work hardening etc. are very important factors for wear
resistance, but other factors like surface finish, lubrication, load, speed, corrosion, temperature
and properties of the opposing surface etc. are also equally important. Temperature has an effect
on the wear rate (rate at which a material deteriorates under frictional forces) because friction
generates heat, which in turn can affect the microstructure of the material and make it more
susceptible.
The various types of wear are
(a) Adhesive wear
(b) Abrasive wear
(c) Erosive wear
(d) Corrosive wear
(e) Surface fatigue wear
(f) Fretting wear

(a) Adhesive wear

Adhesive wear is due to the localized bonding between contacting solid surfaces leading to
material transfer between the two surfaces or the loss from either surface. Adhesive wear occurs
when two bodies slides over each other, or are pressed into one another, which promote material
transfer between the two surfaces. However, material transfer is always present when two
surfaces are aligned against each other for a certain amount of time and the cause for material
transfer or wear. Adhesive wear is the most common form of wear and is commonly encountered
in conjunction with lubricant failures. High hardness and low strength are desirable properties for
applications requiring resistance to adhesive wear. The process is as demonstrated in the below
Figure 2.5
24

Figure 2.5: Schematic of Adhesive wear mechanism.

(b) Abrasive wear

Abrasive wear occurs when a solid surface experiences the displacement or removal of material
as a result of a forceful interaction with another surface or particle. Particles can become trapped
in between the two surfaces in contact, and the relative motion between them results in abrasion
(displacement and removal of surface material) of the surface that has a lower hardness.
Gouging, grinding, and scratching are the examples of abrasive wear. Alternatively, abrasive
wear can occur in the absence of loose particles when the roughness of one surface causes
abrasion and/or removal of material from the other surface. The Abrasive wear process is as
demonstrated in Figure 2.6 [60].

Figure 2.6: Schematic of Abrasive wear mechanism.

25

(c) Erosive wear
Erosive wear is caused by the impact of particles of solid or liquid against the surface of an
object [61]. The impacting particles gradually remove material from the surface through repeated
deformations and cutting actions [62]. The rate of erosive wear is dependent upon a number of
factors. The material characteristics of the particles, such as their shape, hardness, impact
velocity and impingement angle are primary factors along with the properties of the surface
being eroded. The Erosive wear process is as demonstrated in Figure 2.7

Figure 2.7: Schematic of Erosive wear mechanism.
There are three types of erosion wear

Solid particle erosion surface wear by impingement of particles carried by a gas or fluid.
Example: wear of helicopter blade leading edges in dusty environments.
Liquid drop erosion surface wear by impingement of liquid drops.
Example: wear of centrifugal gas compressor blades by condensate droplets.
Cavitation erosion surface wear in a flowing liquid by the generation and implosive collapse of
gas bubbles.
Example: Cavitation erosion of a ships propellers and of components in fluid pumps.

26

(d) Fretting wear

Fretting wear is due to the repeated cyclical rubbing between two surfaces, over a period of time
which will remove material from one or both surfaces in contact. It occurs typically in bearings,
although most bearings have their surfaces hardened to resist the problem.
(e) Corrosive wear

When the effects of corrosion and wear are combined, a more rapid degradation of the materials
surface may occur. This process is known as corrosive wear. Films or coatings are often used to
protect a base metal or alloy from harsh environments that would otherwise cause it to corrode.
(f) Surface fatigue wear
Surface or contact fatigue occurs when two material surfaces that are in contact with each other
in a rolling or combined rolling and sliding motion create an alternating force or stress oriented
in a direction normal to the surface. The contact stress initiates the formation of cracks slightly
beneath the surface, which then grow back toward the surface causing pits to form as particles of
the material are ejected or worn away. This form of fatigue is common in applications where an
object repeatedly rolls across the surface of a material, resulting in a high concentration of stress
at each point along the surface. For example, rolling-element bearings, gears, and railroad wheels
commonly exhibit surface fatigue [60]. Figure 2.8 illustrates an example of the surface fatigue
mechanism.

Figure 2.8: Schematic of Surface Fatigue wear mechanism.

Chapter 3
Experimental

Sample Preparation
Plating bath Solution Preparation
Particle Size Analysis
X-Ray Diffraction Studies
Microstructural Studies
Surface Mechanical Property Study

27

CHAPTER 3
EXPERIMENTAL
3.1 Sample preparation

For the deposition of Cu-TiO
2
and Cu-Al
2
O
3
composite coatings, copper was selected as
substrate. The substrates were collected from hot rolled copper strip by cutting it into averagely
20mm15mm size pieces. The approximate dimensions of the substrates were
20mm15mm3mm. Then the substrates were mirror polished by grinding on belt grinder for
oxide layer removal, then on emery papers (1/0, 2/0, 3/0, 4/0), then rough cloth polishing in
which Alundum was used as abrasive agent. Finally the substrates were fine polished by fine
cloth in which diamond paste was used as polishing agent. Then the substrates were cleaned with
soap and then washed with water. Ultrasonication of the substrates was done for 10 minutes by
using deionized water and acetone for the removal of fine particles which adsorbed on the
sample surface during the polishing. In this way the mirror polished substrates were prepared for
deposition. Holes were made on the samples to dip the samples in the electrolyte solution and to
supply current by attaching copper wire to the hole.

