Development of Ws Based Coatings and Nano-Composites

DEVELOPMENT OF WS2 BASED COATINGS AND
NANO-COMPOSITES
A Thesis
Submitted in partial fulfilment of the
Requirements for the award of the Degree of
MASTER OF TECHNOLOGY
In
METALLURGICAL ENGINEERING
By
RAMADURGAM PRATHYUSHA
(13011D7218)
Under the esteemed guidance of
External supervisor Internal supervisor
Dr. Joydip Joardar Dr.S.Devaki Rani
Scientist-“E” Assoc. Professor,HOD
ARCI, Balapur Dept. of. Met. Engg.
Hyderabad-50005 JNTUH,CEH,Hyderabad-500085
DEPARTMENT OF METALLURGICAL ENGINEERING
JAWAHRLAL NEHRU TECHNOLOGICAL UNIVERSITY HYDERABAD
COLLEGE OF ENGINEERING HYDERABAD – 500 085

JAWAHARLAL NEHRU TECHNOLOGICAL UNIVERSITY HYDERABAD
COLLEGE OF ENGINEERING
HYDERABAD – 500 085 (AUTONOMOUS)
DECLARATION
I hereby declare that the work entitled “DEVELOPMENT OF WS2 BASED

COATINGS AND NANO-COMPOSITES” was carried out by me and has not
copied from other sources. I have adequately cited and referenced the original
sources. I also declare that I have adhered to all principles of academic honesty and
integrity and have not misrepresented (or) fabricated (or) falsified any
idea/data/fact/source in my submission. Furthermore, the results embodied in this
report have not been submitted to any other universities or institutes for the award of
any other degree.
R.Prathyusha
(13011D7218)
Metallurgical Engineering
JNTUH,CEH, Hyderabad
JAWAHARLAL NEHRU TECHNOLOGICAL UNIVERSITY
COLLEGE OF ENGINEERING, HYDERABAD-500085
CERTIFICATE BY THE GUIDE
I certify that this is a bonafied record of the dissertation work entitled,

“DEVELOPMENT OF WS2 BASED COATINGS AND NANO-COMPOSITES”,
done by “R. Prathyusha” bearing H.No: 13011D7218 submitted to the faculty of
metallurgical engineering, in partial fulfilment of the requirements for the degree of
MASTER OF TECHNOLOGY with specialization in metallurgical engineering
from Jawaharlal Nehru Technological University Hyderabad college of engineering
(autonomous), Hyderabad.
Dr.Joydip Joardar Dr.S.DevakiRani
Scientist – “E” HeadofDepartment
ARCI, Balapur Assoc.Professor,HOD
Hyderabad-50005 Dept.of.Met.Engg
JNTUH, CEH, Hyderabad-500085
Dr. S. DEVAKI RANI

Assoc. Professor & Head of Department
Department of Metallurgical Engineering
JNTUH College of Engineering
Hyderabad
ACKNOWLEDGMENTS
I am deeply indebted to Principal of JNTUH and Dr. S. Devaki Rani, H.O.D,

and Associate Professor of Metallurgical Engineering Dept, JNTUH-CEH for
suggesting carrying out the project work at ARCI, Hyderabad as well as their valuable
suggestions and constant encouragement throughout the course of this project work.
I sincerely thank many people who contributed to my work, the most

important influence on the successful completion of this synopsis report was my
Guides Dr.Joydip Joardar, Scientist-‘E’ Centre for Nano Materials, International
Advanced Research Centre for Powder Metallurgy and New Materials ARCI-
Hyderabad and Dr. Devaki Rani, Assoc.Prof. And HOD of the Metallurgical
Engineering Dept, JNTU Hyderabad.
I sincerely extend my gratitude to Dr.Joydip Joardar for granting me entire

academic freedom throughout the course of this project work and for the support he
gave.
I sincerely thank Dr.R.Vijay, Scientist-‘F’ Team leader, Centre for Nano

Materials, ARCI-Hyderabad, for his support and encouragement while carrying out
the project work.
I would like to thank personally to the people who supported me for the entire
project work, Amulya, Puneeth, Harish, Moulika, Varun, Yamini, Swatchith , Giriraj,
shravan, keerthi and all.
Last but not the least, I would sincerely thank to my parents who have supported,
encouraged and humoured me, in all of my endeavours.
RAMADURGAM PRATHYUSHA
(13011D7218)
CONTENTS
ABSTARCT ---i
LISTOFFIGURES --- ii
LISTOFTABLES ---v
CHAPTER-I
1. INTRODUCTION ---1
1.1. BEARINGS ---1
1.1.1. Air bearings ---1

1.1.2. Types of air bearings ---1
1.1.2.1. Conventional air bearings ---2
1.1.2.2. Single nozzle air bearings ---2
1.1.2.3. Air bearings with channels and chambers ---2
1.1.2.4. Poruos air bearings ---2
1.1.2.5. Laser drilled micro-nozzle air bearing ---2
1.2. AIRFOILBEARING ---3
1.2.1. Foil air bearings classification ---3
1.2.1.1. First generation ---3
1.2.1.2. Second generation ---3
1.2.1.3. Third generation ---3
1.3. SELF-LUBRICATING BEARINGS ---4
1.4. LUBRICATION ---4
1.4.1. Types ---4
1.4.1.1. Fluid film lubrication ---4
1.4.1.2. Elasto- hydrodynamic lubrication ---5
1.4.1.3. Boundary lubrication ---5

1.5. SOLID LUBRICATION ---5
1.5.1. Classification --5
1.6. TUNGSTENDI-SULPHIDE ---6
1.7. Al-4.5%Cu --7
1.8. POWDER METALLURGY ---7
1.9. POWDERSYNTHESIS ---8
1.9.1. High energy ball milling ---9
1.9.2. Planetary milling ---10
1.9.3. Powder blending ---11
1.9.4. Powder compaction --12
1.9.5. Sintering ---14
1.9.5.1. Conventional sintering ---14
1.10. AGE-HARDENING ---15
CHAPTER-II
2. LITERATU REREVIEW ---17

2.1. Solid lubricants ---17
CHAPTER-III
3. EXPERIMENTALPROCEDURE ---21
3.1. MATERIALSELECTION ---21
3.2. POWDERCOMPOSITION ---21
3.3. MIXINGOFPOWDERS ---22
3.4. DENSITYCALCULATIONS ---23
3.5. POWDERSYNTHESIS ---23
3.5.1. Ball milling ---24
3.5.2. Blending ---24
3.5.3. Compacting --24
3.5.4 Sintering ---24
3.6. COATINGS ---25

3.7. FRICTIONTEST ---27
3.8. HARDNESSANDTOUGHNESS ---28
3.9. VICKERSHARDNESSTESTER ---28
3.9.1. Indentation and fracture toughness ---30
CHAPTER-IV
4. CHARACTERISATION ---32
4.7. PIN/BALL-0N–DISC ---32
4.8. PULSEDLASERDEPOSITION ---33

4.9. X-RAYDIFFRACTION ---34
4.9.1. Principal ---35
4.10. SCANNINGELECTRONMICROSCOPE ---36
4.11. FIELDEMISSION-SCANNINGELECTRONMICROSCOPE ---37
4.12. ENERGYDISPERSIVEX-RAYSPECTROSCOPY(EDAX) ---39
4.13. ENERGYDISPERSIVESPECTROMETER(EDS) ---41
4.14. IMAGEANALYSIS --41
4.14.1. Specimen preparation for optical microscopy ---42
CHAPTER-V
5. RESULTSANDDISCUSSIONS ---44
5.7. X-RAYDIFFRACTION ---44
5.8. SIZEDISTRIBUTION --48
5.9. ENERGYDISPERSIVESPECTROSCOPY --55
5.10. SCANNINGELECTRONMICROSCOPY ---61
5.11. FRICTIONTEST --63
5.12. OPTICALANALYSIS ---66
5.13. HARDNESSANDTOUGHNESS ---69
Conclusion and future scope ---71
References ---72
ABSTRACT
WS2 is the most lubricious material, which finds application as solid lubricant
for critical components used in the aerospace and automotive industries. In the present
work various aspects of self lubricating nano-WS2 based coatings and composites will
be investigated. A novel method for the synthesis of WS2 nanosheets and other form
of nano-WS2 has already been developed at ARCI. Under the present project,
conventional coarse grade as well as in house synthesized WS2 nanosheets will be
blended with various techno-commercially important binary as well as ternary alloy
powders in Ni-Fe-Ti system. These blends will be coated on steel substrates by laser
processing under various conditions. In addition, sintering of these blends will be
carried out using conventional as well as rapid consolidation techniques.
This work will involve powder processing (conventional/high energy) for preparing
WS2-metal/intermetallic blends, followed by development of powder coatings by laser
processing, consolidation of the powders by conventional sintering for bi-metallic
composites as well as sintering by field assisted processing. The products will be
evaluated for coefficient of friction, wear resistance, hardness and toughness apart
from structural studies using scanning electron microscopy and X-ray diffraction.
Keywords:WS2,
i
LIST OF FIGURES
Figure1. Typical image of Air-Bearing
Figure2. Typical image of an Air Foil Bearing
Figure3. AL-Cu phase diagram
Figure4. Flow chart of powder metallurgy
Figure5. Components produced by powder metallurgy
Figure6. Mechanism of high energy ball milling
Figure7. [a]- Planetary milling
[b]- Mechanism inside the milling equipment
Figure8. Schematic diagram for powder compaction
Figure9. Steps of agehardening
Figure10. [a]- As-cast microstructure of Fe-Ni-Ti system
[b]- The enthalpy temperature diagram for the Ni-Ti system
Figure11. Schematic diagram of Vickers hardness tester
Figure12. [a]- Macro Vickers hardness tester
[b]- Schematic diagram for calculating Vickers hardness
Figure13. Pin/Ball – on – Disc Tribometer
Figure14. ND: YAG pulsed laser Deposition equipment
Figure15. Schematic diagram of X-Ray diffraction
Figure16. Schematic diagram of X-Ray Beam incident on a

crystallographic material
Figure17. X-Ray Diffractometer
ii
Figure18. Photograph of the sample holder
Figure19. Schematic representation of FE-SEM
Figure20. Schematic representation of Energy Dispersive X-Ray

Spectroscopy
Figure21. Scanning Electron Microscopy
Figure22. Optical Microscope
Figure23. XRD patterns of Ternary and Binary alloy powders
Figure24. XRD patterns for Al-Cu with and without WS2
Figure25. Size distribution of the ternary and binary alloy’s
Figure26. 1066-EDS of ternary (Fe-NI-Ti) alloy powder
Figure27. 1067- EDS of ternary (Fe-NI-Ti) alloy powder
Figure31. 1071- EDS of binary (NI-Ti) alloy powder
Figure32. EDS of coarse grain Al-cu
Figure33. EDS of fine grain Al-Cu
Figure34. EDS of coarse grain Al-Cu-5%WS2
Figure35. EDS of coarse grain Al-Cu-10%WS2
Figure36. EDS of fine grain Al-Cu-5%WS2
Figure37. EDS of fine grain Al-Cu-10%WS2
Figure38. EDS of Al-5%WS2

iii
Figure41. SEM Images of Al-WS2
Figure42. SEM Images of Al-Cu-WS2
Figure43. The Co-efficient of Friction of Al-Cu with and without WS2
Figure44. The Co-efficient of Friction Al-WS2
Figure45. Optical analysis of aged [a] coarse grain Al-Cu-10%WS2
[b] Fine grain Al-Cu- 10%WS2
[c] Al-Cu fine grain
Figure46. Microstructure of [a] Al-20%WS2
[b] Al-10%WS2
[c]Al-20%WS2
Figure47. Microstructure of [a] Fine grain Al-Cu
[b] Fine grain Al-Cu-5%WS2
[c] Fine grain Al-Cu-10%WS2
iv
LIST OF TABLES
Table1. Density of Ternary and Binary alloys
Table2. Sintering temperatures and sintering cycles
Table3. The particle size of ternary and binary systems
Table4. Macro-Vickers hardness values of sintered Al-Cu
Table5. Macro-Vickers hardness values of aged Al-Cu
v
CHAPTER-I
CHAPTER-I
INTRODUCTION
1.1 BEARINGS
A bearing is a machine element that constrains relative motion to only the
desired motion.
1.1.1. Air bearings
An air bearing belongs to slide bearings. In this type air will act as lubricant in
the gap between moving parts and the bearing. The load is carried by the cushioning
effect of the pressurised air. Air bearing uses pressurized air of thin film is provided
for the low-friction between surfaces. Fig1.1. Shows the typical air bearing.
Classification of air bearings:
a. Hydro-static
b. Hydro-dynamic
a. Hydro-static
Hydro static air bearings have no friction at little or no movement of bearings.

