BULK MODIFICATION OF LM 25 ( AL-7.

5 % -SI ALLOY )
WITH TUNGSTEN USING STIR CASTING PROCESS

A PROJECT REPORT
Submitted by

SANTHOSH KRISHNA S (CB.EN.U4MEE14144)

VIGNESH RAMKUMAR (CB.EN.U4MEE14157)
POZHILAN C (CB.EN.U4MEE14511)
SURYA PRAKAASH N (CB.EN.U4MEE14154)

In partial fulfillment for the award of the degree of

BACHELOR OF TECHNOLOGY
IN
MECHANICAL ENGINEERING

AMRITA SCHOOL OF ENGINEERING, COIMBATORE

AMRITA VISHWA VIDYAPEETHAM

COIMBATORE-641112

MAY 2018

AMRITA SCHOOL OF ENGINEERING, COIMBATORE, 641112

AMRITA VISHWA VIDYAPEETHAM

i
 BONAFIDE CERTIFICATE

This is to certify that the thesis entitled “BULK MODIFICATION OF LM25 ( AL-7.5%-SI
ALLOY ) WITH TUNGSTEN USING STIR CASTING PROCESS ” submitted by “
SANTHOSH KRISHNA S (CB.EN.U4MEE14144), VIGNESH RAMKUMAR R
(CB.EN.U4MEE14157), POZHILAN C (CB.EN.U4MEE141511), SURYA
PRAKAASH (CB.EN.U4MEE14157) ” in partial fulfillment of the requirements for the
award of the degree of Bachelor of Technology in Mechanical Engineering is a bonafide
record of the work carried out under my guidance and supervision at Amrita School of
Engineering, Coimbatore.

Dr. R. Saravanan Dr. R. Sellamuthu Dr. S.Thirumalini

Project Advisor Co project Advisor Chairperson
Assistant professor Professor Dept. of Mechanical Engineering
Dept. of Mechanical Dept. of Mechanical
Engineering Engineering

The report was examined and the candidate underwent Viva-Voce examination on

……………….

INTERNAL EXAMINER EXTERNAL EXAMINER

ii
 AMRITA SCHOOL OF ENGINEERING

AMRITA VISHWA VIDYAPEETHAM, COIMBATORE - 641112.

DEPARTMENT OF MECHANICAL ENGINEERING

DECLARATION

We, Santhosh krishna (CB.EN.U4MEE14144), Vignesh ramkumar r

(CB.EN.U4MEE14157), pozhilan c (CB.EN.U4MEE141511), surya prakaash
(CB.EN.U4MEE14154) hereby declare that this thesis entitled “BULK
MODIFICATION OF LM25 ( AL- 7.5% -SI ALLOY ) WITH TUNGSTEN USING
STIR CASTING PROCESS”, is a record of the original work done by me under the
guidance of Dr. R. Saravanan, Assistant Professor, Department of Mechanical
Engineering, Amrita School of Engineering, Coimbatore. To the best of my knowledge,
this work has not formed the basis for the award of any
degree/diploma/associateship/fellowship or a similar award to any candidate in any
University.

Place: Coimbatore Signature of the students

Date:

Santhosh Krishna s vignesh Ramkumar

Pozhilan c Surya prakaash N

COUNTERSIGNED

Dr .R. Saravanan Dr. R. Sellamuthu

Project Advisor Co Project Advisor

Assistant professor Professor

Department of Mechanical Engineering Department of Mechanical Engineering

iii
 ACKNOWLEDGEMENT

The author is grateful to Mata. Amritanandamayi Devi, founder and Chancellor,

Br. Abhayamrita Chaitanya, Pro-chancellor, Dr. P. Venkat Rangan, Vice Chancellor, Dr.

Sasankan Ramanathan, Dean- Engineering and Dr. S. Thirumalini, Chairman, Department

of Mechanical Engineering, Amrita School of Engineering – Coimbatore, for the valuable

support extended by them and for providing the necessary infrastructure.

The author would like to express heart full gratitude to Dr. R. Saravanan, Ph. D.,

Assistant Professor, Department of Mechanical Engineering, who incessantly guided

throughout the project and provide with timely advice and suggestions throughout the

course work.

The author also like to thank the Manufacturing Engineering project review

committee members of the Department of Mechanical Engineering, Dr. Padmanaban R.

Assistant Professor, Dr Illangovan s, Associate professor, , Assistant Professor,

Shanmugasundaram A, Assistant Professor, Sumesh A, Assistant Professor, for the timely

suggestions and directions.

Dr. R. Sellamuthu Ph.D, Professor, Department of Mechanical Engineering, Amrita

School of Engineering, deserves special thanks for the encouragement and advice

throughout the work, and sincere gratitude for his constant support.

The author would like to thank all the faculties, lab assistant and office staffs of the

Department of Mechanical Engineering of our School of Engineering for their help and

support to carry out this work successfully.

May 2017 Krishna kumar M

iv
 ABSTRACT

Stainless steel is mostly used in nuclear power plants, aeronautical industries and
petrochemical industries widely resistance towards corrosion is of prime importance.
Stainless steel materials are mostly subjected to surface alloying for the improvement of
hardness and decrease in wear rate. The surface treated stainless steels are widely used in
gears, surgical instruments, tools, chemical industries, nuclear power plants and in
aeronautical parts. AISI 304 stainless steel has low surface hardness and relatively high
wear rate. AISI 304 stainless steel bar of size 150 × 30 × 30 mm and commercially pure
Titanium sheet (grade 2) of thickness 0.3 mm was chosen as the substrate and the alloying
material. The surface alloying process was carried out using heat generated by a Gas
Tungsten Arc. The surface alloyed AISI 304 stainless steel specimens were heat treated in
a resistance type heat treatment furnace for 6 Hr. Microstructure of the surface alloyed
layer is observed using a metallurgical microscope. The austenitic microstructure of
equiaxied grain structure of Ti surface alloyed layer was revealed during the observation.
Composition of the surface alloyed layer was analyzed using EDAX. The result of the
EDAX analysis confirmed the increase in the Ti content on the surface alloyed layer
compared to the substrate. Further the presence of intermetallic compounds were found
during the EDAX analysis of the Ti surface alloyed layer. Hardness measurements were
carried out using Vickers hardness testing machine. The hardness increased by 718 HV on
the surface alloyed layer compared to the 267 HV hardness of the substrate. The wear rate
of the Ti surface alloyed layer and the substrate were calculated after conducting dry sliding
wear test using a pin-on-disc wear tester. The wear rate of the top surface changed from
8.4×104 mm3/m for the substrate to 3.8×104mm3/m for the Ti surface alloyed layer. The
coefficient of friction is 0.47
The conclusion of this investigation is that the surface alloying process with Ti using
GTA is effective for modifying the surface properties of AISI 304 stainless steel.

v
 LIST OF FIGURES

Figure 1.1 Surface Alloying Process 04

Figure 3.1 GTA equipment 20
Figure 3.2 Machined specimen of AISI 304 Stainless steel
specimen 22
Figure 3.3 Resistance Heat treatment Furnace 24
Figure 3.4 Zeiss metallurgical microscope 25
Figure 3.5 Vicker’s hardness tester 26
Figure 3.6 Wear test specimen 26
Figure 3.7 Pin-On-Disc wear tester 27
Figure 3.8 Zeiss Zigma Field Emission Scanning
Electron Microscope 28
Figure 3.9 PAN analytical X’Pert Pro XRD machine 29
Figure 4.1 Ti surface alloyed AISI 304 Stainless steel specimen 31
Figure 4.2 Heat treated surface alloyed specimens 31
Figure 4.3 Graph between Tip angle(60°) Vs. Width 32
Figure 4.4 Graph between Tip angle(60°) Vs. Depth 33
Figure 4.5 Graph between Tip angle(180°) Vs. Width 33
Figure 4.6 Graph between Tip angle(180°) Vs. Depth 34
Figure 4.7 Penetration comparison graph 35
Figure 4.8 Graph between Tip angle (60°) Vs. Hardness 36
Figure 4.9 Graph between Tip angle(180°) Vs. Hardness 36
Figure 4.10 Microstructure of AISI 304 stainless steel substrate 37
Figure 4.11 Microstructure of heat treated AISI 304 Stainless steel
Substrate 37
Figure 4.12 Microstructure of the Ti surface alloyed AISI 304
stainless steel 38
Figure 4.13 Fusion zone, Heat affected Zone, Substrate of the heat
Treated Ti alloyed surface 38
Figure 4.14 SEM image showing the presence of Ni3Ti 39
Figure 4.15 EDAX Spectrum of heat treated specimen 40
4Figure4.16 EDAX spectrum of Ni-Ti Phase 40