3.2 Plating bath solution preparation

Parallel plate electrode configuration and Copper sulfate bath without addition of surfactant and
additives, is used for the codeposition of TiO
2
and Al
2
O
3
in the copper matrix. The bath
compositions and parameters used for Cu-TiO
2
composite coatings are reported in the Table 3.1
and Table 3.2 respectively. As the isoelectric point of TiO
2
was determined around 4.2, so the pH
of the solution maintained below this value (pH 2) so that the particles in the suspension acquire
positive charge in the acid solution and deposited into the growing metal on cathode. Same bath
compositions and plating parameters were also used for Cu Al
2
O
3
system except the pH value.
pH 4 was fixed for Cu-Al
2
O
3
system as no incorporation of Al
2
O
3
in copper matrix at pH 2 was
reported in the literature [43]. Pure copper strip was used as Anode and prepared copper
substrates as cathodes on which composite deposition takes place. Before deposition the solution
was allowed for Ultrasonication for 25minutes and magnetic stirring for 30minutes for
homogenous dispersion of the TiO
2
powder in the solution. Magnetic stirring was also allowed
28

for stirring of the bath during entire deposition so that the sedimentation of powder particles in
the solution is prevented and they can be homogeneously dispersed during deposition in the
copper matrix. Pure copper deposits were also done by using the parameters which have used for
TiO
2
deposition for comparison of the results obtained, with the results obtained by using
particle incorporation. After deposition the samples were washed with distilled water, kept in the
paper and preserved for Characterizations.
Table 3.1: Composition of Copper sulfate bath solution for Cu-TiO
2
/ Cu- Al
2
O
3
and pure
copper coatings
Electrolyte
(Acidic copper sulfate bath)
Copper Sulfate (CuSO
4
.5H
2
O): 200 gm/l
Sulfuric acid (H
2
SO
4
): 50 gm/l
pH 2.17
Current density 5 A/dm
2
, 8 A/dm
2
, 11 A/dm
2
, 14 A/dm
2

Temperature 27 C
Plating time 20 minutes
Dispersion TiO
2
/ Al
2
O
3
: 0 gm/l, 10 gm/l, 30 gm/l

Table 3.2: Deposition parameters of Cu-TiO
2
/ Cu-Al
2
O
3
and un reinforced Copper coatings
S .No 1 2 3 4 5 6 7 8 9 10 11 12
TiO
2
/Al
2
O
3
concentration
in bath(gm/lit) __ __ __ __ 10 10 10 10 30 30 30 30
Current density(A/dm
2
) 5 8 11 14 5 8 11 14 5 8 11 14

3.3 Particle size analysis

The particle size of TiO
2
and Al
2
O
3
powder which were procured from Inframat Advanced
Materials, Formington, USA was checked by Malvern Zetasizer nano series Nano- ZS model
instrument. Before measuring the particle size, very small amount of powder particles were
dispersed in deionized water and magnetic stirring was allowed for 30minutes followed by
10minutes ultrasonication for homogeneous dispersion of particles in the solution. The below
Figure 3.1 shows the photograph of Malvern Zetasizer which can measure particle sizes from
29

nanometer size to micron size, and which can also used to measure zeta potential of suspended
particle in a solution.

Figure 3.1: Nano zeta sizer (Model: Nano ZS, Malvern instrument)

The zeta potential of the particles (TiO
2
& Al
2
O
3
) were also measured with this Zetasizer at
different pH values of the suspensions and the values are drawn against different pH values to
find the isoelectric point and also to estimate the stable suspension pH value required for
cathodic deposition of the ceramic particles.

3.4 X-ray diffraction studies

X- Ray Diffraction studies of all the deposited samples were performed by using, Philips XPert
system with Cu K
radiation (= 1.5418A) to judge the phases formed, to calculate the

crystallite sizes and also to determine the Relative Texture Coefficient (RTC) of the deposits.
The same was also done for pure copper sample which was used as substrate and for raw
powders of TiO
2
and Al
2
O
3
. The XRD was carried out with 2 range of 20-100 with scan rate
of 3 degrees per minute.

30

3.5 Microstructural studies

3.5.1 Scanning Electron Microscope (SEM) studies

Scanning Electron Microscopic studies were performed to view the morphology of the coatings,
distribution of the particles, to determine the composition and thickness of the coatings by using
JEOL 6480 LV scanning electron microscope (SEM) equipped with an energy dispersive X-ray
(EDX) detector of Oxford data reference system which is shown in the below Figure 3.2. Field
effect scanning electron microscope (FESEM) of model ZEISS: SUPRA 40 was also used to
determine the compositions and for high resolution micrographs of the coatings deposited.

Figure 3.2: JEOL JSM-6480LV Scanning Electron Microscopy

31

3.6 Surface mechanical property studies

3.6.1 Microhardness Measurement
Microhardness of the composite coatings (Cu-TiO
2
& Cu-Al
2
O
3
), pure copper coatings and the
pure copper (substrate) were determined by using LECO LM700 michrohardness tester which is
shown in Figure 3.3. The machine have minimum 1gf and maximum 1000 gf load, Dwell time
5-99sec and Knoop or Vickers indenter is included . The test was carried out with 10 gf load for
15 seconds to ensure that the indentation is up to the coating surface only. The hardness values
were taken at 5 different places on the surfaces and average of these values were considered in
the results.

Figure 3.3: LECO LM700 Microhardness tester

3.6.2 Wear Behavior of the Coatings
The sliding wear resistance of the composite coatings and pure copper coatings were evaluated
by using ball on plate type wear testing instrument having a hardened steel ball (SAE 52100)
indenter of 2 mm diameter. DUCOM TR-208-M1 ball on plate wear tester was used for this
study to evaluate the wear resistance of all the coated samples with 500 gm load, 10rpm speed
and 5minutes duration time. Graphs were plotted against Sliding distance vs. wear depth to
32

compare the wear resistances of the different samples. Scanning Electron Microscope (SEM)
was used to analyze the surface damages caused by the wear testing machine to get an idea about
the wear mechanism.