This will give the bearings a very high repeatability and life time.
b. Hydro dynamic
Hydro dynamic bearings do not require any external air pressure. In this wear
and friction problem will be there at start and stops. In static conditions compressed
air is supplied by a compressor.
1.1.2 Types of air bearings

Conventional air-bearing
Single-nozzle air-bearing
Air bearings with channels and chambers
Porous air bearings
1
Laser drilled micro-nozzle air bearings
1.1.2.1 Conventional air-bearings

In this, the compressed air flows through large nozzles into the bearing gap.
Due to this, the air consumption has only some flexibility to adjust the bearing’s
feature (bearing surfaces, forces, damping). These air bearings can cause dead
volumes and it is harmful for bearing’s dynamics and sometimes causes self-excited
vibrations.
1.1.2.2 Single-nozzle air bearings

The chamber around a centralized nozzle consist a pre-pressured chamber.
This chambers ratio is usually between 3% and 20% of the bearing surface. In this
type of bearings dead volumes is very high. Sometimes instead of these chambers,
they may be replaced by a concave bearing surfaces. These bearing’s have a very poor
tilt stiffness.
1.1.2.3 Air bearings with channels and chambers

The conventional air-bearings are usually implemented with channels and
chambers. By distributing the air uniformly in the gap will decrease the dead volume.
In 1980’s without chambers micro canal structures are manufactured, this may lead
for dead volume. The increase in the gap height decreases the stiffness and micro
canal’s load and it may cause a serious disadvantage.
1.1.2.4 Porous air bearings

Porous bearings utilize porous material like graphite to allow uniform
distribution of air. In this there is metal-on-metal contact and graphite has a natural
lubricity so that if there is any pressure drop in the air the bearing still works without
damage.
1.1.2.5 Laser drilled micro-nozzle air bearings

The laser drilled air bearing uses the technology of computerized
manufacturing and design to optimize efficiency and performance. This allows
manufacturers more flexibility in manufacturing.
Friction is the force that resists relative motion between two bodies in contact,
so a lubricant is a substance that reduces friction, heat and wears when introduced as a
film between solid surfaces.
2
Fig1.1. Typical image for an Air bearing
1.2 AIR FOIL BEARINGS
Air foil bearings are self-acting hydrodynamic bearings made from sheet metal
foils comprised of at-least two layers. The inner most top foil traps a gas pressure film
that supports a load, while the other layer/layers provide an elastic foundation. Fig1.2
shows the typical air foil bearing [2].
1.2.1 Foil bearings are classified into three generations

1.2.1.1 First generation: These are the bearings whose load carrying structure
comprises only visco-elastic foil whose properties are fined in all directions. It
comprises a foil element which overlaps the internal surface of the bearing sleeve.
1.2.1.2 Second generation: The geometry of the support structures changes in

one of the directions. The variability in axial direction is noted frequently. Due to this
it eliminates leakage caused by gas lubricant and also increases the load capacity of
bearings.
1.2.1.3 Third generation: The properties of load carrying structures are

changing in two directions. The elastic properties of load carrying structure vary in
the radial direction.
3
Fig1.2. Typical image for an Air foil bearing [2]
1.3 SELF-LUBRICATNG BEARINGS

It is a metallic component with high porosity impregnated in a lubricant. The
lubricant present in the porous metal will provide the lubrication to the bearing and
shaft. The bearing is manufactured with a flexible tape backing or metallic backing
that utilizes a wear resistance with appropriate filers to give the material the specific
properties required a self-lubricating bearing.
A self lubricating bearing performs in dirty and high-heat environments and

requires less maintenance and can handle higher load capacities. These properties will
provide the bearing to work under hydro-dynamic conditions. Foil gas bearings
operate by generating a self-acting gas film between surfaces in relative motion.
1.4 LUBRICATION
Lubrication is the process employed to reduce friction between and wear of
one or both surfaces in proximity and moving relative to each other, by interposing a
substance called a lubricant between them. The lubricant can be a solid, (e.g MoS2) a
solid/liquid dispersion, a liquid such as oil (or) water, a liquid-liquid dispersion (a
grease) or a gas.
1.4.1 Types
Fluid film lubrication
Hydro-static lubrication
Hydrodynamic lubrication
Elasto hydrodynamic lubrication
Boundary lubrication
4
1.4.1.1Fluid film lubrication
In this lubrication viscous force supports the load within the space between the
parts in motion relative to one another object.
HYDRO-STATIC LUBRICATION:
An external pressure is applied to the lubricant in the bearing, to maintain the

fluid lubricant film where it would otherwise be squeezed out.
HYDRODYNAMIC LUBRICATION:
The bearing design and motion of the contacting surface is used to pump
lubricant around the bearing to maintain the lubricating film [3].
1.4.1.2 Elasto hydrodynamic lubrication

For higher load conditions, the bodies suffer elastic strains at the contact. Such
strain creates a load bearing area, which provides an almost parallel gap for the fluid
to flow through. Like hydrodynamic lubrication, the motion of the contacting bodies
generates a flow induced pressure, which acts as the bearing force over the contact.
1.4.1.3 Boundary lubrication

At the elevated temperature and pressure conditions chemically reactive
constituents of the lubricant react with the contact surface forming a highly resistant
tenacious layer, (or) film on the moving solid surface [4].
1.5 SOLID LUBRICANTS

Solid lubricants are used where the liquid lubricants can’t sustain i.e. (under
vacuum and high temperatures and high pressures). Some solid materials will have
low shear strength and when applied on a surface which is sliding, they can actually
lower the friction and wear. These materials which actually lower the wear and
friction are called solid- lubricants.
Metal dichalcogenides MX2 (where M is (Mo or W) and X is (S or Se)) are

used as solid lubricants. These lubricants are characterised by its layered structure and
it has weak vanderwall forces which allows easy shearing.
1.5.1 Classification
Soft- solid lubricants
Hard-solid lubricants
5
The hard solid lubricant coatings exhibits lower friction and higher wear
resistance, whereas the soft solid lubricant coatings exhibits lower friction but not
always higher wear resistance.
Hard solid lubricants include some of the carbon-based coatings (like DLC
and diamond) and certain oxides. Soft solid lubricants include soft metals, sulphates,
polymers, lamellar solids including transition metal dichalcogenides, graphite and
boric acid and halides of alkaline earth metals [5].
The commercially successful solid lubricants like MoS2 and WS2 coatings
with and without alloying elements (like Ti, Ni, Au, Sb, and Pb). To increase the life
time of these solid lubricants an adhesion interlayer is necessary. The addition of
these alloying elements may reduce the environmental susceptibility of these solid
lubricants. The lamellar solids and the transition metal dichalcogenides owe their
lubricity to their layered crystal structure [5].
1.6 TUNGSTEN DI-SULPHIDE (WS2)

Tungsten disulphide is one of the transition metal disulfides with lamellar
structure. It occurs naturally as the rare material called tungstenite. It adopts layer
structure with W atoms situated in trigonal prismatic co-ordination sphere. The
chemical bonding with in the plane atoms is strong covalent bond while weak Vander
walls force links the layers together where lateral shear of layers occurs easily, and
previous investigations reveal that WS2 has an improved oxidation resistant, thermal
stability and has self-repairing capability [6,7].
Self-repairing property:
It is the ability to reorganize the molecules into original state on itself after
mechanically disturbed. For reorganizing the molecules should be free to move on the
surface, this mobility indicates that these molecules are not chemically bonded
therefore it has low bonding strength.
1.7 Al-4.5%Cu
This group of alloy is commercially known as duralumin, it belongs to family
of 2xxx series of aluminium alloys. Duralimin has copper as the principal alloying
element about 4-5%copper and 0.5-1.5%Mg. These are relatively soft, ductile and
workable in normal state their light weight and consequent high strength suits for
6
aircraft construction. The structure in the as cast state consists of α-aluminium, with a
very heterogeneous and eutectic located in solution, with dendritic morphology and
eutectic located between dendrite arms and grain boundaries. The micro structural
evolution is complex and the precipitation sequence varies depending on the degree of
super saturation and the aging temperature. Fig1.3. Shows the phase diagram of Al-
4.5% Cu alloy. Maximum hardening effect in Al-Cu alloy is a result of in-situ
transformation of GP zones into transient phase ʺ. Increase in aging temperature
leads to decrease of the hardness of the solid solution due to precipitation of
equilibrium ‘’ phase on the grain boundaries [8].
Fig1.3. Al-Cu phase diagram [8]
1.8. POWDER METALLURGY

Powder metallurgy is defined as “material processing technique used to
consolidate particulate matter i.e. powders both metal and/or non-metals.” This
consists of simple steps like powder mixing, compacting, sintering at subsequent
loads and sintering at elevated temperatures. Fig1.4. shows the flow chart of these
powder metallurgy basic steps. The final product achieved will be satisfactory with
mechanical properties as well as chemical properties.
7
Fig1.4. Flow chart of powder metallurgy
The properties of the final product processed by powder metallurgy greatly

depends on the accuracy of the processing techniques which is common in all powder
metallurgy produced parts and on the secondary operations employed to the product
depending on the applications. The reason behind the spreading and the usage of the
powder metallurgy technique in many applications starting from house-hold tools and
automotive industry lies in the ability to process a variety of material having different
physical properties [1]. Fig1.5. shows some major bearing components produced by
powder metallurgy technique.
8
Fig1.5. Components produced by powder metallurgy
1.9 POWDER SYNTHESIS

Powder synthesis is the process which converts the raw material to the
required composition with definite size and shape and properties. This process is
achieved through a series a steps:
1.9.1 High energy ball milling

Particle size reduction or combination is an important step in many
technological operations. The process itself is defined as the mechanical breakdown
of solids into smaller particles without changing their state of aggregation. It may be
used to create particles of a certain size and shape (including nanosize), to increase
the surface area and induce defects in solids which is needed for subsequent
operations such as chemical reactions, sorption, etc. Milling not only increases the
surface area of solids. It is likely to increase the proportion of regions of high activity
in the surface. This increase is really dramatic: if a cubic solid is broken down into
smaller cubes, each of side 1/n of the side of the original cube, the specific surface
area is increased n-times, but the broken down mass contains n2-times the original
length of edge and n3-times the number of corners.
The size reduction of solids is an energy intensive and highly inefficient process: 5%
of all electricity generated is used in size reduction. Conventionally, the term fine
milling is used for size range below 100 µm and the ultra fine (or very fine) milling
for particles size less than 10 µm. In mechano-chemistry, the term high energy milling
9
is frequently used in order to stress the character of applied milling equipment. Fig1.6.
Shows the mechanism of high energy ball milling.
Fig1.6. Mechanism of high energy ball milling
PARAMETERS
The milled powders obtained vary depending upon various parameters. It

depends upon type of mill used, material of milling media, milling atmosphere, extent
of filling of milling chamber, milling speed and time and most important ball to
powder ratio (BPR). This parameter represents the weight ratio of milling balls to the
powder charge. A wide range of BPR has been used in a variety of investigations
from values as low as 1:1 to as high as 220:1.
1.9.2 Planetary milling
The planetary ball mill owes its name to the planet-like movement of its vial(s). Since
the vials and the supporting disc rotate in opposite directions, the centrifugal forces
alternatively act in like and opposite directions. This causes the milling balls to run
down the inside wall of the vial – the friction effect, followed by the material being
milled and milling balls lifting by of and travelling freely through the inner chamber
of the vial and colliding against the opposite inside wall. Planetary mills exploit the
principle of centrifugal acceleration instead of gravitational acceleration. The
enhancement of the forces acting on the balls in relation to the conventional ball mill
is achieved by the combined action of two centrifugal fields. The charge inside vials
performs two relative motions: a rotary motion around the mill axis and a planetary
motion around the vial axis. The application of laboratory-scale planetary mills for
mechanical activation has been studied intensively by Russian scientists. By
observing certain conditions, these mills produce high mechanical activation after a
relatively short milling time. In principle, it is possible to obtain the gravitational
10
accelerations in values 50–100 g. The energy density in these mills is 100–1000 g
higher than the energy density used earlier in conventional milling equipment. Fig1.7.
Shows the schematic diagram of planetary milling and the mechanism of planetary
milling.
[a] [b]
Fig1.7.[a]. Planetary milling
[b]mechanism inside the milling equipment.
1.9.3 Powder blending