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Figure 4.17 EDAX spectrum of Fe-Ti Phase 41
Figure 4.18 XRD analysis of Ti surface alloyed specimen 41
Figure 4.19 Hardness Vs. Depth from top surface 43
Figure 4.20 Hardness data comparison 44
Figure 4.21 Wear plot of NHT Substrate 45
Figure 4.22 Wear plot of NHT Ti surface alloyed layer 45
Figure 4.23 Wear plot of heat treated substrate 46
Figure 4.24 Wear plot of heat treated Ti surface alloyed layer 46
Figure 4.25 Comparison of wear rate with NHT AISI 304
Specimen with heat treated specimen 47
Figure 4.26 Coefficient of friction of heat treated AISI 304 SS
with Ti 47
Figure 4.27 Coefficient of friction of heat treated AISI 304 SS
Substrate 48
Figure 4.28 Frictional force of heat treated surface alloyed layer 48
Figure 4.29 Frictional force of heat treated substrate 48

vii
 LIST OF TABLES

Table 1.1 Typical Physical Properties of AISI 304 stainless

steel 02
Table 1.2 Typical Physical properties of CP-Ti 03
Table 3.1 GTA Process variables 21
Table 3.2 Composition (wt %) of AISI 304 Stainless steel 22
Table 3.3 Experimental matrix 23
Table 3.4 Wear and Friction testing parameters 27
Table 4.1 GTA Process Variables 30
Table 4.2 Width and Depth of Ti surface alloyed layer 32
Table 4.3 Hardness Values 35
Table 4.4 XRD Pattern list for the Ti surface alloyed layer 42
Table 4.5 Hardness Data 43

LIST OF EQUATIONS
Equation 4.1 Equation of wear calculation 45

viii
 LIST OF SYMBOLS AND ABBREVIATIONS
% Percentage

A Ampere

Al Aluminum

Al203 Alumina

ASTM American Society for Testing and Materials

ADI Austempered Ductile Iron

AISI American Iron and Steel Institution

at.% Atomic Percentage

B4C Boron Carbide

Be Beryllium

C Carbon

cm Centimeter

cm2 Square centimeter

CO2 Carbon dioxide

CoF Coefficient of Friction

Cr Chromium

Cu Copper

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CVD Chemical Vapour Deposition

DCEN Direct Current Electrode Negative

ebeam Electron Beam

EDAX Energy Dispersive X-ray Spectroscopy

EDS Energy Dispersive Spectroscopy

Fe Iron

GTA Gas Tungsten Arc

Hr Hour

HV Vickers Hardness

l Arc length

ltr Liter

LVDT Linear Variable Differential Transformer

m Meter

mA milli Ampere

Mg Magnesium

min Minutes
mm millimetre

Mn Manganese

x
meV/s milli electron Volt per second

N Newton

Nb Niobium

Nd:YAG Neodymium:Yttrium-Aluminium-Garnet

Ni Nickel

P Phosphorous

Pa Pascal

PLC Programmable Logic Control

PVD Physical Vapour Deposition

Rc Rockwell hardness

rpm Revolutions per minute

s Seconds

SAL Surface alloyed Layer

SEM Scanning Electron Microscopy

Si Silicon

SiC Silicon Carbide

SMP Surface Modification Process

Sn Tin

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SRP Surface Refining Process

SS Stainless steel

Ti Titanium

TiC Titanium Carbide

T6 Tempered grade

U Travel speed

WC Tungsten Carbide

wt.% Weight percentage

Zn Zinc

α Alpha phase

β Beta phase

γ Gamma phase

δ Delta phase
µm micrometr

xii
 TABLE OF CONTENTS

ACKNOWLEDGEMENT iv

ABSTRACT v

LIST OF FIGURES vi

LIST OF TABLES vii

LIST OF EQUATIONS vii

LIST OF SYMBOLS AND ABBREVIATIONS ix

1. INTRODUCTION 01

1.1 Background 01
1.2 Types of Stainless Steels 01
1.3 AISI 304 Stainless Steel 02
1.4 Commercially pure Titanium (CP-Ti) 02
1.5 Surface modification process 03
1.5.1 Surface alloying process 03
1.6 Types of Heat Sources 05
1.7 Heat treatment 07
1.7.1 Annealing 07
1.7.1.1 Normalizing 08
1.7.1.2 Stress Reliving 08
1.8 Present Work 08
1.9 Objectives 08
1.10 Organization of the report 09
1.11 Summary 09

2. LITERATURE REVIEW 10
2.1 Literature regarding Surface Alloying Process 10

3. EXPERIMENTAL PROCEDURE 19
3.1 Introduction 19
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3.2 Experimental Setup 19
3.3 General Procedure 19
3.3.1. Specimen Preparation 19
3.3.2. Surface Alloying Process 20
3.3.3. Process Parameters Used 21
3.4 Experiments 22
3.5 Testing Methods 23
3.5.1 Heat Treatment 24
3.5.2 Microstructural Examination 24
3.5.3 Hardness testing 25
3.5.4 Wear testing 26
3.5.5 SEM/ EDAX analysis 28
3.5.6. XRD analysis 28
3.6 Summary 29

4. Results And Discussions 30

4.1 Introduction 30
4.2 Results 31
4.2.1 Effect of process variables on hardness of the Surface Alloyed
Layer 31
4.2.2. Comparison of depth (Penetration) 34
4.2.3. Effect of process variables on hardness 35
4.2.4 Microstructure Analysis 37
4.2.5 Phase formation 39
4.2.5.1 SEM Imaging 39
4.2.5.2 EDAX analysis 39
4.2.5.3 XRD analysis 41
4.2.6 Hardness 42
4.2.7 Compression of Hardness data 43
4.2.8 Wear rate 44
4.3 Summary 49

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5. Conclusion and Scope for Future work 50
5.1 Conclusion based on effect of heat treatment on Ti surface alloyed on
the hardness and the wear rate of AISI 304 SS 50
5.2 Scope for Future Work 51

Reference 52

xv
 CHAPTER 1
INTRODUCTION

1.1 Background
Stainless Steel are mainly used in places where high surface hardness and high wear
rate has been key obstacles to extensive application. SS have been extensively utilized in
aeronautical, aerospace, food processing, nuclear and biomedical and maritime industry
because of its high corrosion resistance. The SS inherently possesses good corrosion
resistance, because, in the atmosphere, chromium in its structure combines with oxygen of
the air to form a thin passive coating of chrome oxide on the surface of the SS. However,
in case the SS is brought into contact with a corrosive fluid, such as hydrogen sulfide,
chlorine ion and a hot water containing oxygen, pitting corrosion or cracks due to corrosion
are liable to occur in the surface of the SS. Typical products of SS that are subjected to
surface treatment processes are surgical instruments, control rod cases in nuclear power
plants, tools and moulds, gears, screws, valves, pump parts, bearings, filters, orthopedic
parts.
Traditionally, coatings are applied onto the surface of the parent material in order
to obtain the desired properties. For the coating purpose, various traditional methods like
electroplating, electro-less plating, Physical Vapour Deposition (PVD), Chemical Vapour
Deposition (CVD) and thermal spraying were commonly used. However, the coatings
obtained by these methods are likely to delaminate under severe loading conditions. In
order to overcome such difficulties, researchers have adopted a new method called Surface
Modification Process (SMP).

1.2 Types of Stainless steel

SS are defined as iron base alloys which contain at least 10.5% chromium. The thin
but dense chromium oxide film which forms on the surface of a SS provides corrosion
resistance and prevents further oxidation. There are five types of SS depending on the other
alloying additions present, and they range from fully austenitic to fully ferritic. Austenitic
SS include the 200 and 300 series of which type 304 is the most common. The primary
alloying additions are chromium and nickel. Ferritic SS are non-hardenable Fe-Cr alloys.
Types 405, 409, 430,422 and 446 are representative of this group. Martensitic SS are
similar in composition to the ferritic group but contain higher carbon and lower chromium
xvi
to permit hardening by heat treatment. Types 403, 410, 416 and 420 are representative of
this group. Duplex SS are supplied with a microstructure of approximately equal amounts
of ferrite and austenite. They contain roughly 24% chromium and 5% nickel. Their
numbering system is not included in the 200, 300 or 400 groups. Precipitation hardening
SS contain alloying additions such as aluminum which allow them to be hardened by a
solution and aging heat treatment. They are further classified into sub groups as martensitic,
semi-austenitic, and austenitic precipitation hardening SS. They are identified as the 600-
series of SS.

1.3 AISI 304 Stainless steel

SS types 1.4301 are also known as AISI 304. AISI 304 is the most versatile and
widely used SS. It is still sometimes referred to by its old name 18/8 which is derived from
the nominal composition of AISI 304 being 18% chromium and 8% nickel. AISI 304 SS
has excellent corrosion resistance in a wide variety of environments and when in contact
with different corrosive media. AISI 304 SS has good resistance to oxidation. AISI 304 SS
cannot be hardened by heat treatment. Table 1.1 shows the typical physical properties of
AISI 304 SS. AISI 304 SS is typically used for manufacture of tubes, brewery equipment,
pharmaceutical production equipment, springs, nuts, bolts, screws and medical implants.

Table 1.1 Typical Physical Properties of AISI 304 SS

Sl.No Property Value
1 Density 8.00 g/cm3
2 Melting Point 1400-1450°C
3 Modulus of Elasticity 193 GPa
4 Tensile strength 520(MPa)
5 Compression Strength 210 (MPa)
6 Hardness Vickers( HV) 220

1.4 Commercially pure Titanium (CP-Ti)

Titanium is recognized for its high strength-to-weight ratio. It is a strong metal with
low density that is quite ductile, lustrous, and metallic-white in color. The relatively high
melting point makes it useful as a refractory metal. It is paramagnetic and has fairly low
electrical and thermal conductivity. Commercial (99.2% purity) grades of titanium have
xvii
ultimate tensile strength of about 434 MPa, equal to that of common, low-grade steel alloys,
but are less dense. Titanium is 60% denser than aluminium. The titanium used for surface
alloying of AISI 304 SS was CP-Ti, grade2, 200µm thick sheet. The typical physical
properties of CP-Ti are shown in Table 1.2.