Figure 3.4: DUCOM TR-208-M1 Ball on plate wear tester

Chapter 4
Results and Discussions

Particle size
Zeta potential measurement
XRD analysis
Microstructural characterization
Surface Mechanical properties
Brief comparison of TiO2 and Al2O3 systems
33

CHAPTER 4
RESULTS AND DISCUSSIONS

4.1 Particle Size

The below Figure 4.1 (a) & (b) shows the particle size distributions of TiO
2
and Al
2
O
3
powders
obtained by using Malvern Zeta sizer. From the figure it can be seen that no sharp peak was
observed in both the cases, it indicates that a range of different sized particles were present in the
bulk powder. In case of titania minimum size was observed at 91 nm and maximum 295 nm.
But higher volume percentage of particles having sizes between 105 nm to 190 nm. From the
cumulative study the mean size obtained for TiO
2
was 202 nm. In case of Alumina, the minimum
size observed was 190 nm and the maximum size was 342 nm, but the higher volume percentage
of particles was having sizes between 220 nm to 295 nm. The mean size obtained for Al
2
O
3
was
287 nm.

(a)

(b)

Figure 4.1: Particle size distribution of (a) TiO
2
powder (b) Al
2
O
3
powder.

34

4.2 Zeta potential Measurement
Zeta potential of TiO
2
& Al
2
O
3
ultrafine particles in de-ionized water at different pH values was
measured to determine the iso-electric point for stable suspension by using Malvern Zetasizer
nano series Nano- ZS model instrument prior to the electrodeposition. From the below Figure
4.2(a) it can be observed that the iso-electric point of TiO
2
was around 4.2 in pH, where as it is
around 5.5 [63] according to the literature. The pH maintained in our case for Cu-TiO
2
system
was around 2.0 pH, which was lower than the obtained iso-electric point pH, which signifies the
acidic nature of the solution and the particles were positively charged in the suspension.
Similarly from Figure 4.2 (b) the iso-electric point of Al
2
O
3
was observed around 5.3 in pH,
according to literature it is 8-9 [64] in pH. In our case for Cu-Al
2
O
3
system the pH was
maintained at 4.0 pH, which also signifies the acidic behavior of the solution and the particles
were positively charged in the suspension.

(a) (b)

Figure 4.2: pH Vs Zeta potential for iso electric point determination of (a) TiO
2
(b) Al
2
O
3

powder in water.

35

4.3 XRD Analysis

X-Ray diffractograms of Raw Powders (TiO
2
& Al
2
O
3
) procured from Inframat Advanced
Materials, Formington, USA, all developed coatings and Pure Copper (substrate) was performed
by using Philips XPert System. Figure 4.3(a) shows the XRD pattern of raw TiO
2
powder shows
tetragonal crystal structure. But there is no appreciable peak broadening was observed though the
crystallite sizes are in nanometric size. The powder source was confirmed to be synthesized by a
chemical route which does not introduced any strain in the powder material. So, the broadening
observed was only due to the fine crystallite size, not due to the strain.

Figure 4.3: XRD peaks of (a) Raw TiO
2
powder (b) Raw Al
2
O
3
powder.

Thus the XRD peaks do not show broadening though the crystallite sizes are small. Figure 4.3(b)
shows the XRD peaks of Al
2
O
3
Raw powder, indicating the Rhombohedra crystal structure. The
features of Al
2
O
3
are also same that as TiO
2
powder.
The below Figures 4.4 & 4.5 shows the comparable XRD patterns of Cu-TiO
2
and Cu-Al
2
O
3
at
10 g/l, 30 g/l along with XRD pattern of substrate (pure copper). The crystallite sizes of all the
coated samples were calculated by using Scherrer formula [65-66] given by equation (1) with
(111) peak as reference peak and are given in below Table 4.1, 4.2 & 4.3. The crystallite sizes
observed were all are less than100 nm. The Scherrer equation is given by

(b)
(a)
36

D =

------------------------ (1)

Where D is the crystallite size, is the full width at half maximum (FWHM) of the diffraction
peak, is the wavelength of the incidental X-ray (1.54 A) and is the diffraction angle.

The Relative Texture Coefficient (RTC
(hkl)
) of 4 peaks namely (111), (200), (220) and (311) of
all coated samples were calculated for texturing study by using below equation (2) and the
results were given in below tables along with the crystallite sizes. The RTC [67-68] is defined as

I
(hkl)
/ I
0 (hkl)

RTC
(hkl)
= ----------------------- 100% -----------------------(2)
I
(hkl)
/ I
0 (hkl)

Where I(hkl) is the intensity obtained from textured sample and I
0
(hkl) is the intensity of the
Standard oriented sample i.e., from JCPDS data.
The below Figure 4.4 and Table 4.1 shows the comparable XRD patterns for Cu-TiO
2
system for
10 g/l and 30 g/l TiO
2
in the bath. From the figure it is evident that all the peaks showing were
belonging to the Cu. Though TiO
2
is present in all Cu-TiO
2
coated samples evidenced by the
EDS compositional study but no peak of TiO
2
was not clearly observed because of very less
intensity of TiO
2
peaks which is due to the higher intensity of the Cu peaks and small wt% TiO
2

(less than 10%) co deposited in the composite coating. The TiO
2
(Anatase type, JCPDS No: 84-
1285) peaks were observed with very less intensity at 2 angles of 25.24, 48.0 degrees in Cu-
TiO
2
coatings, to judge this only the XRD peaks of TiO
2
10 g/l, 8 A/dm
2
was enlarged which is
shown in Figure 4.5.

37

(a) (b)
Figure 4.4: Comparable XRD pattern of Cu-TiO
2
coatings (a) 10 g/l TiO
2
(b) 30 g/l TiO
2
in the
bath along with substrate (pure Cu) XRD pattern.

Figure 4.5: Enlarged XRD pattern of Cu-TiO
2
coating at TiO
2
10 g/l, current density 8 A/dm
2
.