This stage is done for several reasons such as: achieving uniform distribution
of powder particles and composition. Blending could also be done for mixing more
than one powder type to form a composite. Using a liquid media is essential to avoid
agglomeration that may arise as a result of particles cold welding together.
Blending is an operation of thorough mingling of different powders of the

same composition (or substance) or various grades of same powders, while mixing
refer to the thorough mingling of powders more than one material. However both
terms are frequently employed interchangeably. Blending or mixing is extremely
desirable in the preparation of alloys from elemental powders, in the production of
dispersion strengthened alloys, porous bearing, sintered friction material, electric and
magnetic materials, etc.
11
Additives such as binders and lubricators are usually included in both the
processes to facilitate pressing and achieve the required green strength and controlled
porosity in the finished part. Both these operations not only mingle the powder but
also exert a grinding action on the powder particle.
Mixing of powders is a most complex and relatively little understood process

which relies on the movement of mass of one powder component into that of another
powder component. This movement is dependent not only on the powder material,
particle size and shape and surface conditions but also on the environment conditions.
The main purpose of mixing is to produce uniform distribution of powder,

usually metallic and different specific gravities and of different particle size and
shapes which will give consistent performance during pressing and sintering. A
uniform mixture is that mixture which has one and the same chemical composition in
sample taken from any place or locality in the mixture volume. The other purpose is
the ability to control the powder characteristics. Mixing must be efficient i.e., it must
produce a homogeneous mixture in the least possible time [9].
Mixing can be dry or wet, based on the medium in which the milling is carried
out. Wet mixing is used to produce a more fine and uniform mixture of powder
particles. This may be accomplished by the addition of alcohol, benzene, toluene,
distilled water, glycerine or acetone as a liquid medium in adequate amount so as to
bring powder to the consistency of a thin paste. On completion of mixing the liquid
medium used is driven off by drying the mix in air, if possible in a well-ventilated
area. Forced drying may also be used carefully by heating the powder mix [9].
1.9.4 Powder compaction

Compaction in metal dies is one of the most important methods for shaping
metal powders and this still account for the bulk of commercial production. Both
experimental and theoretical works have been carried out by numerous workers in
attempts to explain exactly the behaviour of metal powders when subjected to external
pressure in a metal die [10-12]. Unidirectional pressing is a traditional and one of the
well-known compaction techniques. Compaction results in the particles becoming
rearranges by plastic deformation because of the applied force resulting in a
remarkable volumetric reduction. The particles rearrange during the compaction
process and the force applied on the particles helps in filling the voids by deforming
12
these particles plastically. The application of the excessive pressures may result in
particle interlocking, which may form stress concentrations at these points. When the
die cavity is uniformly filled with metal powder it gives rise to a certain packing
density, but a certain amount bridges are also formed, when the powder is slightly
pressed by the application of one punch or more punches: the first densification
occurs by particles movement and rearrangement causing improved packing density.
If the pressure is further increased, clean particles are brought close enough
together and they adhere to each other with some strength. This metal to metal contact
has been described as “cold welding” or adhesion. Further increase in pressure causes
deformation of the particles and large areas of contact and mechanical interlocking of
neighbouring grains will take place as well as filling of voids by the squeezing of
small particles. Strength and density are thus increased. After the compaction the
produced part is called green compact or a preform that is ejected from the die in one
piece.
Deformation is the major mechanism of densification with regard to production of

high density parts. Both the types of deformation – elastic and plastic may take place.
Most of the elastic deformation will be recovered on removal of stress from the
compact. This may occur before, during and after ejection from the die cavity. Fig1.8.
Shows the schematic diagram of powder compaction.
In general, the compacts have dimensions slightly greater than the die
dimension due to this reason. The magnitude of elastic deformation will depend on
elastic modulus values and particles stress values relative to the yield stress of the
material. In the case of very hard and brittle powders such as Cr, refractory metals and
carbides, density may increase after initial packing stage without plastic deformation.
The elastic recovery is much greater for hard metal powders and thus it decreases the
size of contact areas and consequently its strength.
13
Fig1.8. Powder compaction schematic diagram
During compaction several types of friction occur as follows:
 Friction between moving punches and die wall which is relatively small and
the pressure loss caused by it is practically negligible
 Friction between adjacent particles which are insignificant and play a major
part in compaction
 internal friction within the powder particles during deformation
 Friction between the powder particles and die wall, (this is one of the most
important factors which affects the uniformity of density throughout the
compacted part. This is the primary source of pressure loss during pressing
and the magnitude of its distribution, particle shape and surface condition and
the inter-particle pressure) and
 Friction between the green compact and the die wall during ejection.
This type of friction depends upon the powder material, die finish and tolerance and
the compacting pressure.
Another method of minimizing the loss of transmitted compacting pressure is

to reduce the fractional effects thereby decreasing the density variation by the use of a
die wall or powder lubricant. As a result of work done on the die wall lubrication and
the admixture of lubricant with the powder, it has been well established the die
lubricant is superior and more effective with regard to both densification and ejection
[13]. Die wall lubrication is also beneficial to minimize punch travel and powder-fill
14
depth. The other advantage of die wall lubricant is that it is not essential “dewax” as a
first step in the sintering operation. Also much lubricant is required here to obtain the
same effect when compared with the amount of admixed lubricant.
MoS2, stearic acid and sterides of Li, Zn, Ba, Al, Pb, Mg, particularly Zinc and
lithium-strides are employed where adhesion; in small percentages (say, <1.5-3%) is
most effective on the other hand, a large number of lubricants can be tolerated then a
acrawax, prefill wax, camphor or animal parts are mostly employed.
1.9.5 Sintering
It is the process of compacting and forming a solid mass of material by heat
and/or pressure without melting it to the point of liquefaction. The atoms in the
materials diffuse across the boundaries of the particles, fusing the particles together
and creating one solid piece because the sintering temperature does not have to reach
the melting point of the material, sintering is often chosen as the shaping process for
materials with extremely high melting points such as ‘W’ and ‘Mo’.
Sintering is effective when the process reduces the porosity and enhances
properties such as strength, electrical conductivity, translucency and thermal
conductivity. During the firing process, atomic diffusion drives powder surface
elimination in different stages, starting from the necks between powders to final
elimination of small pores at the end of the process. The driving force for
densification is the change in free energy from the decrease in surface area and
lowering of the surface free energy by the replacement of solid vapour interfaces.
Sintering is static when a metal powder under certain external conditions may
exhibit coalescence, and yet reverts to its normal behaviour when such conditions are
removed. In most cases, the density of a collection of grains increases as material flow
into voids, causing a decrease in overall volume.
1.9.5.1 Conventional sintering

It is the process in which internal heating is used for the baking of the tools in
the furnace. Conventional sintering is the oldest form of sintering process.
Conventional sintering is equipped with an isolated chamber with internal heating
fitting and cooling around the chamber. Conventional sintering has slow rates of
heating and has a long holding time. In this process the powders are initially mixed
15
thoroughly and then compacted or pressed using a die and punch assembly to a certain
pressure to get a green compact. This green compact is then sintered in the furnace.
Sintering is done in either a vacuum medium or any air medium required such as
nitrogen or hydrogen. Vacuum is created to prevent any reaction of the compact with
the surrounding atmosphere. The main advantage of using conventional sintering is
that lots of tools can be manufactured in a single run and it has good cooling rates.
Tools are manufactured mostly using conventional sintering technique process itself.
1.10. Age hardening

Age hardening is a heat treatment technique used to increase the yield strength
of malleable materials. It depends on changes in solid solubility with temperature to
produce fine particles of an impurity phase which impede the movement of
dislocation. Since, dislocations are often the dominant carriers of plasticity, this serves
to harden the material. The strength and hardness of some metal alloys may be
enhanced by formation of extremely small uniformly dispensed second phase particles
within the original phase matrix in a process known as precipitation (or) age-
hardening. Fig1.9. Shows the steps involved in precipitation hardening.
The precipitate particles act as obstacles to dislocation movement and there by

strengthen the heat-treated alloys. In order for an alloy system to be able to be
precipitation- strengthened, there must be a terminal solid solution that has a
decreasing solid solubility as the temperature decreases.
The Al-Cu shows this type of decrease along the solvus between ‘α’ and ‘α+’
regions. 96% Al (by weight) and 4% Cu (by weight) is chosen. Since, there is a larger
decrease in the solid solubility of solid solution ‘α’ in decrease the temperature from
5500Cto 750C.
16
Fig1.9. Steps in agehardening
17
CHAPTER-II
18
CHAPTER-II
LITERATURE SURVEY
2.1. SOLID-LUBRICANTS
A solid-lubricant is defined as any material used as a thin film or a powder on
a surface to provide protection from damage during relative movement and to control
friction and wear under severe conditions like high pressures, high temperatures and
vacuum conditions. Some solid metals possess low shear strength and when applied
on sliding surfaces they can lower friction and wear. A solid lubrication is achieved
by self-lubricating solids or by imposing a solid material between the interacting
surfaces in relative motion.
In recent years strides have been made in the formulation of solid-lubricant

coatings for a wide range of industrial applications. Solid lubricant films are used in a
variety of mechanisms on various space craft and launch vehicles. These coatings are
now available in nano-structured composites to provide better performance and
durability even under severe sliding conditions.
Nano-composite coatings like MoS2/C2, WC/C2 and WS2/C and nano diamond.
Lamellar film coatings like MoS2, graphite, WS2.
Solid lubricant films can be produced on a given surface by wide range of

technologies such as sputtering, ion-plating, arc-PVD; pulsed laser deposition, IBAD
(or) plasma enhanced chemical vapour deposition. These methods result in strong
adhesion between solid lubricant films and substrate materials.
Al-Cu alloys are the most important high strength “Al” alloys. They have been
employed extensively in the aircraft and military industries.
Malcolm k. Stanford et.al [14] in this paper Cu alloy was applied by novel
deposition technique and the journal bearing was coated with Ps304, a plasma spray
deposited high temperature composite solid lubricant coating. Ion diffusion (novel
technique) gives smoother surface than cathodic arc deposition. Tribological
performances are done with and without Cu-4Al foil coatings through start-stop tests
19
at 250C and 6500C.Cu-4Al gives more stable friction performance at initial break-in
period with respect to temperature and it also prevents top foil wear even at high
temperatures.
Arindam ghosh et.al [15] in this context, Al- alumina compacts with varying
alumina weight% were compacted in the range of 115-290 MPa pressure. Compacts
were prepared with pressure of 290 MPa and sintered in an argon atmosphere at
873,773,673 and 573k for 1 hour. The green density, %spring back, % porosity and
hardness of the green compacts were determined. To identify the morphology of
alumina particles and pores in green and sintered compacts were carried out by
scanning electron microscopy. This study indicates that compact density increases
with increasing compacting pressure and decreases with addition of alumina content.
93% of maximum density is achieved with pure aluminium and it decreased to 85%
for alumina compacts. Grain growth of aluminium particles is noticed in the compacts
after sintering at 773 and 873k. Dispersion in the aluminium matrix of fine alumina
particles occurs predominantly when sintered at 773k in the compacts which results in
increase in the hardness value.
L.I durate et.al [16] investigated phase relations in the Fe-Ni-Ti system, two
isothermal sections at 800oc and 1000oc and revised liquidus projection were
established. For as-cast alloys as well as samples equilibrated at 800oC and 1000oC,
the micro-structural characterisation was performed by SEM. The chemical
compositions of the phases were analysed by electron probe micro analysis (EPMA),
and for different thermal analysis liquidus temperatures were examined. This study
confirms that “Ti” solubility varies in dependence of Fe-Ni ratio.
G.Cacciamani et.al [17] evaluated the Fe-Ni-Ti alloy system with Fe-Ni and
Fe-Ti binary subsystems. In this present study they mainly concentrated on phase
constitution and phase equilibria, thermo-chemical and diffusion data.
Bing-Yun Li et.al [18] studied porous Ni-Ti shape memory alloys (SMA’s). In
this study a porous bulk Ni-Ti with channels of banded structure and 54% porosity
has been successfully prepared by self-propagating high temperature synthesis (SHS).
Mao-sheng yang et.al [19] studied about high temperature self-lubricating