Table 1.2 Typical Physical properties of CP-Ti

Sl.No Property Value
1 Density 4.50 g/cm3
2 Melting Point 1600-1670°C
3 Modulus of Elasticity 116 GPa
4 Tensile strength 434(MPa)
5 Compression Strength 182 (MPa)
6 Hardness Vickers( HV) 210

1.5 Surface modification process

Surface modification process (SMP) is emerging as a method alternate to the
traditional coating processes in order to enhance the tribological and corrosion properties
of nonferrous and ferrous alloys. SMP can be defined as the process of modifying the
surface of a material by bringing out changes in the properties different from those found
originally on the surface of a material. The principal aim of the application of surface
modification technique is to form hard and ultra-fine structure on the surface layer so that
the properties are improved. SMP can be classified into two categories: namely, i) Surface
Refining Process (SRP) and ii) Surface Alloying Process (SAP).

1.5.1 Surface alloying process

In the method of surface alloying, first alloying elements or ceramic particulates
are placed in the form of coatings, sheets, powder or paste onto the surface of the base
metal (substrate). Following it, using a chosen heat source, both the element or particulates
and the base metal are melted to create a fusion zone. The heat source is then, progressively
moved along the length of the base metal so as to form a unified fusion layer on the surface
of the base metal upon solidification. Figure 1.1 illustrates the surface alloying process
with a coating of the alloying element on the surface of the substrate. In this process, an
alloy different from the substrate may form. Further, there is a possibility of forming
xviii
intermetallic compound in the modified layer due to the addition of various types of
alloying elements onto the surface. Also, due to the rapid cooling experienced during the
solidification stage, the surface of the base metal (substrate) is refined into fine structure
throughout the surface. The formation of the intermetallic compounds and the refinement
of the surface are the main reasons for the improved properties of the modified layer. The
surface alloying process differentiates itself from the conventional coating techniques with
the alloyed modified layer remaining integral to the base metal. Hence, researchers
envisage that such surface alloyed metals can withstand higher loads in the service
compared to those coated by the conventional techniques. The alloyed surface is also
expected to have a high wear resistance.

Figure 1.1 Surface Alloying Process

There are three main approaches have been practiced for carrying out the surface alloying
process. With the first approach, the conventional coating techniques such as electro-
plating or electro-less plating have been employed to coat the base metal with the alloying
element. The element fuses onto the surface of the base metal during the progress of the
process. Another approach followed for alloying the base metal is to powder the alloying
element and mix it with appropriate binders. The formed paste is then laid on the base
metal, followed by the melting and fusing with the base metal using a heat source. The last

xix
method involves feeding the alloying element or ceramic particulates (powdered form) into
the molten pool by employing a powder feeder apparatus.
In SAP, a fine grain structure of the modified layer can be achieved upon
solidification due to fast cooling of the molten layer. The improvement in surface
properties is achieved as a result of the formation of a fine grain structure. Various alloying
elements like Ni, Cr, Ti, Mo etc., can be added to the molten pool so that a new alloy with
desired properties can be formed upon solidification. Further, due to the rapid cooling
and/or alloy addition, hard intermetallic compounds may also form in this process.
Additionally, highly refractive ceramic particulates like TiC, B4C, SiC etc., can also be
added to the molten pool in order to form a metal matrix composite. As a result, the
modified layer exhibits a high hardness due to the presence of the ceramic particles. The
modified layer can also act as a thermal barrier in some instances and hence it may find
applications where the component is used in a high temperature environment. The
geometry of the modified layer and the concentration of the alloying element in the
modified layer are the critical factors that decide the surface properties like wear resistance,
corrosion resistance as well as the surface hardness. The molten pool geometry and the
alloying element concentration depend upon the coating method and the heat source used.

1.6 Types of Heat Sources

In the literature, it has been reported that the electron beam and laser beam heat
sources have been selected for this application. The Gas Tungsten Arc (GTA) heat source
has been considered by a few researchers.
The process of laser surface melting involves the use of an energy-intensive laser
heat source to melt the surface of the base metal. The popular heat source is a continuous
wave CO2 or a Nd: YAG laser beam. The shielding gas preferred is the noble Argon gas.
The laser heat source shows a variation in intensity because of the reflectivity of the base
metal surface and therefore, it is difficult to achieve a uniform modified layer. The
efficiency of the laser is around 16%. Due to the high intensity of the laser beam, it is likely
that the alloying element may vaporize. The width of the modified layer is not high and
therefore, it requires a several passes to completely cover a given surface. As a result, the
productivity of the laser beam process is very low.
In the electron beam, process a power density of 100 kW/cm2 is used. Due to the
high intensity of the e-beam, it is likely that the alloying element may vaporize. The
xx
limitations associated with the e-beam process are the high cost of the equipment, the
requirement of a high vacuum environment that restricts the size of the component, low
productivity and low efficiency. Further, the depth of the modified layer is very low that
limits the service life of the components. Finally, the e-beam process is considered to be
not cost effective for the surface allo ying process.

Plasma arc (PA) is an arc welding process similar to GTA. The electric arc is
formed between an electrode and the work piece. The key difference from GTA is that in
PA, by positioning the electrode within the body of the torch, the plasma arc can be
separated from the shielding gas envelope. The plasma is then forced through a fine-bore
copper nozzle which constricts the arc and the plasma exits the orifice at high velocities
and a temperature approaching 28,000 °C or higher. Just as oxy-fuel torches can be used
for either welding or cutting, so too can plasma torches, which can achieve plasma arc
or plasma cutting. The gas gets ionized after passage of electric current through it and it
becomes a conductor of electricity. In ionized state, atoms break into electrons (−) and
cations (+) and the system contains a mixture of ions, electrons and highly excited atoms.
Such states exist as more electrons are pulled from their orbits. The energy of the plasma
jet and thus the temperature is dependent upon the electrical power employed to create arc
plasma..

In view of the limitations of the e-beam and laser beam heat sources, the GTA has
been considered as an alternate heat source for the surface refining/alloying processes. The
GTA heat source is characterized with its high thermal efficiency (75%), high productivity,
inexpensive equipment cost and ease of operation. Also, the width and depth of the
modified layer are high when compared to those of e-beam/laser beam process. Further,
the GTA process variables can be easily controlled so that the desired width and depth of
the modified layer can be achieved. Finally, large components can be easily processed with
the GTA heat source.
1.7 Heat Treatment
Engineering properties are modified by heat treatment processes so that structural
components are able withstand specified operating conditions and have desired useful life.
Heat treatment is the heating and cooling of metals to change their physical and mechanical
properties, without letting it change its shape. Heat treatment could be said to be a method
for strengthening materials but could also be used to alter some mechanical properties such
as improving formability, machining, etc. The most common application is metallurgical
xxi
but heat treatment can also be used in manufacture of glass, aluminum, steel and many
more materials. The process of heat treatment involves the use of heating or cooling,
usually to extreme temperatures to achieve the wanted result. It is very important
manufacturing processes that can not only help manufacturing process but can also
improve product, its performance, and its characteristics in many ways

1.7.1 Annealing

. Annealing consists of heating a metal to a specific temperature and then cooling

at a rate that will produce a refined microstructure, either partially or fully annealed. The
rate of cooling is generally slow. Annealing is most often used to soften a metal to improve
machinability, and to enhance properties.

In ferrous alloys, annealing is usually accomplished by heating the metal beyond

the upper critical temperature and then cooling very slowly, resulting in the formation of
pearlite. In both pure metals and many alloys that cannot be heat treated. The metal is
heated to a temperature where recrystallization can occur, thereby repairing the defects
caused by plastic deformation. In these metals, the rate of cooling will usually have little
effect. These may be slowly cooled to allow full precipitation of the constituents and
produce a refined microstructure.

Ferrous alloys are usually "full annealed". Full annealing requires very slow
cooling rates, in order to form coarse pearlite. The main goal of process annealing is to
produce a uniform microstructure. Non-ferrous alloys are often subjected to a variety of
annealing techniques, including "recrystallization annealing," "partial annealing," "full
annealing," and "final annealing." Not all annealing techniques involve recrystallization,
such as stress relieving

1.7.1.1 Normalizing

The uniform grain size and the composition of the alloy can be
achieved using normalizing technique. The term is often used for ferrous
alloys. Normalizing not only produces pearlite, but also martensite and sometimes bainite,
which gives harder and stronger steel, but with less ductility for the same composition than
full annealing

xxii
1.7.1.2 Stress Reliving
To remove or reduce the internal stresses created in a metal Stress
relieving technique is used. These stresses may be caused in a number of ways, non-
uniform cooling to ranging from cold working. Stress relieving is usually accomplished by
heating a metal below the lower critical temperature and then cooling uniformly

1.8 Present Work

Most of the research works cited in the literature were conducted to investigate the
effect of alloying using laser or e-beam, ion implantation, plasma nitrating and carburizing.
However, an investigation on the surface alloying of the AISI 304 SS with Ti by using the
GTA as the heat source has not been reported in the literature. SS is a widely used
engineering alloy in liquid-handling systems and hydraulic machinery because of its good
corrosion resistance, good processibility, and relatively low cost. Since AISI 304 SS has a
low hardness and a low wear resistance, present investigation is undertaken to improve
these properties by the surface alloying process and to understand the changes to the
corrosion behavior post surface alloying process.
In the present study, the effects of Ti addition as a surface alloying element on
microstructure, hardness, and wear rate of heat treated AISI 304 SS were investigated. In
addition, the formation of intermetallic phases between Ni and Ti, and their impact on the
surface properties of the modified AISI 304 SS is investigated in this study.