38

(hkl)
) of Cu- TiO
2
TiO
2
2
.
_____________________________________________________________________________
Sample details RTC (%) Crystallite size (nm)
__________________________
(111) (200) (220) (311)
_____________________________________________________________________________

10 g/l, 5 A/dm
2
22 13 41 24 50
10 g/l, 8 A/dm
2
3 2 88 7 65
10 g/l, 11 A/dm
2
0.2 0.2 98 1.6 57
10 g/l, 14 A/dm
2
26 22 30 22 65
30 g/l, 5 A/dm
2
20 17 40 23 65
30 g/l, 8 A/dm
2
1 1 96 2 76
30 g/l, 11 A/dm
2
9 6 75 10 51
30 g/l, 14 A/dm
2
17 11 56 16 41
______________________________________________________________________________

From the Table 4.1, Table 4.2 & Figure 4.4 it can be observed that (220) is the most intense
diffraction line (texture) in both composite coatings and pure copper deposition at all current
densities except at 11A/dm
2
, whereas the substrate shown a strong (111) texture. The quality of
the (220) texture was obviously affected by the incorporation of particles and the current density.
At 5 A/dm
2
in both of cases 10 g/l and 30 g/l the intensity of (220) is less (41%) which is
accompanied by increase in the intensities of (111), (200) and (311) lines which is attributed to
the higher amount of TiO
2
embedded in the coatings (Table 4.4). As the current density
increased from 5 A/dm
2
to 8, 11 A/dm
2
the intensity of (220) texture increased by 47% and 57%,
the increase was accompanied by decrease in the intensities of (111), (200) & (311) lines, this is
due to the lower content of TiO
2
embedded in the composite coatings compare to 5A/dm
2
. At 14
A/dm
2
, 10 g/l the (220) texture was changed to (220)+(111) mixed preferred orientations, this
might be due to higher over potential which affects the nucleation and growth of crystallites and
also due to the hydrogen evolution at higher current densities.
39

Below Figure 4.6 and Table 4.3 shows the comparable XRD patterns of Cu-Al
2
O
3
for 10 g/l and
30 g/l in the bath. From the Figure 4.6 it can be seen that (111), (200), (220), (311) and (222)
peaks of Cu were present along with the peaks of Copper Oxide (Cu
2
O, JCPDS NO: 05-0667) at
2 angles of 29.555, 36.419, 42.298 and 61.369. In pure copper & Cu-Al
2
O
3
depositions
(220) was the texture orientation, but the quality of (220) texture was affected by the Al
2
O
3

presence in the coatings, current density and the Copper oxide similarly as Ni(OH)
2
in Nickel
deposition[69]. From the Figure 4.6 it can be seen that the intensity of (220) texture was
increased with the decrease in the intensity of copper oxide peaks at 36.419 and 61.369 as the
current densities increased from 5 A/dm
2
to 14 A/dm
2
.

(a) (b)

Figure 4.6: Comparable XRD pattern of Cu-Al
2
O
3
coatings (a) 10 g/l Al
2
O
3
(b) 30 g/l Al
2
O
3
in
the bath along with XRD pattern of substrate (pure Cu).

40

(hkl)
) of Cu-Al
2
O
3
Al
2
O
3
2
.
______________________________________________________________________________

__________________________
(111) (200) (220) (311)
_____________________________________________________________________________

10 g/l, 5 A/dm
2
26 22 29 23 41
10 g/l, 8 A/dm2 18 21 36 25 45
10 g/l, 11 A/dm
2
9 16 48 27 50
10 g/l, 14 A/dm
2
7 12 57 24 62
30 g/l, 5 A/dm
2
20 19 37 23 53
30 g/l, 8 A/dm
2
14 19 41 26 45
30 g/l, 11 A/dm
2
14 16 43 27 64
30 g/l, 14 A/dm
2
16 11 49 24 64
______________________________________________________________________________
At 5 A/dm
2
, 10 g/l two preferred diffraction lines (220) & (111) were observed, this is attributed
to higher percent of copper oxide formation. As the current density increased further to 8, 11
A/dm
2
the (220) texture changed to (220)+(311) mixed preferred orientations with (220)
intensity increased by 7%, 19% respectively, this is due to the higher co deposition of Al
2
O
3
and
decreased intensity of copper oxide, the increase is balanced by the decrease in intensities of
(111) and (200) lines. At 14 A/dm
2
less co deposition of Al
2
O
3
and smaller formation of copper
oxide leads to increase in (220) texture further by 28%. The similar trend was observed in case of
30 g/l Al
2
O
3
in bath as observed in 10 g/l Al
2
O
3
in the bath.
In the summary from the above discussions on texture study of Cu-TiO
2
and Cu-Al
2
O
3
systems it
can be conclude that the observed texture is due to the influence of current density, embedding
second phase ceramic particles and copper oxide formation in the composite coatings.

41

(hkl)
) of unreinforced Copper coatings at current
densities 5, 8, 11 and 14 A/dm
2
.
______________________________________________________________________________
__________________________
(111) (200) (220) (311)
_____________________________________________________________________________
5 A/dm
2
2 1 90 7 41
8 A/dm
2
1 0.5 95 3.5 56
11 A/dm
2
51 14 19 16 53
14 A/dm
2
6 8 74 12 64
______________________________________________________________________________
4.4 Microstructural Characterization

4.4.1 EDS Analysis

The below Figure 4.7 (a) shows the Energy Dispersive Spectrum (EDS) of Cu-TiO
2
coating
surface prepared at 10 g/l, 5 A/dm
2
, with this it is evident that Ti (0.76wt%) of particles were
present in the composite coating along with copper (97.12wt%) and oxygen (2.13wt%).
Similarly the Figure 4.7(b) shows the EDS of Cu-Al
2
O
3
coating prepared at 30 g/l, 11 A/dm
2

which gives the evidence of presence of Al (4.69wt%) particles along with oxygen (5.96wt%)
and copper (89.35wt%). Different wt% of TiO
2
and Al
2
O
3
reported in the composite coatings
depending on particle concentrations in the bath and current densities, those are given in Table
4.4 and shown in Figure 4.10