wear-resistant NiCr3-30%ws2 coatings and wear resistant NiCr3C2 coatings. These
coatings were fabricated on 0Cr18Ni9 austenitic S.S by laser cladding. Tribological
20
properties were evaluated using a Ball-on-disk wear tester under dry sliding condition
at room temperature, 3000C and 6000C respectively and phase constitutions and
microstructures were investigated. The wear tests gave the results that the co-efficient
of friction of both coatings decreases with decreasing temperature while both wear
rate increased. The COF is lower in NiCr3C2-30%WS2 than without WS2 at all
temperatures. But its wear rate is lower at 3000C.
A.Shankara et.al [20] studied MoS2 based solid lubricant mixtures containing
zirconia and graphite. These were coated on steel specimens and scratch test was
performed for several numbers of cycles. The results showed that the addition of
zirconia and graphite into the MoS2 lubricant has improved its properties. At high
temperatures the moisture evaporation enhanced the coating performance of the film.
G.Aggarwal et.al [21]. In this research a new coating process called cold spray
for self-lubricating coatings on Ti-6Al-4V alloy. The cold spray process is used to
deposit Ni-MoS2 and Ni-HBN self-lubricating coatings.
Jie yaoet.al [22] identified the as-prepared sample of NiAl-15% (by weight)
MLG (multilayer graphene) – 5%WS2 (by weight) exhibited excellent tribological
properties. And a continuous film was formed during the sliding process to provide
the low-strength junction at the interface reduces the wear and friction COF rates.
Kazuhisa miyoshi et.al [23] examined the surface chemistry friction and wear
behaviour of untreated and annealed WS2 coatings in sliding contact with a 440c S.S
and 6mm Dia ball. The WS2 coatings and annealing were performed using pulsed
laser deposition technique. The friction test were carried out with a constant load
rotating speed 120rpm, with a load of 0.98N (100g) and an average Hertzian contact
pressure of 44 GPa and sliding velocity from 31-107 mm/s at three environment, dry
nitrogen, humid air and ultra high vacuum conditions. Characterisations including
SEM, EDX, XPS, surface profilometry, and Vickers hardness testing was performed
on WS2 coating surfaces. The laser annealing decreases the wear of WS 2coating in
vacuum and the annealed WS2 coating had a low COF (<0.1).
S.M.Muzakkir et.al [24] investigated the effectiveness of WS2 by employing it

in varying quantities [0.5,1.0,1.5 % by weight] in commercial lubricant on the wear of
the sliding surfaces subjected to heavy load and slow speeds is reduced by using WS 2
particles as lubricant. 1% (by weight) showed the minimum wear rate in this study.
21
William A.Brainard et.al [25] studied the thermal stability and friction
experiments with disulfides, diselenides and ditellurides of Molybdenum and
Tungsten in vacuum (10-9 to 10-6 torr). Friction test was performed and diselenides
showed the best performance where as ditellurides showed the poorest because of a
low thermal dissociation temperature. The disulfides are the most thermal stable of
the inorganic compounds at elevated temperatures in vacuum. The weight loss rate of
WS2 is slower than MoS2 above 9300C. Thermal dissociation in vacuum was observed
for MoS2 at 10900C and WS2 at 10400C. WS2, MoS2 did not showed effective
lubrication above 7300C and 6500C.
N.M.Renevier et.al [26] reported that the properties of MoS2 coatings coatings
can be improved by the co-deposition of small of Ti are harder, much more wear
resistant and a less sensitive to atmospheric water vapour during tribological tests and
showed low wear rate of 4x10-17 m3/n m, a low friction co-efficient of 0.02-0.1 and a
high load-bearing capacity upto 5GPa.
C.Dellacorte et.al [27] studied the tribological properties of one chrome oxide
and one chrome carbide based solid-lubricant coating were evaluated in a partial arc
foil bearing at 250C and 5000C. Chrome-oxide coating which contains both Ag and
BF2/CaF2 exhibited low friction at both at both temperatures in sliding against Al2O3
coated foils. The chrome-carbide coating exhibited high friction at 250C and low
friction at 5000C.
R. Holinski et.al [28] studied the properties of MoS2 properties will be

explained by the strong polarization of the sulphur atoms which provide a layer
structure, good adhesion to metal surfaces, adhesion between MoS2 basal planes, easy
sliding of MoS2 lamallae and the formation of a continuous homogeneous films.
A.A. Voevodin et.al [29] studied the tribological properties of three phase
composite coatings consisting of nano crystalline WC, amorphous Diamond-Like
Carbon (DLC) and nano crystalline WS2. These coatings have a 5µm thickness, 7-8
GPa hardness, excellent wear resistance and low friction co-efficient (0.03 in vacuum
and 0.15 in air).
Chaman lall et.al [30] achieved better wear strength with Al-14%Si alloy and
a ceramic reinforced composite, a high strength Al-Zn alloy showed poor wear
22
resistance, while pure aluminium showed excellent wear resistant when a liquid was
present.
23
CHAPTER-III
24
CHAPTER-III
EXPERIMENTAL PROCEDURE
3.1. MATERIAL SELECTION

WS2 is used as a solid-lubricant. It has lamellar structure, with in the planes it
has strong covalent bond and between the planes it has week vandervalls forces. This
layered structure allows this sliding movement to this WS2 and hence it has low
friction.
Various ternary and binary systems are added as binders to this WS2 of various
weight percentages of WS2 in these ternary and binary alloys (i.e. 5, 10, and 20%).
The ternary and binary systems like Fe-Ni-Ti, Ni-Ti, and Al-Cu are used as binders
since the foil bearings are made up of Ni-Cr based alloys i.e. inconel x-750. It is easy
to incorporate the coatings on these bearings if the solid-lubricant like WS2 is blended
with these ternary and binary alloys.
3.2. POWDER COMPOSTION

All powder composition percentages are by weight.
TERNARY SYSTEMS:
 Fe-Ni-Ti
 Fe4.6%, Ni14.8%, Ti80.6%.
 Fe22.5%, Ni43.5%, Ti34.0%.
 Fe18.3%, Ni15.0%, Ti66.7%.
 Fe67.8%, Ni9.4%, Ti22.8%.
 Fe50.0%, Ni29.6%, Ti20.4%.[16]
BINARY SYSTEMS:
 Ni-Ti
 Ni59%, Ti41%.[31]
 Al-Cu
 Al95.5%, Cu4.5%.
25
 Al (100%)
The Figure3.1. [a], [b] shows the compositions, the phases and the liquidous
temperatures of the alloys selected.
[a] [b]
Fig3.1. [a]: As-cast microstructures of: (1) alloy 35: Fe 18.3 Ni 15.0 Ti 66.7 ; (2) alloy
15: Fe 4.6 Ni 14.8 Ti 80.6 ; (3) alloy 20: Fe 22.5 Ni 43.5 Ti 34.0 [16]
[b]: The enthalpy–temperature diagram for the Ni/Ti system [36]
3.3. MIXING OF POWDERS:

Above mentioned ternary and binary alloy powders are mixed in a planetary
ball milling for 20 hours with 15 minutes of pause for every hour. The powders are
mixed with a ball to powder ratio of 10:1 at 200 rpm and Al-Cu powder alloy is
milled at 150 rpm for 10 hours with the same 15 minutes of pause.
Milled powders of these ternary and binary alloy powder compositions are
blended with various weight percentages of WS2 (i.e. 5, 10, and 20%) for 24 hours.
And Al (100%) is blended with WS2 of 5, 10 and 30 wt%.
3.4. DENSITY CALCULATIONS

Density calculations of main material WS2 and binders like ternary and binary
alloys like Fe-Ni-Ti, Ni-Ti, and Al-Cu with and without WS2.
WS2: 7.5g/cc
26
Density calculation for an alloy:
1/Da= x1/d1 + x2/d2 + x3/d3
Where Da is density of final alloy
X1, x2, x3---: are mass of each element
d1, d2, d3---: are the densities of each element.
Table1.1. Densities of Ternary and binary alloys (with and without WS2)
Alloy Without WS2 With 5%WS2 With 10%WS2 With 20%WS2
Fe4.6%, Ni14.8%, 4.87 g/cc 5.017 g/cc 5.2 g/cc

Ti80.6%
Fe22.5%, Ni43.5%, 6.34 g/cc 6.43 g/cc 6.54 g/cc
Ti34.0%
Fe18.3%, Ni15.0%, 5.5g/cc 5.34 g/cc 5.52g/cc
Ti66.7%
Fe67.8%, Ni9.4%, 6.7 g/cc 6.77 g/cc 6.84 g/cc
Ti22.8%
Fe50.0%, Ni29.6%, 6.9 g/cc 6.95 g/cc 7.01 g/cc
Ti20.4%
Ni59%, Ti41% 6.11 g/cc 6.22g/cc 6.34g/cc
Al95.5%, Cu4.5% 2.79 g/cc 2.88 g/cc 2.977 g/cc 3.19 g/cc
Al100% 2.7 g/cc 2.78 g/cc 2.88 g/cc 3.09 g/cc
These ternary alloy powders are blended with WS2 are coated on steel substrates of
size 25x 25 mm size with less than 0.5mm thickness and laser processed the samples
to impregnate that coating on to the substrate.
3.5. POWDER SYNTHESIS

Powder synthesis consists of three basic steps milling/blending, compacting,
sintering and finishing if required.
27
3.5.1 Ball milling
The metal powders are synthesized initially to the required nano size. High
energy ball milling is done to prepare the intermetallics of required compositions of
alloys discussed above with even distribution of particles. The ternary Fe-Ni-Ti and
binary Ni-Ti, Al-Cu are milled according to the compositions [16, 31] by using high
energy ball milling.
Pure metals of powders Fe, Ni and Ti (Alfa Aesar, -325 mesh and with 98%,
99.8% and 99% purity resp.) are mixed appropriate with the given compositions and
poured into the vials of milling according to the ball to powder ratio of 10:1 to
maintain the uniformity of alloy particles and toluene is used as a liquid dispersive
during the milling process to prevent the formation of oxides during the milling and
milled in high energy ball milling with 250 rpm for 20 hours with 15 of pause for
every hour. The balls that are used in this high energy ball milling are WC balls to
ensure the uniform mixing of powders at high speeds. And Al-Cu powders (Alfa
Aesar, -325 mesh and 99.5% purity) are milled with 150 rpm for 10 hours with the
same parameters which are used for Fe-Ni-Ti alloys.
3.5.2. Blending
The milled powders thus obtained are blended with the varying weight
percentages of WS2 (5,10and 20% by weight) in a pot blending apparatus. In this pot
blending steel balls are used for mixing of powders to ensure thorough mixing of
powders. These ternary and binary systems are blended with 5%, 10% and 20% of
WS2 with appropriate ball to powder ratio of 5:1 for the uniform mixing of metal
powders for 24 hours for the uniform mixing and in toluene medium to ensure the
continuous flow of powders during the blending process.
3.5.3. Compacting
The milled and blended alloy powders of ternary alloys Fe-Ni-Ti with and
without WS2 powders and binary alloys Ni-Ti with and without WS2 are compacted
with 300MPa pressure [33, 34] to produce the green compacts. And the pure
Aluminium with WS2 and Al-Cu with and without WS2 are compacted with 240MPa
pressure [15] to produce the green compacts by using WC die in a compression
machine.
28
3.5.4. Sintering
The green compacts obtained are conventionally sintered at different
temperatures because of the varying mechanical properties of the alloys prepared. At
12000C, [32] 10000C,[17] 6000C,and 5000C[15]sintering is done for the Fe-Ni-Ti with
and without WS2, Ni-Ti with and without WS2, Al with WS2 and Al-Cu with and
without WS2 respectively. Sintering is done in Nitrogen and Argon medium with
2hours of dwell time and furnace cooling till it reaches room temperature. Argon and
nitrogen are used to prevent oxidation occurs at high temperatures and reactions occur
between elements in the alloys at high temperatures. The argon and nitrogen flow
should be kept till the furnace temperatures reaches to room temperature to ensure
that no oxides formed during sintering.
29
Table1.2. Sintering temperatures and sintering cycle
Alloy composition Sintering temperature Sintering cycle
Fe22.5%, Ni43.5%, Ti34.0% 10000C 00C-10000C at 60c/min