1.9 Objectives

The objectives of the present research work are as follows:

1. To form a Ti SAL on the surface of the AISI 304 SS substrate by using the surface
alloying process.
2. To observe the microstructure of heat treated AISI 304 SS and changes to it due to
surface alloying with Ti.
3. To determine the formation of any intermediate phase between Ni and Ti in the
alloyed layer due to the addition of Ti in heat treated specimens.
4. To assess the effect of Ti addition to the surface of the AISI 304 SS substrate on
the hardness, the wear rate of the heat treated Ti surface alloyed AISI 304 SS.
5. To assess the advantages of using GTA as the heat source for the surface
modification process when compared to the laser/e-beam source.
xxiii
1.10 Organization of the report

Chapter 1 is an overview of the thesis comprising of an introduction to surface

modification processes and classifications, various coating techniques used and the heat
sources available surface modification and their comparison. The justification for carrying
out the present study is highlighted. The objectives of the present study are presented.
Chapter 2 is the literature survey of the previous research works. The literature
survey includes surface modification process, types of heat sources used and various
alloying elements added on to the surface. Further, the results of the previous studies are
also discussed.
Chapter 3 describes the experimental setup and the procedures for the surface
refining and surface alloying processes. It further reports on microstructural examination,
hardness measurement, wear testing method, EDAX and XRD analysis of the chemical
composition.
Chapter 4 reports the results and discussion of the effect of surface alloying
Titanium on the Hardness and the Wear Rate of AISI 304 SS.
Chapter 5 describes conclusions of this study and the detailed suggestions for future
work that may be attempted, and is followed by References section.

1.11 Summary

This chapter introduces the surface refining process and surface alloying process
the relevance of surface alloying AISI 304 SS in order to improve the surface properties,
namely hardness, wear resistance of the alloy. Additionally, the justification for carrying
out the present study, objectives and organization of the thesis are presented.

xxiv
 CHAPTER 2
LITERATURE REVIEW

2.1 Literature regarding Surface Alloying Process

Akao. T. et al. (2014) by using diverse technologies fatigue strength and wear
resistance has improved by surface modification of cold-working die steels. Widely
utilized machine tools have a hard layer on the surface of the tool due to the formation of
CrN, TiN, TiCN, etc. on the surfaces. Therefore, in this study, investigate the irradiation
of electron beam on the formation of cemented carbide composite layer. First, the influence
of electron beam irradiation on the SKD11 surface was studied. Microstructural
observations and phase analysis shows there is no precipitation and small dendritic
structures with austenitic phase are found, the hardness is improved from 200 to 430 HV.
This hardening is most likely to be due to grain refinement and solution hardening of
carbon and chromium atoms into the austenitic phase, Further, a composite layer of WC-
Co matrix was formed through solidification after the irradiation-induced melting. The
composite layer shows a marble-like texture with WC-rich regions. The hardness of the
layer reaches up to 1000 HV, however, it is revealed that there exists highly
inhomogeneous distribution of WC particles on the irradiated surface.

Anandan. S. et al. (2012) this study is about the

detailed investigation of laser surface alloying of WC + Ni + NiCr on AISI 304 SS and the
characteristics and properties of the alloyed zone. Continuous wave (CW) of 5kW,
Nd:YAG laser with the output power ranging from 1 to 3 kW and scan speed from 0.005
m/s to 0.1 m/s Argon gas flow rate of 5 L/min was used for laser surface alloying. The
effect of laser power and scan speed on the characteristics of the SAL and property have
been investigated in details. Development of fine grained SS with the dispersion of WC,
W2C, M6C and M23C6 was achieved by using Laser surface alloying. The hardness of the
laser surface alloyed zone was found to be 1350 HV whereas the hardness of the substrate
was found to be 200 HV. The optimum parameters for laser processing were derived.

Çelik. O. N. et al. (2011) used TIG method for surface modification process to
improve the surface properties of AISI 8620 steel. Constant energy input of 135A and the
xxv
0.5 g of constant SiC particle were addition and variable C content. Optical microscopy
and SEM were used to illustrate the microstructure of the materials tested. The hardness
distribution test was performed. Under dry friction conditions wear tests were performed
with WC balls at a 5 N load in a ball-on-disk geometry. The results of this study indicated
that the surface properties of the material could be modified with the TIG method and by
using SiC/C particles and that the newly formed structure could improve the wear
characteristics and the hardness of the surface.

Chen. H. T. et al. (2014) induced martensite transformation by plasma

nitrocarburizing in AISI 304 austenitic SS is investigated. The optical micrographs and
XRD results indicate the dual-layer structure of the nitrocarburized layer: the outer
martensite transformation layer and the inner C supersaturated austenite layer. The initial
transformation microstructure presents as nanoscale qusai-pealite which is composed of
a0-martensite and NaCl-type MX (M ¼ Cr, Mn, Fe, Ni; X ¼ C, N) phase. The martensite
transformation layer possesses high hardness and good ductility.

Enver Atik et al (2002) has reported on the effects of conventional heat treatment
and boronizing on SAE 1010 and SAE 1040 structural steels, D2 tool steel, and 304 SS
were investigated. During this investigation, layer thicknesses, corrosion and wear strength
were examined by applying carburization, nitriding, transformation hardening and
boronizing to the specimens. Abrasive wear tests were carried out in a wear cup model
device. Sand of 1 mm diameter was used and the test duration was 40 hours with a velocity
0.157 m/s. Corrosion tests were undertaken in a 10% H2SO4 solution at a temperature of
56°C. Through metallographic analyses, hard layer thicknesses and Vickers hardness
values were determined for each hardening treatment

Hao. S et al. (2016) carried out High current pulsed electron beam (HCPEB)
treatment on 40CrNiMo7 steel with accelerating voltage 27 kV, energy density 3 J/cm 2,
pulse duration 2.5 ls and 1–50 pulses. The evolutions of surface microstructure were
investigated by using optical microscopy (OM), X-ray diffraction (XRD), scanning
electron microscope (SEM) and transmission electron microscopy (TEM) techniques. It
was found that the carbides in the surface remelted layer of depth 4 lm were dissolved
gradually along with the increasing number of HCPEB pulses. Eventually, the surface

xxvi
microstructure of 40CrNiMo7 steel was transformed to a complex structure composed of
very refined 150 nm austenite as the main part and a little quantity of martensite phases.
After 15 pulses of HCPEB treatment, the surface microhardness was doubled to 553 HV,
and the wear rate decreased to one third of the initial state correspondingly.

Hao. S. et al. (2015) conducted High current pulsed electron beam (HCPEB)
surface treatment on FV520B steel with accelerating voltage 27 kV, pulse duration 2.5 ls,
energy density 5 J/cm2 and 1–25 pulses. The surface microstructure and element
distribution were examined by using scanning electron microscope (SEM), electron probe
micro-analysis (EPMA) and X-ray diffraction (XRD) methods. After HCPEB treatments,
the surface microstructure became refined and uniform with an average grain size less than
2 lm and a preferential solidification orientation in h200i direction. The thickness of surface
remelted layer was 4 lm. The initial precipitated particles in surface layer of depth 10 lm
were dissolved into the base matrix and gave a homogenous element distribution. The
HCPEB modified surface exhibited an effective improvement in corrosion and wear
resistance. The corrosion potential shifted towards positive and the corrosion rate
decreased nearly one order of magnitude, while the wear resistance after 25 pulses of
HCPEB treatment increased by 3 times as compared with the initial FV520B steel.

Hojjatzadeh. S. M. H. et al. (2012) investigated the effects of varying the addition

of nitrogen to the shielding gas during GTA (gas tungsten arc) surface alloying of an AISI
1045 steel substrate with a preplaced layer of ferrotitanium (FeTi) powder. The penetration
and cross-sectional area of the alloyed layers increased with the nitrogen content in the
shielding gas. Different nitrogen contents in the shielding gas also caused the formation of
two main microstructures: (1) TiN dendrites distributed in a ferrite (Fe3C) matrix at a high
nitrogen content and (2) Ti(CxNy) in a matrix of ferrite and eutectic structure of ferrite and
Fe2Ti at a low nitrogen content. Specimen melted under pure argon (0 vol% N2) was
comprised of TiC in a matrix of ferrite and eutectic structure of ferrite and Fe2Ti. The latter
also showed the highest hardness, which could be attributed to the presence of the fine
eutectic structure and low dilution of the layer.