Figure 4.7: EDS of (a) Cu-TiO
2
deposited at 10 g/lTiO
2
, 5 A/dm
2
(b) Cu-Al
2
O
3
deposited at
30g/l Al
2
O
3
, 11 A/dm
2
.
(a) (b)
42

The below Figures 4.7 (c) & (d) shows the spot EDS on Cu-TiO
2
& Cu-Al
2
O
3
coating surfaces
particularly on the powder particles found in the coating surfaces. Such spot EDS on Cu-TiO
2

coatings (Fig 4.7(c)) also resulted the presence of Ti particle (2.31wt%) and Oxygen (16.90wt%)
in the copper matrix. Similarly Figure 4.7 (d) shows the presence of Al (1.59wt%) and oxygen
(3.14wt%) in the Cu-Al
2
O
3
composite coating.

Figure 4.7: Spot EDS on surface of (c) Cu-TiO
2
(d) Cu-Al
2
O
3
composite coatings.

Table 4.4: Co-deposited TiO
2
(in terms of Ti), Al
2
O
3
(in terms of Al) wt% in Cu-TiO
2
& Cu-
Al
2
O
3
composite coatings at 10 g/l, 30 g/l in the bath and current densities 5, 8, 11 and 14 A/dm
2

______________________________________________________________________________
Current density (A/dm
2
) TiO
2
(wt%) Al
2
O
3
(wt%)

__________________ ____________________
10 g/l 30 g/l 10 g/l 30 g/l
______________________________________________________________________________
5 0.76 2.59 0.59 0.95
8 0.68 0.78 0.32 4.46
11 0.70 1.51 2.21 4.69
14 0.48 1.35 0.27 0.69
______________________________________________________________________________

(d)
(c)
43

4.4.2 Scanning Electron Microscope (SEM) Studies
The surface morphology and particle distribution of the electrodeposited composite coatings
were performed by using SEM (JEOL JSM-6480LV) and Field Effect Scanning Electron
Microscope (FESEM) of ZEISS: SUPRA 40. The below Figure 4.8 shows SEM surface
micrographs of the electrodeposited Cu-TiO
2
composite coatings prepared at 10 g/l, 30 g/l TiO
2

in the bath and current densities 5 A/dm
2
, 11 A/dm
2
without adding any surfactant to the bath.

Figure 4.8: Surface morphology of electrodeposited Cu-TiO
2
coatings (a) & (b) TiO
2
10 g/l in
2
, (c) & (d) TiO
2
30 g/l in bath current density 5, 11 A/dm
2
.

From the above Figure 4.8 it can be observed that smooth coating surfaces at all deposition
conditions and also absence of nodules, cracks and dendrites like structure was observed on the
coating surfaces. But the current density had greatly influenced the crystal structure of the copper
matrix. As no surfactant is added to the bath, large agglomeration of the particles was observed
in both Cu-TiO
2
and Cu-Al
2
O
3
systems (Figure 4.9(f)). At 10 g/l TiO
2
and 5, 11 A/dm
2
current
densities (Figure 4.8 (a) & (b)) the micrographs were smooth and fully compacted, but small
micro pits were observed at 11 A/dm
2
current density this is attributed to evolution of hydrogen
(a)
(b)
(c )
(d)
44

at the cathode surface. At 30 g/l, 5 A/dm
2
the surface morphology of the coating observed as
ropes like structure with void space and loosely compacted on the surface which is completely
different microstructure compare to other micrographs of the Cu-TiO
2
coatings. At 30 g/l, 11
A/dm
2
the micrograph shows the cauliflower like structure that smaller grains are agglomerated
and formed larger grains with well defined grain boundaries, and also grain refinement have
been observed at this current density and particle concentration.
Figure 4.9 (e) & (g) shows the SEM surface morphologies of the Cu-Al
2
O
3
composite coatings
developed at 10 g/l, 30 g/l Al
2
O
3
and current density 5 A/dm
2
. At 10 g/l the powder is not
distributed uniformly, some powder segregated zones can be seen where the actual crystal
growth is disturbed. Similar features observed at 30 g/l, 5 A/dm
2
with bigger morphology.
Figure 4.9(f) & (h) shows the surface morphologies of Cu-Al
2
O
3
coatings at 10 g/l, 30 g/l Al
2
O
3

and current density 11 A/dm
2
, agglomerated powder can be seen from Fig. 4.9 (f), where as the
powder was distributed over all grains is observed at 30 g/l, 11 A/dm
2
current density.

Figure 4.9: Surface morphology of electrodeposited Cu-Al
2
O
3
coatings (e) & (f) Al
2
O
3
10 g/l in
2
(g) & (h) Al
2
O
3
30 g/l in bath, current density 5, 11 A/dm
2
.