1 hour holding
cooling till room temperature
Fe18.3%, Ni15.0%, Ti66.7% 12000C 00C-12000C at 60c/min
1 hour holding
Ni59%, Ti41% 10000C and 12000C 00C-10000C at 60c/min
1 hour dwell
00C-12000C at 30c/min
2 hours holding
0
Fe18.3%, Ni15.0%, Ti66.7% with 1000 C 00C-10000C at 60c/min
20%WS2 1 hour holding
Al with and without WS2 5000C, 6000C 00C -5000C at 2.50c/min
00C -6000C at 2.50c/min
1 hour holding
Cooling till room
temperature
Al-Cu with and without WS2 6500C 00C -6500C at 2.50c/min
1 hour holding
6500C-5500 cooling at
30c/min
1 hour holding
Cooling till room
temperature
3.6. COATINGS
The powders blended and milled Fe-Ni-Ti and Ni-Ti with WS2 are coated on
the steel substrates and dried in dessicator and laser processed to impregnate the
coating onto the substrate. The thickness of the coating is < 1 µm.
30
Laser parameters:
Speed: [1-overlap] x repetition rate x spot diameter
For
50%overlap with ratio: 182 and focus: 777
Repetition rate: 60hz and
Spot dia: 1mm
Therefore speed = [1-0.5] x 60 x 1
=30mm/s
With energy- 1 joule, lamp power L1= [0.1-0.2] kW
L2= [0.2] kW
For
75%overlap with ratio: 182 and focus: 777
Repetition rate: 60hz and
Spot dia: 1mm
Therefore speed = [1-0.75] x 60 x 1
= 15mm/s
With energy- 1 joule, lamp power L1= [0.1-0.2] kW
L2= [0.2] kW
Pulse duration- 3millisec.
3.7. FRICTION TEST:

The laser coated samples and the sintered compacts prepared are tested
to obtain the co-efficient of friction with pin/ball on disc apparatus. Friction test is
done on the samples of laser coated on ball-on-disc apparatus with steel ball with load
of 1 Kg F; speed of 200 rpm; and for 30 minutes with track diameter of 20mm. And
for Al-Cu sintered samples the friction test is done on pin-on-disc apparatus with “Al”
31
pin with 500g of load; speed of 150 rpm; with track diameter of 4mm and for 15
minutes.
3.8. HARDNESS AND TOUGHNESS
3.8.1. Vickers hardness tester

Micro and macro hardness of the metals, ceramics and composites is
useful for a variety of applications. Micro-hardness testing per ASTM-384
gives an allowable range of loads for testing with a diamond indenter; the
resulting indentation is measured and converted to a hardness value. The
actual indenters used are Vickers (more common; a square base diamond
pyramid with an angle apical angle of 136°) or knoop (a narrow rhombus
shaped indenter). The result for either Vickers or Knoop micro hardness is
reported in HV and is proportional to load divided by the square of the
diagonal of the indentation measured from the test. A schematic diagram
showing a Vickers hardness indenter with a diamond pyramid tip and a sample
indentation is given in Figure3.2.
Figure3.2. Schematic diagram of Vickers Indentation
The load on the Vickers micro-hardness indenter usually ranges from a few
grams to a kilogram. In contrast in ‘Macro’ Vickers hardness loads vary from 1 to 120
kg. The indentations must be as large as possible, within the confines of the geometry,
to minimize errors in measuring the indentation. Vickers hardness is also sometimes
called ‘Diamond Pyramid Hardness (DPH)’ owing to the shape of the indenter. The
test samples should have a smooth surface and be held perpendicular to the indenter.
The Vickers Hardness test consists of indenting the test material with a diamond
indenter, in the form of a right pyramid with a square base and an angle of 136
32
between opposite faces subjected to a load of 1 to 100 KgF. The full load is normally
applied for 10 to 15 seconds. The two diagonals of the indentation left on the surface
of the material after removal of the load are measured using their microscope and
their average is calculated. The area of the sloping surface of the indentation is
calculated. The Vickers hardness is the quotient obtained by dividing the KgF load by
the area of the indentation given in square millimetres. A schematic figure to explain
the hardness calculation is shown in Figure3.3.
[a] [b]
Figure3.3. (a)Vickers hardness tester, (b) Schematic diagram for calculating Vickers
hardness
The Vickers hardness of the tool is found out using following equation:
1854.4 × 𝑃
𝑎2
Where P = load applied, a = Average length of the diagonal = [𝑑1+𝑑2]/ 2
𝑑1 = length of diagonal 1, 𝑑2 = length of diagonal 2
The advantages of the Vickers hardness test are that extremely accurate
readings can be taken and just one type of indenter is used for all types of metals and
surface treatments. Although thoroughly adaptable and very precise for testing the
softest and hardest of materials, under varying loads, the Vickers machine is a floor
33
standing unit that is more expensive than the Brinell or Rockwell machines. The
photograph of Vickers macro hardness testing machine is shown in Figure3.3. (a).
There is now a trend towards reporting Vickers hardness in SI units (MPa or

GPa) particularly in academic papers. Unfortunately, this can cause confusion.
Vickers hardness (e.g. HV/30) value should normally be expressed as a number only
without the units’ (KgF/mm2). Rigorous application of SI is a problem.SI would
involve reporting force in Newton which is practically meaningless and messy to
engineers and technicians. To convert a Vickers hardness number to Pascal, the force
applied needs to be converts from KgF to Newton and the area needs to be converted
from mm2 to m2 or otherwise the following conversion formulae can be used to get
results in Pascal. To convert HV to MPa multiply by 9.807 and to convert HV to GPa
multiply by 0.009807
3.8.2. Indentation fracture toughness

Accurately measuring the fracture toughness of brittle materials can often be
challenging. Creating sharp pre-cracks can be difficult without catastrophically failing
the specimen, while fracture toughness data using notched specimens can give
erroneously high values. For those reasons, assessing fracture toughness by making
direct measurements of cracks created using a sharp diamond indenter, such as
Vickers, Knoop, Berkovich, or cube corner, can appear to be an attractive alternative
to more traditional fracture toughness testing techniques. Such tests can be relatively
quick and easy to perform, require little specialized equipment, and can allow probing
of localized microstructural features. Accordingly, such techniques are finding
considerable usage in studying the fracture behaviour of biomaterials and hard tissues.
As with all fracture toughness testing techniques, the ultimate goal is to

quantify the fracture toughness accurately in a way that can be universally compared
with results generated using other techniques and from other studies. Unfortunately,
techniques involving direct measurements from indent cracks are often unsuccessful
in this regard. A secondary goal may be to provide a quick semi-quantitative way to
rank the toughness of different materials. In this case, indentation techniques can have
some merit, but cannot be used indiscriminately.
Vickers Hardness and Indentation fracture toughness of reference tools and

sintered tool inserts are tested using LECO LV700AT tester. A load of 10KgF with 13
34
seconds hold time is applied on the tools. The lengths of the indent diagonals are
measured along with the crack lengths produced at the tips of the indent. The crack
lengths and the indent diagonal lengths are used to calculate the Indentation fracture
toughness which is evaluated using Shetty’s equation [35].
Shetty’s Equation:
0.03 × 𝑃
𝑎
× √𝑙
2
This equation is prominently used to evaluate the fracture toughness of the

ceramic tools. Where P = Load applied,
a = Average length of the diagonal = [𝑑1+𝑑2]/ 2
𝑑1 = length of diagonal 1, 𝑑2 = length of diagonal 2, 𝑙 = length of crack.
The indents were made at certain points on the tool which are at specific
distance from the boundary. Five indents are made from one boundary to another the
indents are 0.6mm, 3.1mm from their respective boundary. And an indent at the
centre of the tool at 6.3mm from the boundary is made.
35
CHAPTER-IV
36
CHAPTER-IV
CHARACTERIZATION
Characterisation is done to the powders selected to analyse particle size, shape

and composition of the powder by using FESEM, XRD, SEM and EDS. By using
these characterisation techniques one can find the composition of powders by using
EDS, and by using XRD we can analyse the phase analysis, and by using FESEM and
SEM particle size can be analysed at higher magnification and at lower magnification
respectively. The tribology part of material can be done by using pin/ball on disk.
4.1. PIN/BALL – ON - DISC:

A tribometer is an instrument that measures tribological quantities like co-
efficient of friction, wear volume and friction force, between two surfaces in contact.
A simple tribometer is described by a hanging mass and a mass resting on a horizontal
surface, connected to each other via a string and pulley. The co-efficient of friction, µ
is determined by increasing the hanging mass until the moment that the resting mass
begins to slide when the system is stationary.
The general equation for friction force, F=µN
Where, N is the normal force and
F is the loading force
A Pin/Ball on Disc Tribometer consists of a stationary “pin/ball” under an

applied load in contact with a rotating disc; usually for pin-on-disc the pins used are
spherical to simplify the contact geometry. This test has proved useful in providing a
simple wear and friction for low friction coatings such DLC coatings. The co-efficient
of friction is determined by the ratio of the friction force to the loading force.
i.e
µ=F/N.
37
Fig4.1. Pin/ball- on- disc tribometer
4.2. PULSED LASER DEPOSITION
Laser was first developed in 1960’s. This is useful mainly in material

processing. It possesses many properties such as narrow frequency bandwidth, high
power density and coherence. The light beam is intense enough to vaporize the
hardest and most heat resistant materials. It is widely used in the industry for
machining of thin films, welding, micro pattering, and modification of materials and
also to deposit poly component materials on the substrates. The deposition is the so-
called pulsed laser deposition.
A pulsed laser beam is focused onto the surface of solid target. The strong absorption
of the electromagnetic radiation by the solid surface leads to rapid evaporation of the
target materials. The evaporated material consists of highly excited and ionized
species. They presented themselves as a glowing plasma plume immediately in front
of the target surface if the ablation is carried out in vacuum.
By controlling the number of pulses, a fine control of film thickness down to atomic
monolayer can be achieved. The most important feature of PLD is that the
stoichiometry of the target can be retained in the deposited films. This is the result of
the extremely high heating target surface (108 k/s) due to pulsed laser irradiation.
It leads to the congruent evaporation of the target irrespective of the evaporating point
of the constituent elements or compounds of the target.
38
Fig4.2. Nd: YAG pulsed laser
4.3. X- RAY DIFFRACTION:

Bruker AXS P8 advanced system with Cu K radiation =1.5406 A.This
method is used to determine the atomic and the molecular structure of the crystal, in
which the crystalline atoms cause a beam of the X-rays to diffract into many specific
directions. By measuring the angle and intensities of these diffracted beams, a
crystallographer can produce a three-dimensional picture of the density of electron
within the crystal. From this electron density, the mean position of the atoms in the
crystal can be determined, as well as their chemical bonds their disorder and various
other informations.
X-ray diffraction is a non-destructive method to analyze crystalline state under

normal atmospheric conditions. XRD works on the principle of diffraction of X-ray
when striking a polycrystalline material in which each crystal is oriented in different
direction. The 1 dimensional imaging is obtained by calculating the resulting
diffraction from the sample. It maps intensity with 2θ.
39
Figure4.3. Schematic diagram of X-ray diffraction
4.3.1. Principle:
When a monochromatic x-ray beam with wavelength (λ) is projected onto a
crystalline material at an angle (θ), diffraction occurs when the distance travelled by
the rays reflected from successive planes differs by a complete number n of
wavelengths. These x-rays are generated by a cathode ray tube, filtered to produce
monochromatic radiation, focused, and directed on to the sample. The interaction of
the incident rays with the sample produces a diffracted ray when conditions
satisfy Bragg's Law.
4.3.2. Bragg's Law:
Bragg’s Law: nλ=2dsinθ
This law explains why the cleavage faces of crystals reflect X-ray beams at
certain angles of incidence (θ).
Figure4.4. Schematic representation of X-ray beam incident on a Crystallographic material.
40
This law gives the relation between wavelength of electromagnetic radiation to
the diffraction angle and the lattice spacing in sample. These diffracted x-rays are then
detected, processed and counted. By scanning the sample through a range of 2θ
angles, all possible diffraction of the lattice should be attained due to the random
orientation of the polycrystalline material. From XRD we can also get the chemical
composition, major and minor traces of various compounds in sample, name of
chemical formula, crystalline structure.
[a] [b]
Figure4.5. X- Ray Diffractometer Figure4.6. Photograph of the sample

holder
4.4. Scanning Electron Microscope:

Hitachi SEM of Model No S-3400N operated at an accelerating voltage of 20
kV was used to study the surface morphology of materials in this study. The SEM was
with EDAX for elemental analysis and Elemental Mapping for distribution of carbon.
A (SEM) is a type of electron microscope that images a sample by scanning it

with a high-energy beam of electrons in a raster scan pattern. The electrons interact
with the atoms that make up the sample producing signals that contain information
about the sample's surface topography, composition, and other properties such as
electrical conductivity.
41
The types of signals produced by an SEM include secondary electrons, back-scattered
electrons (BSE), characteristic X-rays, light (cathodoluminescence), specimen current
and transmitted electrons. Secondary electron detectors are common in all SEMs, but
it is rare that a single machine would have detectors for all possible signals. The
signals result from interactions of the electron beam with atoms at or near the surface
of the sample. In the most common or standard detection mode, secondary electron
imaging or SEI, the SEM can produce very high-resolution images of a sample
surface, revealing details less than 1 nm in size.
Due to the very narrow electron beam, SEM micrographs have a large depth of
field yielding a characteristic three dimensional appearance useful for understanding
the surface structure of a sample. A wide range of magnifications is possible, from
about 10 times (about equivalent to that of a powerful hand-lens) to more than
500,000 times, about 250 times the magnification limit of the best light microscopes.
Back-scattered electrons (BSE) are beam electrons that are reflected from the sample
by elastic scattering. BSE are often used in analytical SEM along with the spectra
made from the characteristic X-rays.
In a typical SEM, an electron beam is thermionic ally emitted from an

electron gun fitted with a tungsten filament cathode. Tungsten is normally used in
thermionic electron guns because it has the highest melting point and lowest vapour
pressure of all metals, thereby allowing it to be heated for electron emission, and
because of its low cost. Other types of electron emitters include lanthanum hex boride
(LaB6) cathodes, which can be used in a standard tungsten filament SEM if the
vacuum system is upgraded and field emission guns (FEG), which may be of the cold-
cathode type using tungsten single crystal emitters or the thermally assisted Schottky
type,
The electron beam, which typically has an energy ranging from 0.2 KeV to
40 KeV, is focused by one or two condenser lenses to a spot about 0.4 nm to 5 nm in
diameter. The beam passes through pairs of scanning coils or pairs of deflector plates
in the electron column, typically in the final lens, which deflect the beam in the x and
y axes so that it scans in a raster fashion over a rectangular area of the sample surface.
When the primary electron beam interacts with the sample, the electrons lose energy
by repeated random scattering and absorption within a teardrop-shaped volume of the
42
specimen known as the interaction volume, which extends from less than 100 nm to
around 5 μm into the surface. The size of the interaction volume depends on the
electron's landing energy, the atomic number of the specimen and the specimen's
density.
4.5. FIELD EMISSION-SCANNING ELECTRON MICROSCOPE:

Scanning Electron Microscope is mostly widely used electron microscope. It
examines microscopic structure by scanning the surface of the materials. Whether the
size of the particles is in nano range or not can be found easily by using this
technique. Surface morphology of the coated substrates and their cross section images
can be easily studied by using field emission scanning electron microscopy.
Field emission scanning electron microscope is a microscope which uses

electrons for illumination of the sample. SEM produces different signals which
include secondary electrons, back-scattered electrons rays, cathode luminescence
light, and specimen current and transmitted electrons. Secondary electron detectors
are standard equipment in all SEMS. The common mode of detection is when an
electron beam is acted on an atom; secondary electrons are emitted by it. The angle
between the surface and the beam controls the flow of secondary electrons. On a flat
plane, the plume of secondary electrons is mostly contained by the sample, but on a
tilted plane, the plume is partially exposed to rays, and results in emission of more
electrons. By scanning the sample and detecting the secondary electrons, an image
displaying the tilt of the surface is created. A wide range of magnifications is possible,
from about 10 times to > 500,000 times, about 250 times the magnification limit of
the best light microscopes.
Two types of electrons are emitted when an electron beam hits the specimen;
they are back-scattered electrons and secondary electrons. Back scattered electrons
are used to collect the crystallographic information of the specimen and the secondary
electrons are used for studying the morphology. High vacuum of 10 -5-10-3 Torr is
required to operate FE-SEM. Vacuum is necessary to prevent scattering of electrons,
ionization of air particles, contamination of sample, and contamination of the electron
source which can result in increased work function and wastage of energy. So the
43
samples to be analyzed by FE-SEM must be completely dry. Live samples and non-
conductive samples cannot be analyzed by FE-SEM.
Charging of the specimen takes place if a non-conducting specimen is

analyzed and materials like polymers may burn. So these non-conducting samples
must be coated with gold or platinum with a very thin layer to prevent from charging.
Coating is done by using gold sputtering machine not more than 10nm thick to allow
the electrons to interact with the actual specimen.
Figure4.7. Schematic representation of FE-SEM
4.6. ENERGY DISPERSIVE X-RAY SPECTROSCOPY

EDAX is a characterization technique which is used to find the elemental
composition of a sample. If a sample is excited under high energy of electron beam or
any other electromagnetic radiation, the inner shell of electrons is ejected to vacuum
creating a vacancy in that shell. Electrons from the outer shell jump into the vacant
site for filling the inner shell. During this process, the sample fluorescence X-ray of
energy same as the energy difference between the initial state and final state. Since
each atom has its unique and discretized energy levels, the x-Ray fluorescence is also
44
characteristic of that atom. Energy dispersive X ray spectroscopy is a technique that
detects the x-ray fluorescence to characterize the elements present in a material. EDS
systems are relatively faster because the detector collects the signals of characteristic
X-rays energies from a whole range of elements in a specimen at the same time rather
than collecting signals from X-ray wavelength individually.
Figure4.8. Schematic representation of Energy Dispersive X-ray Spectroscopy
EDAX is typically found as an attachment on Scanning Electron Microscope

(SEM) and Transmission Electron Microscope (TEM), where a high energy electron
sources are already present. This technique is limited to elements above atomic
number 4. Analyzing the data should be done carefully, as several atoms have
overlapping peaks at a particular energy. Sometimes, peaks arise due to secondary
fluorescence of the sample holder or from the microscope components. In EDX,
incoming X-ray ejects an inner shell electron, leaving a vacancy which is filled by an
outer shell electron, releasing a photon. Si (Li) is the most commonly used detector in
an EDS system. Si (Li) detectors operating at LN2 temperature are commonly used in
EDX experiments. X-Ray striking the detector produces photoelectrons which in turn
produces electron-hole pairs within the Si. These migrate to opposite ends of the
detectors producing a current pulse whose size is proportional to the energy of the
incident X-Ray.
45
Figure4.9. Schematic Representation of Energy Dispersive X-ray Spectroscopy
4.7. ENERGY DISPERSIVE SPECTROMETER

One of the instruments most commonly used in conjunction with the SEM is
the EDS. The x-ray spectrometer converts an x-ray photon into an electrical pulse
with specific characteristics of amplitude and width. A multi-channel analyzer
measures the pulse and increments a corresponding "energy slot" in a monitor display.
The location of the slot is proportional to the energy of the x-ray photon entering the
detector. The display is a histogram of the x-ray energy received by the detector, with
individual "peaks," the heights of which are proportional to the amount of a particular
element in the specimen being analyzed.
Combining the EDS system with the SEM allows the identification, at microstructural
level, of compositional gradients at grain boundaries, second phases, impurities,
inclusions, and small amounts of material. In the scanning mode, the SEM/EDS unit
can be used to produce maps of element location, concentration, and distribution.
46
Figure4.10.scanning electron microscopy image
4.8. IMAGE ANALYSIS

Microscopic and Field Emission Scanning Electron Microscopy (FESEM) are
done in the image analysis. This analysis helps to find out the tool wear and indents
measurements using microscope. The distribution of grains and the sintering quality is
checked in the FESEM analysis. FESEM also helps to know the particle size and
shape. The metallic binders, secondary and additional secondary carbides and
Titanium Carbonitride images are taken using FESEM.
The optical microscope (Figure 22) is the primary tool for the morphological
characterization of microstructure in science, engineering and medicine. Microscopes
are required for the examination of the microstructure of the metals. Optical
microscopes are used for resolutions down to roughly the wavelength of light (about
half a micron) and electron microscope are used for detail below this level, down to
atomic resolution [37].
With optical microscopy, the light microscope is used to study the microstructure;
optical illumination systems are its basic elements. For materials that are opaque to
visible light (all metals, many ceramics and polymers), only the surface is subject to
observation, and the light microscope must be used in a reflective mode. Contrasts in
the image produced result from differences in reflectivity of the various regions of the
microstructure. Careful and meticulous surface preparations are necessary to reveal
the important details of the microstructure. The specimen surface must first be ground
and polished to a smooth and mirror like finish. This is accomplished by using
47
successively finer abrasive papers and powders. The microstructure is revealed by a
surface treatment using an appropriate chemical reagent in a procedure termed
etching. The etching reagents depend on the material used and after etching the
specimen must be washed with alcohol and ether to remove the grease. The atoms at
the grain boundaries are chemically more active, and consequently dissolve more
readily than those within the grains forming small grooves. These grooves become
discernible when viewed under a microscope because they reflect light at an angle
different from that of the grains themselves. When the microstructure of a two phase
alloy is to be examined, an etchant is chosen that produces a different texture for each
phase so that the different phases may be distinguished from each other [37].
4.8.1. SPECIMEN PREPARATION FOR OPTICAL MICROSCOPY

The examination of materials by optical microscopy is essential in order to
understand the relationship between properties and microstructure. Metallography is
the study of metals by optical examination. This is most commonly done using a
conventional light microscope. However useful information can be gained by
examination with the naked eye of the surface of metal objects or of polished and
etched sections. Structures which are coarse enough to be discernible by the naked
eye is termed macrostructures. Those which require magnification to be visible are
termed microstructures. The images are taken using OLYMPUS GX 51 microscope.
Fig 4.11.optical microscope
48
CHAPTER-V
49
CHAPTER-V
RESULTS AND DISCUSSIONS
5.1. X-RAY DIFFRACTION