Jiang. P. et al. (2000) Laser surface alloying with gaseous nitrogen was utilized to
improve the wear resistance of a Ti6Al4V alloy. Wear-resistant composite coatings
reinforced by hard TiN dendrites were produced ‘in-situ’ on a substrate of a Ti6Al4V
xxvii
alloy. The hardness and wear resistance of the laser alloyed coating under two-body
abrasive and block-on-ring full-sliding wear conditions were significantly enhanced.

Karthik. D. et al. (2015) examined the influence of laser peening without

protective coating (LPwC) process on surface mechanical properties of recipitation
hardened SS 17-4 PH. Pulse densities, 2500 and 6250 pulses/cm2, using a constant laser

power density of 5.97 GW/cm2 were chosen and their effect on residual stresses, micro-
structure, micro-hardness, surface roughness and topography were investigated. Higher
pulse density induced large compressive residual stresses and influenced up to depth of
600 μm. It was confirmed from resulted larger lattice strain in LPwC processed 17-4 PH
steel with higher pulse density. No phase transformation and microstructural change were
observed, which represented pure mechanical effect of
LPwC. Hardness was increased with depth of hardened layer up to 600 μm for higher pulse
density. However, the surface roughness was increased by the process, and resulted in more
pronounced peening pattern. Surface topography revealed columnar structure after LPwC
process.

Liang. W. (2003) carried out plasma nitriding of austenitic SS samples using pulse
dc glow discharge plasma of NH3 gas at substrate temperature ranging from 350 to 520
8C. A nitriding time of only 4 h has been found to produce a compact surface nitride layer
composed of gN0 phase with a thickness of around 7–12 mm as processing temperature
remained between 420 and 450 8C. The thickness of gN phase was found to be very thin
only about 2 mm after plasma nitriding at temperature below 400 8C.Microhardness
measurements showed significant increase in the hardness from 240 HV (for untreated
samples) up to 1700 HV (for nitrided samples at temperature of 460 8C). For nitriding at
higher temperature, i.e. above 460 8C, the chromium nitrides precipitated in the nitrided
layer and caused austenite phase transform into ferrite phase or iron nitrides (g0 or e). The
consequent result of chromium nitride precipitation is the reduction of corrosion resistance
of nitrided layer. Compressive residual stresses existed in the nitrided layer due to nitrogen
diffusion into austenitic SS.

xxviii
 Majumdar J. D. et al. (2006) carried out a study concerning the development of a
hard in situ boride-dispersed composite layer on the surface of AISI 304 SS substrate to
improve the wear resistance property. Laser processing was carried out by melting the
surface of sand-blasted AISI 304SS substrate using a continuous wave CO2 laser and
simultaneous deposition of a mixture of K2TiF6 (potassium titanium hexafluoride) and
KBF6 (potassium hexafloroborate) (in the weight ratio of 2:1) using Ar as shrouding
environment. Powder feed rate was maintained constant at 4 g/min. Irradiation results in
dissociation of a pre-deposited mixture along with a part of the SS substrate, intermixing
and rapid solidification to form the composite layer on the surface. The micro-structure of
composite layer consists of dispersion of titanium boride particles in AISI 304 SS matrix.
Volume fraction of particles is found to be uniform throughout the composite layer, though
varied with laser parameters. The micro-hardness of the surface was improved 250–350
VHN as compared to 220 VHN of the AISI 304 SS substrate with a significant
improvement in wear resistance property. The mechanism of wear was found to be a
combination of adhesive and abrasive in as-received SS. However, it was predominantly
abrasive for laser composite surfaced SS.

Rotshtein. V. P. et al. (2006) investigated the surface morphology, chemical

composition, microstructure, nanohardness, and tribological properties of a film (Cu)–
substrate (SS 316) system subjected to pulsed melting with a low-energy (20– 30 keV),
high-current electron beam (2–3 μs, 2.8–8.4 J/cm2). The film was deposited by sputtering
a Cu target in the Ar plasma of a microwave discharge. To prevent the local delamination
of the film due to the cratering, the substrates were repeatedly pre-irradiated with 8–10
J/cm2. Single pulsed melting of this system resulted in the formation of a diffusion layer
of thickness 120–170 nm near the interface, irrespective of the energy density. The layer
has the subgrain structure consisting of the γ-Fe-solid solution and submicrometer or
nanocrystalline Cu particles. The nanohardness and the wear resistance of the surface layer
of thickness 0.5–1 μm, including the molten film and the diffusion layer, non-
monotonically vary with energy density, reaching a maximum in the range of 4.3–6.3
J/cm2. As the pulse number is increased to five in the same range of energy density, the
film dissolves in the substrate, and a 0.2-μm-thick surface layer is formed which contains
20 at.% Cu. Under these conditions, the segregation of Cu during resolidification leads to
the formation of two-phase nanocrystalline layers separating γ-phase grains.

xxix
 Samih. Y. et al. (2014) subjected the surface of the AISI 420 martensitic SS to
High Current Pulsed Electron Beam (HCPEB) treatment. The microstructure in the melted
layer consisted of a three phase mixture: (i) fine δ-Fe grains formed via epitaxial growth
from the substrate, (ii) larger γ–grains nucleated from the top surface of the melt and (iii)
some needles-like variants issued from the solid state martensitic transformation. Despite
this complex multiphase microstructure, the corrosion performance, tested in a sulfuric
acid solution, was significantly enhanced by the HCPEB treatment. The increase in
corrosion potential and delayed pitting are essentially attributed to an increase in Cr
content, rising from 13.3 wt. % in the bulk to about 14 wt. % at the surface, together with
a very limited amount of surface craters. This low density of craters did not give rise to
significant deep hardening in the subsurface but the top surface melted layer hardness was
increased by more than 50% because of the triggering of the martensitic transformation.

Sun. G. F. et al. (2014) fabricated alloyed layers on 304 SS blades with Cr– CrB2
powders by laser surface alloying. Microstructure evolution, element and phase
distribution, microhardness and corrosion performance of the alloyed layers were
investigated. Corrosion potentials of all alloyed layers are higher than that of 304 SS. Most
of the alloyed layers have lower corrosion current densities than 304 SS does. All alloyed
layers fabricated at laser power 2.5 kW show improved corrosion resistance and
significantly improved microhardness and wear resistance. Improvement of the above-
mentioned properties is attributed to the unique mechanical properties of various
microstructures and chemical composition in the laser treated layers.

Vijay Narayanan et al. (2016) SS are mainly used where prevention of corrosion
attack is the main criteria, but low surface hardness and high wear rate are key obstacles to
extensive application. The surface alloying of AISI 304 SS with titanium was carried out
using the heat generated from the Gas Tungsten Arc (GTA). Experiments were conducted
by varying the GTA parameters and the optimal parameter was determined. Composition
of the SAL was analyzed using atomic emission spectrometer. The Ti alloyed surface
layers were characterized using SEM imaging/EDAX analysis. Composition of the SAL
was analyzed using atomic emission spectrometer and the results confirmed an increase in
the Ti content on the surface layer when compared to the composition of the substrate. The

xxx
EDAX analysis showed that intermetallic alloys are present in the Ti alloyed surface layers.
The hardness was measured using the Vickers microhardness testing machine and the
hardness increased from 267.5 HV for the substrate to 2098 HV for the SAL. The wear
was measured using the pin-on-disk wear tester and the wear rate decreased from 14.78 x
10-4 mm3/m for the substrate to 1.84 x 10-4 mm3/m for the SAL. The observation of the
microstructure revealed that there is grain refinement in the Ti alloyed surface layer. The
modified specimens can be used as medical implants, control rods in nuclear power plants,
pump barrels petrochemical industry. This method can be used to improve the properties
in specific area of a product.

Yılmaz. S. O. (2006) coated AISI 1018 low-alloy steel by using FeCr, FeCrC and
WC–FeCrC alloy powders and the gas tungsten arc processing (GTA) method. The friction
and the wear behavior of the coated surfaces were tested under dry sliding conditions
against WC–Co slider. The dry sliding wear tests were performed on a pin on disc machine,
and the influence of sliding speed on wear rate was determined. The test results indicate
that the wear resistance of AISI-1018 steel can be improved by means of GTA surface
alloying, and high chromium ferrochromium powders can be used for high speed
applications to reinforce the surface of low carbon steel with a WC particulate mixture.

Ying. L. X. et al. (2007) obtained modified coatings including carbide of iron,

nickel, chromium, silicon, and titanium on 9Cr18 SS surface by laser alloying. The
processing method, the microstructure, the interface, the tribological properties, and the
forming mechanisms of the coatings are analyzed. The results show that the microstructure
of the alloyed coatings is mainly irregular FeC crystals. Carbides of chromium and iron are
around the FeC crystals. Small granular TiC disperses in the alloyed coatings, The
microhardness of the alloyed coatings is greatly improved because of the occurrence of
carbide with high hardness. At the same time, the wear resistance of the alloyed coatings
are higher than that of 9Cr18 SS.

xxxi
 CHAPTER 3
EXPERIMENTAL PROCEDURE

3.1 Introduction
This chapter discusses the materials and methods used in this research. The
chapter presents details on the experimental work carried out including the experimental
set up, experimental matrices and various testing methods used for the present
investigation. The experimental setup and procedures are explained as follows.