(e)
(f)
(g)
(h)
45

4.5 Effect of TiO
2
& Al
2
O
3
concentration in bath
The Figure 4.10 (a) & (b) shows relationship between the particle (TiO
2
& Al
2
O
3
) loading in the
plating bath for 10 g/l, 30 g/l and the co deposited wt% of TiO
2
(in terms of Ti) and Al
2
O
3
(in
terms of Al) in the composite coatings at four current densities 5, 8, 11,14 A/dm
2
. From the
Figure 4.10(a) it can be observed that a sharp increase in the co deposited wt% of TiO
2
at all
current densities as the TiO
2
loading in bath increased from 10 g/l to 30 g/l. Thus the amount of
codeposited TiO
2
wt% increased in the composite coating as the amount of TiO
2
increased in the
plating bath [56]. The same was reported in earlier [56]. This is due to increased amount of TiO
2

supply to the cathode region as the amount of TiO
2
increases in the plating bath. In other words,
a higher concentration of TiO
2
particulates in the electrolyte enhanced the adsorption rate, thus
resulting in a higher weight percentage of the codeposited TiO
2
nano-particulates in the coating.
However, the increase in the amount of co-deposited titania particles is not quantitatively
comparable with the amount of particles charged to the electrolyte. For example, by increasing
the amount of TiO
2
from 10 to 30 g/l with three times, the particle concentration in the deposited
layer was increased only 2 times. Higher amount of TiO
2
wt% observed at 5 A/dm
2
in both the
cases this is evident from the EDS compositional study. The Codeposition of TiO
2
nanoparticles
on the cathode surface was suggested by Guglielmis two-step adsorption model [56].

Figure 4.10: Effect of TiO
2
/Al
2
O
3
concentration in bath on co deposited wt% of (a) TiO
2
(in
terms of Ti) (b) Al
2
O
3
(in terms of Al) in composite coatings at current densities 5, 8, 11 and 14
A/dm
2
.
46

According to this model in the first step the particles are loosely adsorbed on the cathode surface
due to the weak vander waal forces, and in the second step the particles are strongly adsorbed on
the cathode surface due to the Columbic attractive forces acting between the cathode surface and
the anions adsorbed on the particles, then consequently the particles are encapsulated in the
growing metal matrix.
Same features were observed in case of Cu-Al
2
O
3
system also the Figure 4.10(b) demonstrates
the results obtained. As the Al
2
O
3
concentration in the bath increases from 10 g/l to 30 g/l the
wt% of the co deposited Al
2
O
3
is also increased. Higher amount of Al
2
O
3
found as 4.69wt% at
30 g/l, 11 A/dm
2
.

4.6 Surface Mechanical Properties
4.6.1 Microhardness study
The microhardness of the composite coatings and pure copper coatings were measured by using
Leco LM700 microhardness tester by applying 10gf load for 15 seconds in order to ensure that
the microhardness values are not affected by the substrate. Figures 4.11 (a) & (b) shows the
effect of current density on microhardness of Cu-TiO
2
and Cu-Al
2
O
3
composite coatings
developed at current densities 5, 8, 11 and 14 A/dm
2
without addition of any surfactant and
additives to the bath. Generally the strengthening mechanism of poly crystalline metals, alloys
and MMCs mainly due to (a) grain refinement strengthening from HallPetch relationship (b)
dispersion strengthening due to Orowan mechanism (c) solid solution strengthening (d) crystal
orientation. In the present work the hardness values were observed are mainly depending on
dispersion strengthening due to the dispersed second phase particles and preferred crystal
orientation (Texture) of the matrix phase and marginal effect of grain size.
The hardness values obtained for the composite coatings (Cu-TiO
2
& Cu-Al
2
O
3
) are higher than
pure copper (50HV-105HV) [70] at all current densities, also higher than the hardness values of
substrate (pure copper) 95.1HV and un reinforced copper coatings (83.3 HV to 129.9 HV). This
is attributed to the dispersion strengthening caused by the dispersed second phase particles in the
composite coatings.

47

Figure 4.11: effect of current density on microhardness of (a) Cu-TiO
2
(b) Cu-Al
2
O
3
coatings at
current densities 5,8,11 and 14 A/dm
2
.
In both the cases Cu-TiO
2
& Cu-Al
2
O
3
the microhardness values obtained were followed the
same trend. When the current density increased from 5 to 11 A/dm
2
, the hardness values
increased and at 14 A/dm
2
a little decrease in hardness values were obtained. In case of Cu-TiO
2

coatings at 5 A/dm
2
in both the cases 10 g/l, 30 g/l TiO
2
less hardness values were reported
which is due to the random crystalline orientation (Table 4.1) which leads to decrease in the
intensity of (220) texture, and increase in intensity of (200) plane this may be co related with
[100] texture associated to deposits with minimum hardness and maximum ductility [73]. The
minimum hardness for (200) diffraction line is attributed to lower angle between (200) and (100)
planes, which leads to lower strain energy, the strain energy increases as the angle increases [74-
75]. At 30 g/l and 5 A/dm
2
the hardness value obtained was less compare to 10 g/l titania, this is
due to the increased intensity of (200) soft mode, increase in grain size and microstructure of the
copper matrix, which looks as ropes like structure with loosely compacted. At 14 A/dm
2
also the
same feature was observed as at 5 A/dm
2
, the preferred (220) texture changes to (220)+(111)
mixed preferred orientations, which leads to decrease in the intensity of (220) plane and
increased intensity of soft mode (200) plane which is associated to [100] texture (soft mode) and
also smaller amount of TiO
2
embedded in the composite coating which leads to decrease in
(a)
(b)
48