The XRD patterns of corresponding ternary and binary alloys with and
without WS2 of Fe-Ni-Ti and Ni-Ti and Al with various percentages of WS2 and Al-
Cu with and without WS2 are shown in the Fig5.1. These XRD’s were obtained from
XRD: BRUCKER D8 setup and the peak identification are done by using ICDD PDF
card. The phases were analysed were verified in JCPDS.
The XRD characterisation of the powders prepared were analysed to find out
the phases present in the compositions.
[a] -1066
50
[b] -1067
[c]- 1068
51
[d]-1069
[e]-1070
52
[f]-1071
Fig5.1.shows the XRD patterns of the Fe-Ni-Ti and Ni-Ti alloys
The XRD patterns of the Fe-Ni-Ti and Ni-Ti samples. The phase analyses and
quantative analyses are done by using XRD-BRUKERS apparatus and by using the
Match software.
Fig5.2. Shows the XRD patterns for the Al-Cu with and without WS2
53
The image shows the XRD patterns of the Al-Cu with and without WS2 of age
hardened samples. Phase analysis is done for the patterns by using Match2 software
and found oxides in the samples. The Al-Cu coarse grained and as well as fine grained
with and without WS2 have showed oxides of Cu oxides, Al oxides and some WC
phase in fine grain powders.
5.2. SIZE DISTRIBUTION
The scherrer equation in X-Ray Diffraction is a formula to find out the particle
size in powder form by using the broadening peak in a diffraction pattern.
The scherrer equation:
𝐾𝜆
𝜏=
𝛽 cos 
Where:
τ = mean size of crystallite
K= shape factor
λ = X-Ray wavelength
β = the line broadening at half the max intensity (FWHM)
 = Bragg’s angle.
By using this equation the size of sub-micrometer particles (or) crystallites can
be analysed.
Fig5.3. Shows the splitting of peaks to estimate the particle size by calculating
the FWHM of the peaks for the ternary Fe-Ni-TI and binary Ni-Ti by using the
scherrer equation. Fig[a]: 1066- Fe4.6%-Ni14.8%- Ti80.6%is the number given to the
sample. And this sample is splitted into 3 main peaks of different phases of Ni and Ti
to analyse the particle size Fig[b]:1067- Fe22.5%-Ni43.5%-Ti34.0% sample is splitted into
2 main peaks of Ni and Ti to analyse the particle size. Fig[c]:1068-Fe18.3%-Ni15.0%-
Ti66.7% sample is splitted into Ni and Ti peaks to calculate the size. Fig[d]:1069-
Fe67.8%-Ni9.4%-Ti22.8%-sample is splitted into one main peak of Fe-Ni to calculate the
size. Fig[e]:1070-Fe50.0%-Ni29.6%-Ti20.4%-sample is splitted into Fe-Ni phase peak to
54
estimate the size. Fig[f]:1071- Ni59%-Ti41%-sample is splitted into Ni and Ti phases to
calculate the size.[16,17]
[a]
[b]
55
[c]
[d]
[e]
56
[f]
Fig5.3. Size distribution of the ternary and binary alloy systems
[a]- 1066-peak-1
[b] ]-1066-peak4
57
[c]- 1067- peak-1
[d]- ]-1067-peak-4
58
[e]- 1070 peak-5
[f]- 1071-peak-2
[g]-1071-peak-3
59
[h]- 1071-peak-5
[i] - 1071-peak-7
Fig5.4. The sample image of estimating the particle size of ternary and binary alloy
60
Fig5.4. shows the particle size of the ternary and binary alloy samples. This
image shows that size of the peak. The software directly shows the size and FWHM
of the peaks. The fig shows the sample peak identification of the 1067 and 1069
ternary sample of Fe-Ni-Ti alloy.
In table5.1 The size of the crystallites and FWHM and breadth are tabulated
for the ternary and binary alloys. The crystallite sizes are in nanometre scale, the
particle sizes varies from the minimum of (7-15)nm range.
Table5.1 The particle size of ternary and binary alloy systems
61
5.3. ENERGY DISPERSIVE SPECTROSCOPY
The powders of ternary and binary systems of Fe-Ni-Ti, Ni-Ti, Al-WS2 and
Al-Cu with and without WS2 and sintered compacts of the same were tested to
analyse the elemental analyses of the alloys and sintered compacts.
Ti-K Fe-K Ni-K W-L

ARCI(523)_pt1 80.63 4.64 12.46 2.27
Fig5.5. 1066-EDS and weight percentage of Fe-Ni-Ti powder
Ti-K Fe-K Ni-K W-L

ARCI(524)_pt1 33.51 22.58 40.58 3.33
Fig5.6. 1067- EDS and weight percentage of Fe-Ni-Ti sample
62
Ti-K Fe-K Ni-K W-L
ARCI(525)_pt1 65.00 16.30 13.31 5.38
Fig5.7. 1068- EDS of Fe-Ni-Ti sample and its weight percentage
Ti-K Fe-K Ni-K W-L

ARCI(526)_pt1 21.31 67.03 8.39 3.28
Fig5.8. 1069-EDS and weightpercentage of Fe-Ni-Ti sample
Ti-K Fe-K Ni-K W-L

ARCI(527)_pt1 20.29 52.44 27.27 0.00
Fig5.9. 1070-EDS of Fe-Ni-Ti sample
63
Ti-K Ni-K W-L
ARCI(528)_pt1 37.55 58.79 3.66
Fig5.10. 1071-EDS and weight percentage of Ni-Ti sample
Images of Fig(5.5-5.10) shows the EDS analyses of the ternary and binary alloys of
Fe-Ni-Ti and Ni-Ti alloy powders which are milled for 20 hours in high energy
ballmilling. Some trace amounts of W formed due to the usage of WC vials for
milling.
O-K Al-K Cu-K
ARCI(1270)_pt1 2.43 92.11 5.46
Fig5.11. EDS and weight percentage of coarse grained Al-Cu
64
O-K Al-K Cu-K
ARCI(1265)_pt1 3.66 90.40 5.94
Fig5.12. EDS and weight percentage of fine grained Al-Cu
O-K Al-K S-K Cu-K W-L

ARCI(1266)_pt1 8.11 79.06 2.65 6.97 3.21
Fig5.13. EDS and weight percentage of coarse grained Al-Cu-5%WS2
65
ARCI(1271)_pt1 8.58 68.92 3.28 4.96 14.27
Fig5.14. EDS and weight percentage of coarse grained Al-Cu-10%WS2
ARCI(1267)_pt1 7.24 78.96 2.14 5.68 5.98
Fig5.15. EDS and weight percentage of fine grained Al-Cu-5%WS2

ARCI(1269)_pt1 7.05 72.51 2.41 5.99 12.05
Fig5.16. EDS and weight percentage of fine grained Al-Cu-10%WS2
The above images show the EDS of Al-Cu fine and coarse grained powders
with and without WS2. The samples are sintered at 600oc. and some oxides have
formed in the samples during sintering of the samples.
66
Al-K W-L
ARCI(1214)_pt1 94.04 5.96
Fig5.17. EDS and weight percentage of Al-5%WS2
Al-K W-L
ARCI(1215)_pt1 89.80 10.20
Fig5.18. EDS and weight of Al-10%W2
67
Al-K W-L
ARCI(1216)_pt1 81.92 18.08
Fig5.19. EDS and weight percentage of Al-Cu-20%WS2
The above images show the EDS of Al with various percentages of WS 2. The samples
are sintered at 6000c. The percentages shown are weight percentages which are nearly
approximate for the original composition.
5.4. SCANNING ELECTRON MICROSCOPY

Scanning electron microscopy is used to take magnified images of the Fe-Ni-
Ti, Al-WS2, and Al-Cu with and without WS2 and Ni-Ti alloys. The powder
distribution can be studied using this SEM and the grain size and the type of powder
prepared can be analysed by using this SEM. The images in this SEM are taken from
the Hitachi SEM of Model No S-3400N machine.
[a] [b]
68
[c]
Fig5.20. SEM images of Al-WS2 (5, 10, and 20%) by weight resp
[a] [b]
[c]
69
[d] [e]
[f]
Fig5.21. SEM images of Al-Cu fine and coarse grained alloys with and without WS2
The SEM images show the distribution of WS2 in the Al and AL-Cu alloy
when sintered at appropriate temperatures. The images show that the fine grained
structure have more distribution than coarse grained. And Al-WS2 image shows that
by increasing the WS2 percentage the distribution of WS2 increases.
5.5. FRICTION TEST

Friction test is carried out on Pin/Ball -On-Disc apparatus. This test is done to
find out the co-efficient of friction of sintered and laser coated samples of Fe-Ni-Ti,
Ni-Ti, Al-4.5%Cu and Al with WS2. The wear behaviour of the samples can be
observed by this test.
70
The equation of COF is:
𝐹
µ=
𝑁
Where:
µ is the co-efficient of friction
F is the friction force
N is the load applied.
[a]: Al-Cu milled [b]: Al-Cu 10% blend
[c]: Al-Cu 5%blend [d]: Al-Cu blended
71
[e]: Al-Cu 5%mill [f]: Al-Cu with 10% mill
Fig5.22. The co-efficient of friction of sintered and aged sample of Al-Cu fine and
coarse grain with and without WS2. [a]: The COF of fine grained structure of AL-Cu;
[b]: The COF of coarse grained structure of Al-Cu-10%WS2; [c]: the COF of coarse
grained structure of Al-Cu-5%WS2; [d]: the COF of coarse grained structure of Al-
Cu; [e]: the COF of fine grained structure of Al-Cu-5%WS2 and [f]: the COF of fine
grained structure of Al-Cu-10%WS2.
The Fig5.22 shows the co-efficient of friction of sintered at 6500cand age

hardened for 24hours at 2000c. Al-Cu-10%WS2 coarse grained structure has the
lowest COF of 0.13. And other alloys have COF of range between (0.3-0.5).
[a]:(Al-5%W [b]:(Al-20%WS2)
Fig5.23. The co-efficient of friction of Al-with WS2
72
Fig shows the coefficient friction of sintered samples of Al- with (5, 10%) by
weight WS2. It shows that with increasing the percentage of WS2 the COF decreases.
For 5%WS2 the COF is 0.3 where as for 20%WS2 it decreased to 0.16.
5.6. OPTICAL ANALYSIS
Optical analysis is done by using the optical microscope. It uses the normal visible
light and magnified lenses to magnify the images of small samples. Optical analysis is
done for the Al-4.5%Cu with and without WS2 samples. By this analysis we can
analyse the distribution of WS2 and the size of the particle and the microstructure of
the alloys.
[a]
[b]
73
(c)
Fig5.24. (a) Al-Cu with 10%WS2 coarse grain (b) Al-Cu with 10%WS2 fine grain
(c) Al-Cu fine grain
The figures 5.24 (a,b,c) shows the microstructures of the Al-Cu alloy cross-
section. Fig (a) shows the crossectional microstructure of the Al-Cu coarse grained
alloy with 10%WS2 in this image the distribution of WS2 was not proper because it is
coarse grained powder. Fig(b) shows the crossectional microstructure of the Al-Cu
fine grained alloy with 10%WS2; this image shows the distribution of WS2 clearly as
it is fine grained structure.
[a] 20%WS2
74
[b] 10%WS2
[c] 5%WS2
Fig5.25. [a] microstructure of Al with 20%WS2 at 40x; Fig: [b] microstructure of Al

with 10%WS2 at 40x and Fig: [c] microstructure of Al with 5%WS2 at 20 x
The Figue5.25.shows the microstructure of the Al-with 5, 10 and 20% weight

percentages of WS2 blended powders sintered at 6000c. The fig[a] shows more
distribution of WS2 than other images this is because of the percentage of WS2. I.e. by
increasing the percentage of WS2 the distribution of WS2 also increasing. The grain
formation is high when the WS2 percentage increases. The optical images are taken
from the optical microscope at 40x and 20x respectively.
75
[a] Al-Cu fine grain [b] Al-Cu with 5%WS2
[c]Al-Cu with 10%WS2
Fig 5.26.[a]- microstructure of Al-Cu fine grained structure at 40x ; [b]-microstructure

of Al-Cu with 5%WS2 at 40x and [c]- microstructure of Al-Cu with 10 %WS2 at 20x.
The Fig5.26. Shows the microstructure of Al-Cu with and without WS2. Fig
[a]: shows the microstructure of Al-Cu fine grain structure of sintered at 6500c. Fig
[b]: shows the microstructure of Al-Cu with 5%WS2 fine grained sintered at 6500c.
Fig [c]: shows the microstructure of the Al-Cu with 10%WS2 fine grained structure
sintered at 6500C.the images are taken from the optical microscope at 40 and 20 x
resolutions. The grain distribution is good when the percentage of WS2 increases. The
formation of grain structure in Al-Cu-WS2 is better when compared with AL-Cu.
5.7. HARDNESS AND TOUGHNESS

Hardness of sintered Al-Cu with and without WS2 is done by using micro and
macro Vickers hardness tester under 500g and 300g load.
76
Hardness of age-hardened Al-Cu with and without WS2 is done by macro
Vickers hardness tester.
Table5.2. Macro-vickers hardness values of sintered Al-4.5%Cu with and

without WS2
Alloy compostion Hardness (Hv) for 500g of load
Al- 4.5%Cu coarse grained 39hv
Al- 4.5%Cu fine grained 41hv
Al-Cu coarse grained with 5%WS2 57hv
Al-Cu coarse grained with 10 %WS2 62hv
Al-Cu fine grained with 5%WS2 54hv
Al-Cu fine grained with 10%WS2 45hv
The table shows the hardness values of sintered samples of Al-4.5%Cu with
and withoutWS2. The samples are compacted with 200 MPa pressure and sintered at
6500C and for 1 hour holding and cooled till 5000c and 1 hour hold. These samples are
taken out and mirror polished to get the hardness values of the sintered samples.
The hardness values of Al-Cu with WS2 have more hardness values than
without WS2. The increase in hardness values is due to the WS2 present in the alloys.
With increase in the percentage of WS2 increases the hardness values.
77
Table5. Macro Vickers hardness values age hardened Al-4.5%Cu with and
without WS2
Alloy composition Hardness (Hv) for 500g Hardness(Hv)for 500g

of load load on 2nd side of the
On1st side of the sample sample
Al- 4.5%Cu coarse grained 24.6hv 23.3hv
Al- 4.5%Cu fine grained 18.6hv 22.9hv
Al-Cu coarse grained with 22.1hv 20.9