3.2 Experimental Setup

The equipment’s used in the present study are;
i) Lincoln Electric V205T Gas Tungsten Arc equipment as the heat source for
Surface Alloying Process at DCEN mode.
ii) Linear manipulator driven by a servo motor with a PLC controller
incorporated in GTA equipment for the substrate movement.
iii) Zeiss Metallurgical Microscope for microstructural examination.
iv) Mitutoyo micro- hardness tester for hardness measurement.
v) DUCOM pin-on-disc wear testing machine with LVDT sensors and data
acquisition software for wear and friction tests.
vi) Zeiss Zigma Field Emission Scanning Electron Microscope for
SEM/EDAX (Energy Dispersive X-ray Spectrometry).
vii) PAN analytical X’Pert Pro X-ray Diffraction Machine.

3.3 General Procedure

3.3.1 Specimen Preparation

The AISI 304 SS substrate is machined into the dimension of 30x30x100 mm and
the surface is polished using emery paper. The surface is then cleaned with acetone to
remove dirt, grease, oil etc. CP-Ti sheet of 200 µm thick is cut into 30x100 mm rectangular
sheets and cleaned with acetone.

xxxii
3.3.2 Surface Alloying Process
The machined specimen (Substrate) was mounted on the working table. On top of
the substrate, the cut CP-Ti sheets were placed. The GTA torch was held stationary for all
the set of experiments. The specimen mounted on the working table was set to move with
a specified speed as per the requirement using the linear manipulator. Thoriated (2.2%)
Tungsten electrode of diameter 2.4 mm was used. The specimen was placed such that the
electrode lies above the specimen at its one end. A ceramic cup holds the electrode and the
height of the electrode can be adjusted using the rubber stopper. Argon gas of ultra-high
purity was used as the shielding gas with a flow rate of 12 L/min. The GTA torch moves
across on the top surface of the specimen melting the CP-Ti and top surface of the substrate
thereby causing surface alloying process to occur. The GTA equipment is shown in Figure
3.1.

Figure 3.1 GTA equipment

33
3.3.3 Process Parameters Used
The GTA equipment consists of an inverter/control unit in which the output current
can be varied from 10 A to 200 A. With the help of the linear manipulator driven by a servo
motor, the working table can be moved with a specified speed varying from 1 mm/s to 10
mm/s. The electrode angle can be varied from 15° to 180° by using an electrode grinder.
The arc length can be varied manually by using the fixtures provided in the GTA
equipment. The procedure starts by switching on the power, and then the substrate was
moved with the specified speed. The surface of the substrate was melted by the arc
generated from the GTA heat source to form a molten pool and subsequently the substrate
was moved progressively along its length so that a SAL is formed on the surface upon
solidification. The same procedure can be repeated by varying the GTA process variables.
The surface alloyed specimen is kept in the resistance heat treatment furnace for 6 Hr at a
temperature of 870° C. The SAL so formed was cut, polished and etched using the usual
metallographic techniques and property evaluation was carried out. The width and the
depth of the modified layer formed after SAP was measured.

The GTA process variables used in the present study are reported in Table 3.1.

Table 3.1 GTA Process variables

Sl.No Process Variable Value

1 Current [A] 200

2 Travel Speed [mm/s] 1,2

3 Arc Length [mm] 3,4

4 Electrode Tip Angle[degree] 60,180

5 Electrode Diameter [mm] 2.4(constant)

6 Argon Flow Rate [L/min] 12(constant)

The process variables had to be optimized to obtain the most effective parameter
for the surface alloying process of AISI 304 SS with CP-Ti. In this regard several
experiments were conducted with different parameter setting.

34
3.4 Experiments
Surface Alloying Process was carried out on the AISI 304 SS with CP-Ti by varying
the GTA process variables. Heat treatment process was carried out after the surface
alloying process. The optimal process parameter was identified and further specimens are
prepared using it. Microstructural examination, hardness measurement and wear behavior
of the substrate and the surface alloyed specimens were studied.

AISI 304 SS specimens were procured in wrought form. The chemical composition
of the alloy specimens were analyzed using arc spectrometry. The chemical composition
was found to be within the range of ±0.2wt% of the nominal composition. The chemical
composition of the alloy used is reported in Table 3.2.

Table 3.2 Composition (wt %) of AISI 304 SS

Element Cr Ni Cu Mn Mo Fe
Wt. % 18.5 8.2 0.4 1.8 0.5 Bal

The AISI 304 SS specimens were machined into square bars of dimension 150 x
30 x 30 mm. The machined AISI 304 SS substrate is shown in Figure 3.2.

Figure 3.2 Machined specimen of AISI 304 SS specimen

Surface Alloying Process was carried out on the AISI 304 SS substrate with CP-Ti
using GTA heat source. The experiments were repeated with varying GTA process
variables. The optimal parameter was identified based on the hardness obtained in each
process parameter set used. The various process parameters for experimental matrix are

35
shown in Table 3.3. A 2.2% thoriated tungsten electrode was used for the surface alloying
process. The fixed parameters are electrode diameter – 2.4 mm, argon flow rate – 12 L/min
Table 3.3 Experimental matrix

Set Set Set Set Set Set Set Set Property

Sl.No Parameters
1 2 3 4 5 6 7 8 studied

1 Current(Amps) 200 200 200 200 200 200 200 200

CP-Ti sheet
2 Yes Yes Yes Yes Yes Yes Yes Yes
placed

Electrode Tip
3 60 60 60 60 180 180 180 180
Angle(deg) Hardness

Welding
4 1 2 1 2 1 2 1 2
speed(mm/sec)

Stand-off
5 3 3 4 4 3 3 4 4
distance(mm)

The heat treated surface alloyed specimens were cut using wire cutting method
to prepare specimens for microstructural observation, SEM imaging, EDAX and XRD
analysis.

The heat treated specimens are analyzed using EDAX analysis is to identify the
composition of the heat treated SAL. XRD analysis is performed to identify the
compounds present in the heat treated SAL.

3.5 Testing Methods

Microstructural examination, hardness and wear testing, SEM/EDAX analysis
and XRD analysis were carried out for the heat treated substrate and the heat treated
surface modified specimens. The testing procedures are explained as follows

36
3.5.1 Heat Treatment
Heat treatment involves the use of heating or chilling, normally to extreme
temperatures, to achieve a desired result such as hardening or softening of a material. It is
noteworthy that while the term heat treatment applies only to processes where the heating
and cooling are done for the specific purpose of altering properties intentionally, heating
and cooling often occur incidentally during other manufacturing processes such as hot
forming or welding. The substrate and the surface alloyed specimens were kept in a
resistance heat treatment furnace with an actual dimension of 150 x 30 x 30 mm at 870°C
for 6 Hr in argon atmosphere. The resistance heat treatment furnace is shown in the figure
3.3

Figure 3.3 Resistance heat treatment furnace

3.5.2 Microstructural Examination
Microstructure of heat treated substrate and refined specimens were examined
using an optical metallurgical microscope (Make: Zeiss; Model: 25CA) as shown in Figure
3.4. The specimens were prepared using standard metallographic techniques and etched
with waterless Kaling’s reagent. The optical metallurgical microscope which is capable of

37
reproducing the microscopic images at a magnification factor ranging from 100X to 500X
was used. The images were captured and recorded using a CCD camera with an image
processing software (Motic Images plus 2.0).

Figure 3.4 Zeiss metallurgical microscope

3.5.3 Hardness testing

To evaluate the effect of Surface Modification Process, the hardness of the heat
treated substrate and the modified alloy specimens were measured using hardness tester
(Make: Mitutoyo; Model: MVK – H11). Several readings were taken at the top surface and
different locations along the depth of the modified layer for each specimen and an average
value was calculated. The specimens were prepared and tested as per ASTM E384
standard. The parameters used in this test were: 100 gm-f applied load for a duration of 15
s. The hardness values varied in each sample was within ±10 HV. The
Vicker’s hardness tester is shown in Figure 3.5.

38
 Figure 3.5 Vickers hardness Tester

3.5.4 Wear testing

The wear and friction tests were performed on the heat treated substrate and the
surface alloyed specimens. The experiments were carried out using Pin-on-Disc wear tester
equipped with LVDT sensors attendant with data acquisition software was used (Make:
Ducom; Model: TR-20LE) under dry sliding condition in air. The test specimens were
made in the form of pin of 5 mm diameter and 40 mm length as shown in Figure 3.6.

Figure 3.6 Wear test specimen

39
The counter face disc material was DLC disk with a hardness of 5000 HV and surface
roughness of Ra 0.15 μm. The data acquisition system provides three kinds of plots:
(a) Height loss versus time (b) Coefficient of friction versus time and (c) Frictional force
versus time. ASTM G99 standard test method was used to conduct the test. The
experimental setup is shown in the Figure 3.7.

Figure 3.7 Pin-On-Disc wear tester

The wear rate was measured from the volume loss per unit sliding distance. It is
3
expressed in mm /m. Volume loss was calculated using the plot, height loss versus time.
The test parameters used for the wear and friction tests are shown in Table 3.4.