hardness values at this current density. The higher intensity of (220) plane leads to higher
hardness this is due to its less active slip systems [76]. At 30 g/l TiO
2
as the current density
increased from 8 to 11 A/dm
2
the wt% of TiO
2
increased from 0.78 to 1.51 which causes
decrease in the intensity of (220) preferred direction from 96 to 75%, but improved hardness
value due to the higher wt% TiO
2
(1.51wt%) embedded in the coating. At 8, 11 A/dm
2
current
densities the increased wt% of TiO
2
modified the crystallite sizes from 56, 64 nm to 50, 41 nm
which leads to the increased hardness values. In the present study at 11 A/dm
2
current density
higher hardness values (122.2 HV at 10 g/l, 234.45 HV at 30 g/l) were obtained which is
associated to preferred crystalline orientation and more amount of TiO
2
embedded in the
composite coating and grain refinement.
In Cu-Al
2
O
3
system the Hardness values obtained were higher compared to Cu-TiO
2
system this
may be attributed to smaller amount of Copper oxide formation in the Cu-Al
2
O
3
composite
coatings which has higher hardness compare to copper. Current density and hardness relationship
obtained in Cu-Al
2
O
3
system is same as in Cu-TiO
2
system. At 8, 11 A/dm
2
the increased wt%
Al
2
O
3
in the coating changed the preferred (220) orientation to (220)+(311) mixed preferred
orientations. Larger hardness values were obtained at 11 A/dm
2
in both 10 g/l (197.3HV) and 30
g/l (247HV) which is attributed to higher amount of Al
2
O
3
. In the present range of study at 30
g/l, 11 A/dm
2
shows highest hardness values in both Cu-TiO
2
and Cu-Al
2
O
3
systems due to the
higher incorporation of dispersed second phase particles and texture effect.

4.6.2 Wear study
The wear test on the surfaces of the composite coatings and coatings without addition of second
phase particles were carried out by using DUCOM TR-208-M1 ball on plate wear tester by
applying load 5 N for 5minutes with 10 rpm sliding speed on a 2 mm diameter track. The below
Figure 4.12 (a) & (b) shows the comparable wear lose graphs ( in terms of vertical penetration of
the indenter or wear depth) as a function of sliding distance of Cu- 10 g/l TiO
2
, Cu- 30 g/l TiO
2
,
and without TiO
2
at the current densities of 11 A/dm
2
, 14 A/dm
2
. The wear performance of
electroplated composite films is known to be mainly dependent on the microstructure of the
metal matrix as well as on the amount and distribution of incorporated particles [71, 72]. That is
the wear behavior is co related to the hardness of the surface. According to the above statement
the wear loss or extent should be high for pure copper (without oxide particles), and also for
49

lower wt% TiO
2
embedded samples. The below Figure 4.12 (a) & (b) shows exactly the same,
wear loss of without TiO
2
samples is higher than composite coatings at 11, 14 A/dm
2
due to its
low hardness and absence of dispersed hard ceramic oxide particles. At 10 g/l TiO
2
and 11, 14
A/dm
2
current densities the wear lose is high than samples at 30 g/l TiO
2
due to the lower wt%
TiO
2
(Table 4.4) in the coatings and less hardness of the coating surfaces. The wear lose
behavior of the coatings developed at current densities 5, 8 A/dm
2
followed the same trend as the
microhardness showed. From the Figure 4.12 it can also observed that the wear lose of annealed
copper (73.33 m) is higher than the pure copper (68.5 m) which can be attributed to the
softness of annealed sample and also the loss is high (72.6 m) for pure copper coating
developed at 11 A/dm
2
than the coating developed at 14 A/dm
2
(47.6m) which is due to the
lower hardness of coating deposited at 11 A/dm
2
which has shown increased intensity of (200)
line corresponds to (100) (soft mode).

(a) (b)
TiO
2
, Cu- 30 g/l TiO
2
and without TiO
2
2
(b) at 14 A/dm
2
current
densities.
Below Figure 4.13a & b shows plots of the comparable wear lose (in terms of vertical
penetration of the indenter or wear depth) as a function of sliding distance of Cu- 10 g/l Al
2
O
3
,
Cu- 30 g/l Al
2
O
3
, and without Al
2
O
3
at the current densities of 11A/dm
2
, 14A/dm
2
. The below
Figure shows the similar trend for Al
2
O
3
incorporation as observed for TiO
2
incorporation.
50

In case of some graphs momentary negative slope could be observed. This may due to cold
welding of soft Cu phase with the hardened steel ball (indenter) resulting in decrease in the wear
depth. In general it be concluded that, with increase in ceramic powder contents, the wear
resistance of Cu coating increases.

(a) (b)
Al
2
O
3
, Cu- 30 g/l Al
2
O
3
and Cu without Al
2
O
3
2
(b) 14 A/dm
2
.

Figure 4.14 shows the SEM micrographs of the worn surfaces of wear tested samples. Figure (a),
(b) & (c) shows the overall wear track of the worn wear surfaces where as Figure (d), (e) & (f)
shows the same wear track at higher magnification of Cu substrate, pure Cu without oxide
powder at 11 A/dm
2
and Cu-10 g/l TiO
2
at 11A/dm
2
. From the figure it can be seen that in case
of pure copper (substrate) the wear track width is huge and also the track is not smooth. This can
be attributed to the inherent ductility and softness of the copper. Slight less wear track width was
observed for copper coating without ceramic oxide at11 A/dm
2
current density. Whereas the
track width is very small for Cu-TiO
2
coating developed at 11 A/dm
2
current density, this is due
to the presence of dispersed second phase TiO
2
particles in the copper matrix which improves the
hardness of the surface. Wear track with ceramic embedded surface shows more rubbing mark
due to three body motion (abrasion by the worn out ceramic particles). So, it can be concluded
51

that addition of ceramic oxide marginally transforms the wear nature from adhesive to abrasive
type.

Figure 4.14: SEM micrographs of wear track of (a) substrate (pure Cu) (b) Pure copper (without
ceramic oxide) at 11A/dm
2
( c ) Cu- 10 g/l TiO
2
at 11 A/dm
2
current density and (d), (e) & (f)
SEM micrographs of same wear tracks at higher magnification.