5%WS2
Al-Cu coarse grained with 28.9hv 18.7hv

10%WS2
Al-Cu fine grained with 29.6hv 21.1hv

5%WS2
Al-Cu fine grained with 24.7hv 21.4hv

10%WS2
The table shows the hardness values of age hardened Al-Cu with and without WS2.
The sintered samples are age hardened for 24hours at 2000c. The results show that the
hardness values are decreased instead of increasing this is due to the oxides formed in
the samples during sintering.
78
CONCLUSION
1. Synthesis of powders are done at 250rpm for Fe-Ni-Ti and Ni-Ti alloy
powders for 20 hours of milling with 15 minutes of pause for every hour, and
at 150 rpm for Al-Cu and Al-WS2 alloy powders for 10 hours with 15 minutes
of pause for every hour. Powder densities and mass are calculated to find the
mass required to make the green compacts
2. The EDS shows the composition of the alloys, Optical microscope images
show the distribution of WS2.
3. The SEM, Optical images shows that the distribution of WS2 in fine grain
alloy is good than in coarse grain alloy.
4. The COF values Al-Cu with WS2 and Al-WS2 show less COF than without
WS2.
79
References:
[1] P.C. Angelo and R. Subramanian, Powder Metallurgy: Science, Technology

and Applications, ISBN-978-81-203-3281-2
[2] I.H. Dudas and W.A. Dean, Int. Jn of P/M, Vol.5, No. 2, 1969, pp. 21-36
[3] San Andrés. L. "Introduction to pump rotordynamics, Part i. Introduction to

hydrodynamic lubrication". ("MEEN626 Lubrication Theory Class:Syllabus
FALL2006").(11 Dec 2007)
[4] Bosman R. and Schipper D.J. Microscopic Mild Wear in the Boundary
Lubrication regime. Laboratory for Surface Technology and Tribology,
Faculty of Engineering Technology, University of Twente, P.O. Box 217, NL
7500 AE Enschede, The Netherlands.
[5] C. Donneta and A. Erdemir, solid lubricant coatings: recent developments and
future trends, Tribology letters, vol.17, No.3, October 2004.
[6] Campbell, M.E.: solid lubricants – A survey. NASA SP -5059 (01), 1972.
[7] Clauss, F.J.: Solid lubricants and self- lubricating solids. Academic press,
newyork, 1972
[8] M.E 3701, Materilas of Engineering Laboratory, LSU.
[9] R.H.T. Dixon and A. Clayton, Powder Metallurgy for Engineers, Machinery
Publishing Co. Ltd., Sussex, 1971.
[10] Metal Progress, Vol. 100, No. 1, July 1971, pp. 74-75.
[11] Metal Progress, Vol. 98, No. 1, July 1970, pp. 100-102.
[12] Metal Progress, Vol. 101, No. 4, April 1972, pp. 72-75.
[13] I.H. Dudas and W.A. Dean, Int. Jn of P/M, Vol.5, No. 2, 1969, pp. 21-36
[14] Malcom K. Stanford and Christopher Della carte, Glenn Research Center,
Cleveland, ohio, NASA/TM 2004-212972
80
[15] Ghosh, A. and chatterjee, S. (2014) Effect of Al2O3 content and process
variables on structure and properties of Al-Al2O3 compacts. Journal of
minerals and materials characterization and engineering, 2, 121-128
[16] L.I.Durate, U.E.Klotz, C.Leinenbach, M.Palm, F.Stcih, J.F.Loffler,

Experimental study of the Fe-Ni-Ti system. Intermetallics 18 (2010) 374-384
[17] cacciamani G, De Keyzer J, Ferro R, Klotz U.E, Lacazej, Wollants p.

Intermetallics 2006; 14:1312-25
[18] Bing-Yun Li, Li-Jian Rong, Yi-Yi Li, V.E.Gjunter, A recent development in
producing porous Ni-Ti shape memory alloys. Intermetallics 8 (2006) 881-884
[19] Mao-Sheng Yang, Xiu-Bo Liu, Ji-Wei Fan, Xiang-Di Wang, Shu-Fa Chan,
Microstructure and wear behaviour of laser clad NiCr/Cr3C2-WS2 high
temperature self-lubricating waer-resistant composite coating. Applied surface
science 258 (2012) 3757-3762
[20] A Shankara, Pradeep L menezes, KRY Simha and Satish V Kailas, Study of
solid lubrication with MoS2 coating in the presence of additives using
reciprocating ball- on – flat scratch tester. Sadhana vol.33,part 3, june 2008,
pp-220
[21] G. Agarwall, Development of self-lubricating coatings via cold spray process:

Feed stock formulation and deformation modelling. Engineering science
mechanics, august 2007
[22] Jie Yao, Xiaoliang shi, Wenzhengzhai, Ahmed Mohamed Mahmoud Ibrahim,
Zengshixu, Long Chen, Qingshhuai Zhu, Yecheng Xiao, The enhanced
tribological properties of Ni Al intermetallics: Combined lubrication of
multilayer Graphene and WS2. Tribol Lett. DOI 10.1007/5 11249-014-0439-4
[23] Kazuhisa Miyushi and Donald R.Wheeler,Surface chemistry, Friction, and

Wear properties of untreated and Laser-Annealed surfaces of Pulsed- Laser-
Depositted WS2 coatings. Lewis research centre, cleaveland ohio, December
1996
[24] S.M Muzakkir, Experimental investigations on effect of tungsten disulfide

(WS2) on wear performance of commercial lubricant under mixed lubrication
81
conditions. Internal journal of current Engineering and Technology, E-ISSN
2277-4106, P-ISSN2347-5161, Vol.5, No.2 (april 2015)
[25] Willaim A. Brainard, the thermal stability and friction of the disulfides,
diselinides and ditellurides of molybdenum and Tungsten in vacuum (10-9 to
10-6 torr). Lewis research centre, National Aeronautics and Space
Administration, Washington D.C april 1969
[26] N.M. Renevier, J.Hamphire, V.C.Fox, J.Witts, T.Allen, D.G.Teer,

Advantages of using self-lubricating, hard, wear-resistant MoS2- based
coatings. Surface and Coatings Technology 142-144 (2001) 67-77
[27] C.Dellacortw, J.A.Fellenstein and P.A.Benoy (1999), Evaluation of advanced

solid lubricant coatings for foil air bearing operation at 250 0c and 5000c.
Tribology transactions, 42:2, 338-342
[28] R.Holinski and J.Gansheimer, A study of the lubricating mechanism of

molybdenum sulphite. Wear, 19 (1972) 329-342
[29] A.A. Voevodin, J.P. O’neill and J.S. Zabinski, WC/DLC/WS2 nano composite
coatings for aerospace tribology. Tribology letters 6 (1999) 75-78
[30] Chaman Lall and Paul Williamson , Wear resistance and mechanical
properties of selected PM Aluminuim alloys and composites, Metal powder
company, 16855 southpark drive, suite 100, westfield, IN46074,USA
[31] K.Otsuka, X.Ren, Physical metallurgy of Ti-Ni based memory alloys. Progress
in materials science 50 (2005) 511-678
[32] P.Riani, G.Cacciamani, Y.Thebaut, J.Lacaze, Phase equlibria and phase

transformations in the Ti-rich corner of the Fe-Ni-Ti system. Intermetallics 14
(2006) 1226-1230
[33] A.V.Sergueeva, V.V.Stolyarov, R.Z.Valiev,and A.K. Mukherjee, Advanced

mecjanical properties of pure titanium with ultrafine grained structure. Scripta
materialia 45 (2001)747-752
[34] S.Nemat-nasser, W.G.Guo and J.Y.Cheng, Mechanical properties of and

deformation mechanisms of commercially pure titanium. PII: S1359-6454 (99)
00203-7, Acta mater, vol.4.7, no.13, pp. 3705-3720 (1999)
82
[35] ASM Materials Engineering Dictionary, Edited by J.R. Davis & Associates,
ASM International, 1992, p.19
[36] B.Y Li, L.J.Rong, Y.Y. Li, V.E.Gjunter, Synthesis of porous Ni-Ti shape
memory alloys by self-propagating high temperature synthesis: Reaction
meachsnism and anisotropy in pure structure. Acta materialia, volume 48,
issue 15, 2000, 3895-3904
[37] David Brandon and Wayne D. Kaplan, Microstructural Characterization of

Materials, WILEY-VCH Verlag GmbH & Co, ISBN: 978-0-470-02785-1
83

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DEVELOPMENT OF WS2 BASED COATINGS AND

Submitted in partial fulfilment of the

Requirements for the award of the Degree of

Under the esteemed guidance of

External supervisor Internal supervisor

Dr. Joydip Joardar Dr.S.Devaki Rani

Scientist-“E” Assoc. Professor,HOD

ARCI, Balapur Dept. of. Met. Engg.

DEPARTMENT OF METALLURGICAL ENGINEERING

JAWAHRLAL NEHRU TECHNOLOGICAL UNIVERSITY HYDERABAD

COLLEGE OF ENGINEERING HYDERABAD – 500 085

HYDERABAD – 500 085 (AUTONOMOUS)

DEPARTMENT OF METALLURGICAL ENGINEERING

I hereby declare that the work entitled “DEVELOPMENT OF WS2 BASED

JAWAHARLAL NEHRU TECHNOLOGICAL UNIVERSITY

COLLEGE OF ENGINEERING, HYDERABAD-500085

CERTIFICATE BY THE GUIDE

I certify that this is a bonafied record of the dissertation work entitled,

Dr.Joydip Joardar Dr.S.DevakiRani

Scientist – “E” HeadofDepartment

ARCI, Balapur Assoc.Professor,HOD

JNTUH, CEH, Hyderabad-500085

Dr. S. DEVAKI RANI

I am deeply indebted to Principal of JNTUH and Dr. S. Devaki Rani, H.O.D,

I sincerely thank many people who contributed to my work, the most

I sincerely extend my gratitude to Dr.Joydip Joardar for granting me entire

I sincerely thank Dr.R.Vijay, Scientist-‘F’ Team leader, Centre for Nano

1.1. BEARINGS ---1

1.1.1. Air bearings ---1

1.4.1.3. Boundary lubrication ---5

2. LITERATU REREVIEW ---17

3.6. COATINGS ---25

3.8. HARDNESSANDTOUGHNESS ---28

3.9. VICKERSHARDNESSTESTER ---28

3.9.1. Indentation and fracture toughness ---30

4.7. PIN/BALL-0N–DISC ---32

4.8. PULSEDLASERDEPOSITION ---33

Conclusion and future scope ---71

Figure2. Typical image of an Air Foil Bearing

Figure3. AL-Cu phase diagram

Figure4. Flow chart of powder metallurgy

Figure5. Components produced by powder metallurgy

Figure6. Mechanism of high energy ball milling

Figure7. [a]- Planetary milling

[b]- Mechanism inside the milling equipment

Figure8. Schematic diagram for powder compaction

Figure9. Steps of agehardening

Figure10. [a]- As-cast microstructure of Fe-Ni-Ti system

[b]- The enthalpy temperature diagram for the Ni-Ti system

Figure11. Schematic diagram of Vickers hardness tester

Figure12. [a]- Macro Vickers hardness tester

[b]- Schematic diagram for calculating Vickers hardness

Figure13. Pin/Ball – on – Disc Tribometer

Figure14. ND: YAG pulsed laser Deposition equipment

Figure15. Schematic diagram of X-Ray diffraction

Figure16. Schematic diagram of X-Ray Beam incident on a

Figure17. X-Ray Diffractometer

Figure19. Schematic representation of FE-SEM

Figure20. Schematic representation of Energy Dispersive X-Ray

Figure21. Scanning Electron Microscopy

Figure22. Optical Microscope

Figure23. XRD patterns of Ternary and Binary alloy powders