Table 3.4 Wear and Friction testing parameters

Sl.No Test Unit Value

1 Rotational Speed Rpm 424
2 Velocity m/s 2.5
3 Track diameter Mm 110
4 Sliding Time S 600
5 Sliding distance M 1500
6 Load applied N 20

40
3.5.5 SEM/ EDAX analysis
The phase identification was carried out using Zeiss Zigma Field Emission
Scanning Electron Microscope and the Ti and Ni concentration was measured using the
EDAX technique. The EDAX technique was also used to identify the composition of the
corrosion compounds present. The Zeiss Zigma Field Emission Scanning Electron
Microscope is shown in Figure 3.8.

Figure 3.8 Zeiss Zigma Field Emission Scanning Electron Microscope

3.5.6. XRD analysis

The intermetallic compound formations in the SAL, corrosion compounds in the

corroded areas of the substrate and the SAL were confirmed using XRD analysis. The XRD
equipment used for the testing purpose is PAN analytical X’Pert Pro shown in Figure 3.9.

41
 Figure 3.9 PAN analytical X’Pert Pro XRD machine

3.6 Summary

The following experimental details and methods were explained in this chapter:

1. Sample preparation for Surface Alloying Process were elaborated.

2. The detailed experimental procedure were explained.

3. The characterization evaluation techniques like microscopic examination, hardness

test, wear test, SEM/ EDAX analysis and XRD analysis process was expounded.

42
 CHAPTER 4
RESULTS AND DISCUSSIONS

4.1 Introduction
This chapter discusses an investigation on the effect of heat treatment and the
surface alloying process on hardness of the surface alloyed AISI 304 SS since a study using
GTA as the heat source and heat treatment in the modified layer has not been reported
previously. The substrate was machined to the required size of 150 x 30 x 30 mm. CP-Ti
sheets of 300µm thickness is used as the source for the Ti addition. Surface alloying process
was carried out on the substrate using GTA heat source to melt the substrate surface and
the CP-Ti sheet so as to form a SAL on solidification. The process variables used namely
current, speed, and arc length is reported in Table – 4.1. Outside this range of the process
variables, it was not possible to obtain a well-defined alloyed layer. The alloyed specimen
was kept in the resistance heat treatment furnace for heat treatment. Arc spectrometry was
used to measure the composition of the surface alloyed layer. The heat treated surface
alloyed specimens were prepared for microstructural observation using the conventional
metallurgical techniques. Hardness measurements were carried out on the cross section of
the SAL. Further, SEM imaging and EDAX analysis were carried to study the phase
formations on the SAL. To confirm the compounds formed during the surface alloying
process of AISI 304 SS with Ti, XRD analysis was carried out.

Table 4.1 GTA Process Variables

Sl.No Process Variable Value

1 Current [A] 200

2 Travel Speed [mm/s] 1,2

3 Arc Length [mm] 3,4

4 Electrode Tip Angle[degree] 60,180

5 Electrode Diameter [mm] 2.4(constant)

6 Argon Flow Rate [L/min] 12(constant)

43
4.2 Results
4.2.1 Effect of process variables on hardness of the SAL
The surface alloyed AISI 304 SS specimen with the SAL formed on the top surface
of the substrate after Surface alloying with 300 µm thick CP-Ti sheet is shown in Figure
4.1. The heat treated surface alloyed is shown in figure 4.2. The width and the depth
achieved for various experiments conditions are tabulated in Table 4.2.

Figure 4.1 Ti surface alloyed AISI 304 SS specimen

Figure 4.2 Heat treated SAL specimen

44
 Table 4.2. Width and Depth of Ti SAL
Travel Arc
Amp Tip Angle Width Depth
Sl.No Speed Length
(A) (deg) (mm) (mm)
(mm/s) (mm)
1 200 1 3 60 7.8 4.6
2 200 2 3 60 8.1 6.1

3 200 1 4 60 9.3 6.8

4 200 2 4 60 9.9 7.1
5 200 1 3 180 8.0 6.6
6 200 2 3 180 8.8 6.4
7 200 1 4 180 9.6 6.9
8 200 2 4 180 11 7.2

It can be observed from Table 4.2 that the width and the depth were the highest
when a current of 200A, travel speed of 2 mm/s, arc length of 4 mm and electrode tip angle
of 180° was used. Figure 4.3 shows the graph between tip angle of 60° vs. width
Figure 4.4 shows the graph between tip angle of 60° vs. Depth similarly Figure 4.5 and 4.6
shows the graph between tip angle of 180° vs. Width and depth

Figure 4.3 Graph between Tip angle (60°) vs. Width

45
 Figure 4.4 Graph between tip angle (60°) vs. Depth

Figure 4.5 Graph between Tip angle (180°) vs. Width

46
 Figure 4.6 Graph between tip angle (180°) vs. Depth

4.2.2. Comparison of depth (Penetration)

Anandan et al. (2012) have reported the depth of penetration was 0.96 mm for the
laser surface alloying of AISI 304 SS with WC+Ni+NiCr. Sun et al. (2014) have reported
the depth of penetration was 0.5 mm for the laser surface alloying of AISI 304 SS with Cr-
CrB2. Majumdar & Manna (1999) have reported the depth of penetration was 1.25 mm for
the laser surface alloying of AISI 304 SS with Mo. Buyotz & Ulutan (2006) have reported
the depth of penetration was 2.8 mm for the TIG surface alloying of AISI 304 SS with SiC.
Based on the above observations, it was concluded the depth is higher in the GTA process
than that was observed in the laser process and in Ebeam process. In the present study, a
penetration of upto 7.2 mm for surface alloying AISI 304 SS with Ti using GTA as heat
source. Figure 4.7 shows the penetration comparison graph between these previous studies
and the current study. Therefore, the GTA heat source can be considered as an alternate
heat source to laser for the surface alloying of AISI 304 SS.

47
 Figure 4.7 Penetration comparison along depth direction

4.2.3 Effect of process variables on hardness

The surface hardness values for various experimental conditions are reported in
Table 4.3. As can be seen from the table, the hardness variation is not significant for various
experimental conditions.

Table 4.3 Hardness Values

Travel Standoff Tip
Amps Hardness
Sl.No Speed distance Angle
(A) (HV)
(mm/s) (mm) (deg)
1 200 1 3 60 708
2 200 2 3 60 705
3 200 1 4 60 712
4 200 2 4 60 713
5 200 1 3 180 709
6 200 2 3 180 718
7 200 1 4 180 711
8 200 2 4 180 720

48
 Therefore, it is concluded that, the process variables have no significant impact on
the surface hardness. Buytoz & Ulutan (2006) has previously reported that the GTA
parameters have little influence on the hardness. Based on this observation, the result of
our study is consistent with that of the previous study. The figure 4.8 and figure 4.9 shows
the hardness observed due to the variation in tip angle

Figure 4.8 Graph between tip angle 60° vs. hardness

Figure 4.9 Graph between tip angle (180°) vs Hardness

49
4.2.4 Microstructure Analysis
Figure 4.10 shows microstructure of AISI 304 SS substrate. The austenitic
microstructure with equiaxed grains and the characteristics annealing twins of the AISI 304
stainless substrate before surface alloying can be seen in the Figure 4.10.

Figure 4.10 Microstructure of AISI 304 SS substrate

Figure 4.11 shows the microstructure of the heat treated AISI 304 SS substrate.

Figure 4.11 Microstructure of the heat treated AISI 304 SS substrate

It is inferred that the microstructure is highly refined due to sudden cooling

occurring in the surface alloying process with GTA as heat source. The dendritic structure
of the grains is also observed. The equiaxed grain structure evolves into a dendritic
structure post surface alloying process. Due to the heat treatment process the equiaxed
grain structure has dissolved without any precipitate formation. The presence of equiaxied
grains has agreed with results reported by Anandan et al. (2012), Sun et al. (2014) and
50
Majumdar & Manna (1999) in case of laser surface alloying and Buytoz & Ulutan (2006)
in case of surface alloying using GTA as heat source. Therefore it can be concluded that
the findings are consistent with the existing literature.
The presence of Ti in the form of precipitate on the surface of the heat treated in
the modified layer is shown in the figure 4.12. The Fusion zone, heat affected zone and the
substrate of the heat treated Ti SAL is shown in the figure 4.13

Figure 4.12 Microstructure of Ti SAL of AISI 304SS

Figure 4.13 Fusion zone, Heat Affected Zone and substrate of the heat treated Ti alloyed
Surface

51
4.2.5 Phase formation

The formation of an intermetallic phase in the SAL was identified and confirmed
using SEM imaging, EDAX and XRD analysis.

4.2.5.1 SEM imaging

Figure 4.14 shows the presence of the intermetallic phase in the heat treated SAL
during SEM imaging. As per the Ni-Ti phase diagram, Ni3Ti, NiTi, NiTi2 are intermetallic
phases that may be formed when Ni and Ti are alloyed together. EDAX analysis
strengthened the argument of the presence of Ni3Ti phase. The intermetallic phase Ni3Ti
was observed as lumps in the AISI 304 SS matrix. This phase is an extremely hard
intermetallic compound usually in the order of 650750 HV, which is one of the reasons
behind the drastic increase in hardness of the AISI 304 SS substrate.