(a) (b) ( c )
(d) (e) (f)
52

4.7 Brief comparison of TiO
2
and Al
2
O
3
systems
Both the systems studied in the present study shows similar trend in general as discussed in the
previous sections. But minute differences can be observed in various chracatezition results
resulting in different final properties. Breif account of such variations are discussed below.
In case of Cu-TiO
2
system at 10 and 30 g/l powder concentration (220) plane is more
pronounced, where as in case of Cu-Al
2
O
3
system it is shifted to (220)+(311) mixed orientation.
With 10 g/l Al
2
O
3
in bath at all current densities smaller crystallite sizes were observed
compared to 10 g/l TiO
2
in bath. Grain size refinement was observed in case of Cu-TiO
2
system
at 30 g/l TiO
2
concentration and 11, 14 A/dm
2
current densities, whereas no such type of feature
was obtained for Cu-Al
2
O
3
system. In both the systems at 5 A/dm
2
random crystalline orientation
was obtained with (220) having little higher intensity.
In case of Cu-TiO
2
system at 10 & 30 g/l TiO
2
in bath with 11 A/dm
2
current density moderate
wt% TiO
2
(Ti=0.70 & 1.51 wt.%) was co deposited in the Cu-TiO
2
coatings, where as with same
conditions for Cu-Al
2
O
3
system Al
2
O
3
amount was higher (Al=2.21 & 4.49 wt.%) in the
coatings.
Higher hardness values were resulted in case of Cu-Al
2
O
3
system compared Cu-TiO
2
system at
both the concentrations. This may be due to lower co deposition of TiO
2
compared to Al
2
O
3
.
Similar effects were observed during wear testing of 10 g/l loaded samples, i.e. wear resistance
in general is better for Al
2
O
3
composite coating mainly at initial sliding distance. After certain
amount of sliding TiO
2
shows better result.

Chapter 5
Conclusions

Conclusions
Scope of future work

53

CHAPTER 5
CONCLUSIONS

5.1 Conclusions
In the present study, Cu-TiO
2
and Cu-Al
2
O
3
nanocomposite coatings were developed
successfully by using Electrodeposition process on the Copper substrate from copper sulfate
bath. From the detailed investigation of the results obtained, the following conclusions can be
drawn:
1. The particle size and zeta potential of TiO
2
and Al
2
O
3
were determined by using Zetasizer and
the particle size obtained was ~202 nm and ~287 nm respectively. And the iso electric points
were around 4.2 pH for TiO
2
and

around 5.3 pH for Al
2
O
3
.

2. From the XRD patterns, Tetragonal and Rhombohedra crystal structures of TiO
2
and Al
2
O
3

respectively were confirmed. The XRD peaks of both powders does not show appreciable
peak broadening though the sizes of both particles are in nanometric size, as the powder were
synthesized by a chemical route which does not introduced strain into the material. The XRD
pattern of Cu-TiO
2
and Cu-Al
2
O
3
coatings does not show TiO
2
and Al
2
O
3
peaks clearly with
much intensity because of less wt% (less than 10%) of powders embedded in the composite
coatings. The Cu-Al
2
O
3
XRD pattern also showing the peaks of Copper Oxide (Cu
2
O, JCPDS
Reference No: 05-0667) with very less intensity.

3. From the Texture calculations of Cu a strong (220) texture was obtained for composite
coatings and pure copper depositions, the intensity of (220) texture and shift of this texture
plane to mixed plane orientations was obtained due to the particle incorporation, the current
density and Cu
2
O in Cu-Al
2
O
3
. At 8, 11 A/dm
2
current density, 10 and 30 g/l Al
2
O
3
in the
bath along with (220) texture (311) preferred plane is also observed. Whereas a (111) texture
was observed for substrate (pure copper). The crystallite size was calculated by using Scherrer
formula from (111) peak and was below 100 nm for all the coated samples.
4. The Energy Dispersive Spectrum (EDS) of Cu-TiO
2
and Cu-Al
2
O
3
coatings gives evidence of
presence of Cu, O
2
, Ti, Al. From the Scanning Electron Microscope (SEM) surface
morphologies obtained the coating surfaces observed at all deposition parameters were
54

smooth, no dendrites, cracks and nodule like structures were observed on the surfaces. As no
surfactant is added to the bath, agglomeration of the particles was observed in the copper
matrix. In case of Cu-TiO
2
coatings at lower current densities (5, 8 A/dm
2
) the coatings were
fully compacted whereas at current densities 11, 14 A/dm
2
the surfaces has cauliflower like
structures. In case of Cu-TiO
2
at current density 5 A/dm
2
, 30 g/l TiO
2
in bath, different
morphology, rope like structure with voids and un compacted feature was obtained. In case of
Cu-Al
2
O
3
at 30 g/l Al
2
O
3
in bath, 5 A/dm
2
current density randomly oriented crystallites with
loose packing was observed.
5. The microhardness values obtained for both the composite coatings are higher than the pure
copper hardness, the improvement is attributed to dispersion strengthening caused by the
embedded second phase particles, texture and modified microstructure of copper matrix. For
Titania, there is maximum of 1.28 and 2.46 times increase, for Alumina there was maximum
of 2.07 and 2.6 times increase in microhardness after addition of dispersion with respect to
substrate and pure copper deposition respectively was observed. At moderate current densities
(8, 11 A/dm
2
) higher hardness values were observed.
6. The wear resistance of the composite coatings was higher than the substrate, annealed and un
reinforced copper. The wear resistance improved with increased weight % of dispersed
second phase particles in the bath compared to unreinforced copper coatings. The increase in
wear resistance is due to the dispersed second phase particles and improved hardness which
decreases friction between the steel ball and the coating surface. The addition of ceramic
oxide particles marginally transforms the wear from adhesive (unreinforced copper) to
abrasive type.
5.2 Scope of Future work
Due to the unstable data, results of Electrical resistivity measurement could not be reported. It
is one of the important future works that can be carried out to justify the application of these
coatings to electrical components.
Chapter 6
References

55

CHAPTER 6
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Surface Property Modification of Copper

radiation (= 1.5418A) to judge the phases formed, to calculate the

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