Figure 4.14 SEM image showing the presence of Ni3Ti

4.2.5.2 EDAX analysis

The Ti and Ni concentration on the surface of the alloyed layer formed in the
surface alloying process was measured using the EDAX analysis. The EDAX spectrum
taken on the top surface of the heat treated substrate and the surface alloyed with Ti is
shown in Figure 4.15, Figure 4.16 and Figure 4.17. From Figure 4.16, and Figure 4.17 it is
inferred that the intermetallic phase formed is between NiTi and FeTi. The atomic
percentage observed in the EDAX results affirms this observation. Figure 4.15 shows
the elemental analysis of the heat treated substrate.

52
Figure 4.15 EDAX spectrum of heat treated substrate

Figure 4.16 EDAX spectrum for NiTi phase

53
 Figure 4.17 EDAX spectrum for FeTi phase

4.2.5.3 XRD analysis

To confirm the presence of Ni3Ti, XRD analysis was performed on the Ti surface
alloyed specimen. The Figure 4.18 shows the XRD pattern for the Ti surface alloyed
specimen.

Figure 4.18 XRD pattern for Ti surface alloyed specimen

54
 Table 4.4 shows the pattern list obtained from the XRD analysis for the Ti SAL.

Table 4.4 XRD Pattern list for the Ti SAL

Visible
Sl. Compound
Chemical Score
No name
Formula

1 Ni 60 Nickel

Nickel
2 Ni3Ti 4
Titanium

The peaks represent the Ni-Ti compound Ni3Ti which was previously identified
using the atomic percentage of Ni and Ti as observed from the EDAX results. This
therefore confirms the presence of Ni3Ti.

4.2.6 Hardness
Figure 4.19 shows the hardness profile of the measurements made in the Ti SAL in
which the hardness decreases from the top surface to the bottom of the SAL. The variation
shown in Figure 4.20 can only be attributed to the cooling rate difference between the top
and the bottom of the SAL and lower penetration of Ti to the lower regions of the SAL.
Anandan et al. (2012) Majumdar & Manna (1999) in case of laser surface alloying and
EnverAtik et al (2002) in case of surface alloying using GTA as heat source have all
reported similar variation in hardness along the depth direction from the top surface to the
bottom layer of the SAL.

55
 Figure 4.19 Hardness vs Depth from Top Surface

4.2.7. Comparison of hardness data

The hardness values measured on the top surface of the SAL formed in this study along
with the data of previous studies of Anandan et al. (2012), Sun et al. (2014), Majumdar & Manna
(1999) in case of laser surface alloying, and Enver Atik et.al (2002) in case of GTA surface
alloying are reported in Table 4.5. All the researches compared were conducted using AISI 304
SS as the substrate.

Table 4.5 Hardness Data

Alloying
Hardness Hardness element
(Surface
Substrate (Substrate) Alloyed) Author
(HV) (HV)
AISI 304 WC+Ni+NiCr
SS 220 1350 Anandan et al.

AISI 304 Molybdenum

SS 220 700 Majumdar & Manna

AISI 304 Boron

SS 267 478 Enver Atik et.al

AISI 304 Titanium

SS 267 718 This Study
56
The data reported in Table 4.5 is illustrated in the form of the bar chart in Figure 4.20.

Figure 4.20 Hardness Data Comparison

Figure 4.20 shows the comparison of hardness values of the substrate with the modified
layer of this study with that of the previously reported works. Anandan et al. have studied with
addition of WC+Ni+NiCr (1320 HV), similarly Dutta Majumdar and Manna have studied with
the addition of Molybdenum (700 HV) without heat treatment, Enver Atlik et al. have studied with
the addition of Boron with heat treatment that reduces the hardness (478 HV). In this study, the
addition of Ti in the SA layer contributes for the improvement in the hardness in SA layer. The
addition of Ti to the substrate have formed a new alloy in the SA layer. The alloy formed in the
SA layer may be a heat treatable alloy
Though the hardness value changes were observed from non-heat treated substrate to heat
treated substrate, a layer was grained to 1.5 mm and the experiment for hardness were conducted
and found to have the hardness of non-heat treated substrate

4.2.8 Wear rate

Figure 4.21 shows wear plot for the NHT AISI 304 SS substrate. Figure 4.22 shows the
wear plot for the NHT Ti surface alloyed AISI 304 SS. It is observed that the wear rate decreases
drastically for the Ti SAL when compared to the AISI 304 SS substrate. Figure 4.23 shows the
wear plot for the HT AISI 304 SS substrate. Figure 4.24 shows the wear plot for HT Ti SA AISI
304 SS

57
 The wear rate of the AISI 304 SS specimen and Ti SAL surfaces were calculated as per
Equation 1.

IA
Wear rate  (mm3 / m) (Equation 1)
N

Where I  slope of graph (mm / s)

A  area of worn surface (mm2) N 
rotational speed (m / s)

Figure 4.21 Wear plot NHT substrate

Figure 4.22Wear plot for NHT modified layer

58
Figure 4.23 Wear plot for heat treated substrate

Figure 4.24 Wear plot for heat treated Ti SAL

The wear rate calculated for the heat treated AISI 304 SS was 8.4 x 10-4 mm3/m, while that

for the heat treated Ti SAL was 3.4 x 10-4 mm3/m. This huge improvement in wear resistance is

attributed to the formation of the hard intermetallic compound Ni3Ti along with the high grain

refinement occurring due to the rapid solidification associated with surface alloying process. The
wear rate was compared with the non-heat treated AISI 304 SS surface alloyed with Ti done by
Vijay Naraynanan et.al (2017) and the comparison graph is shown in the Figure 4.25

59
 Figure 4.25 Comparison of Wear rate with Non heat treated AISI 304 Specimens with heat
treatment AISI 304 Specimens

The Figure 4.26 shows the coefficient of friction which is almost constant of throughout
the time for the heat treated AISI 304 SS alloyed with Ti. The Figure 4.27 shows the coefficient
of friction for the heat treated AISI 304 SS substrate. The frictional force for the modified layer is
almost constant when compared with the heat treated substrate Figure 4.28 shows the frictional
force for the modified layer. The Figure 4.29 shows the frictional force for the heat treated
substrate.

Figure 4.26 Coefficient of Friction of Heat treated AISI 304 SS with Ti

60
Figure 4.27 Coefficient of friction of Heat treated AISI 304 SS substrate

Figure 4.28 Frictional force of Heat treated modified layer

Figure 4.29 Frictional force of heat treated Substrate

61
 From figure 4.26 and figure 4.27 it is observed that the coefficient of friction increased
from 0.46 to 0.6 this is due to the variation of alloy from substrate and the SAL. Due to the
formation of new alloy in the SAL frictional force increases marginally. This shows the formation
of intermetallic compound in the modified layer

4.3 Summary
Based on the results of this investigation, the following summaries were drawn:

1. The surface alloying process of AISI 304 SS with Ti refines the microstructure due to fast
cooling occurring in the process.
2. The hardness value is found to increase from 267 HV for the substrate to 2098 HV for the
Ti SAL.
3. The increase in hardness is attributed to the formation of a very hard intermetallic
compound Ni3Ti and the grain refinement occurring due to the rapid solidification
associated with surface alloying process.
4. The hardness shows a gradient in the depth direction within the Ti SAL due to the
difference in the cooling rate.
5. It is observed that, the process variables have no significant impact on the surface hardness
while it affects the width and depth of the SAL.
6. It is observed that the wear rate decreases from 14.78 x 10-4 mm3/m for the AISI 304 SS
substrate to 1.84 x 10-4 mm3/m for the Ti SAL.
7. The GTA heat source can be considered as an alternate heat source to laser/e-beam for the
surface alloying of AISI 304 SS.

62
 CHAPTER 5

CONCLUSIONS AND SCOPE FOR FUTURE WORK

The following conclusions are drawn based on the results obtained after Surface Alloying
Process of AISI 304 SS with Titanium.

5.1 Conclusion based on effect of heat treatment on Ti surface alloying on the Hardness and
the Wear Rate of AISI 304 SS

1. The surface alloying process of AISI 304 SS with Ti refines the microstructure due to fast
cooling occurring in the process.
2. The hardness value is found to increase o the heat treated AISI 304 SS from 267 HV for
the substrate to 718 HV for the Ti SAL.
3. The increase in hardness is attributed to the formation of a very hard intermetallic
compound Ni3Ti and the grain refinement occurring due to the rapid solidification
associated with surface alloying process.
4. The hardness shows a gradient in the depth direction within the heat treated Ti SAL due to
the difference in the cooling rate.
5. It is observed that, the process variables have no significant impact on the surface hardness
while it affects the width and depth of the SAL.
6. It is observed that the wear rate decreases from 8.4 x 10-4 mm3/m for the AISI 304 SS
substrate to 3.4 x 10-4 mm3/m for the Ti SAL.
7. The GTA heat source can be considered as an alternate heat source to laser/e-beam for the
surface alloying of AISI 304 SS.

63
5.2 Scope for future work

1. Corrosion studies at elevated temperature and different solution medium can be carried out
on the Ti Surface Alloyed AISI 304 SS specimen.
2. The effect of oxidation on the hardness and wear rate of Ti surface alloyed AISI 304 SS
can be carried out.
3. The Wear behavior of the surface alloyed specimens can be studied by changing the wear
testing parameters including temperature.

64
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