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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL i

"CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL"
METALLURGICAL & MATERIALS ENGINEERING DEPARTMENT FACULTY OF
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Research · May 2018

DOI: 10.13140/RG.2.2.16634.24000

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

A Project on

“CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL”

Is submitted to

The Maharaja Sayajirao University of Baroda

In partial fulfilment for the award of degree of

BACHELOR OF ENGINEERING

In

METALLURGICAL & MATERIALS ENGINEERING

Submitted by

BHAVESH R. RANA ( Exam No.: 809011 )

DARSH A. BODHANA ( Exam No.: 809024 )
VRUJAL P. RAJ ( Exam No.: 809032 )

Dr. BHARATI R. REHANI Dr. VANDANA J. RAO Dr. NIRAV I. JAMNAPARA

Associate Professor Associate Professor Scientific officer – F
Metallurgical & Materials Metallurgical & Materials FCIPT – IPR
Engg.Dept Engg.Dept (Institute for Plasma Research),
The M.S. University of Baroda, The M.S. University of Baroda, Gandhinagar
Vadodara Vadodara

METALLURGICAL & MATERIALS ENGINEERING DEPARTMENT

FACULTY OF TECHNOLOGY AND ENGINEERING
THE MAHARAJA SAYAJIRAO UNIVERSITY OF BARODA
VADODARA-390001
YEAR 2017-2018

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

CERTIFICATE

This is to certify that a Project on “CHARACTERIZATION OF GAS

NITRIDED 304L STAINLESS STEEL” is prepared by BHAVESH R. RANA

( Exam No.: 809011 ), DARSH A. BODHANA ( Exam No.: 809024 ), VRUJAL P. RAJ
( Exam No.: 809032 ) in the partial fulfillment of the requirement for the award of the
degree of “Bachelor of Engineering” in Metallurgy & Materials Engineering of The
Maharaja Sayajirao University of Baroda, Vadodara.

This is a record of their work carried out under our supervision and guidance. The matter
embodied in the thesis, to the best of our knowledge, has not been submitted for the award
of any other degree or diploma of any institute or university.

__________________________ ______________________
Dr. BHARATI R. REHANI Dr. VANDANA J. RAO
Associate Professor, Associate Professor
Metallurgical & Materials Engg.Dept. Metallurgical & Materials Engg.Dept
Faculty of Tech.& Engg. Faculty of Tech. & Engg
The M.S. University of Baroda The M.S. University of Baroda
Vadodara Vadodara

Dr. NIRAV I. JAMNAPARA Prof. S.N.SOMAN

(Scientific officer – F) (Head of Dept.)
Facilitation Centre for Industrial Metallurgical & Materials Engg.Dept.
Plasma Technologies (FCIPT), Faculty of Tech.& Engg.
Institute for Plasma Research The M.S. University of Baroda
Gandhinagar Vadodara

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

DECLARATION

We declare that this written submission for the award of Bachelor of

Engineering represents our ideas in our own words and where others ideas or
words have been included; we have adequately cited and referenced the
original sources. We also declare that we have adhered to all principal of
academic honesty and integrity and have not misrepresented or fabricated or
falsified any idea/data/fact/source in our submission. We understand that any
violation of above will be cause for disciplinary action by the institute and can
also evoke penal action from the sources which have thus not been properly
cited or from whom proper permission has not been taken when needed.

iii
CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

ACKNOWLEDGEMENT

After an intensive period of 5 months, today is the day writing this note of
thanks in finishing touch of our thesis. It has been a period of intense learning
for us, not only in the scientific arena, but also on a personal level. This training
period has had a big impact on us. We would like to reflect on people who have
supported & helped us so much throughout this period.

First and foremost, we would like to thank Dr. Bharati R. Rehani Associate
Professor, Metallurgical & Materials Engineering Department, Faculty of
Technology and Engineering, The M.S. University of Baroda for the
continuous support throughout our project work. It cannot be argued with that
you are the most influential person in our career. Your passion, guidance, and
discipline have been indispensable to our growth as a person over these past
two years.

Our sincere thanks goes to Dr. Vandana J. Rao for helping us with the SEM-
EDS characterization. She has inspired us to become independent researchers
& helped us to realize the power of intelligence, over knowledge, simple
fundamental logic behind bigger issues through stories. During our tenure, she
contributed to a rewarding graduate experience our work, engaging me in new
ideas & demanding a high quality of work in all our endeavors.

I feel highly priviledged to give my sincere gratitude and indebtedness to Prof.

S . N . Soman (Head, Metallurgical and materials engg. Dept. MSU, Vadodara)
for their encouragement.

We would also like to express sincere thanks to Institute for Plasma Research
(IPR). There are no proper words to convey my deep gratitude & respect for
our thesis & research advisor Dr. Nirav Jamnapara.

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Our deep sense of gratitude goes to our friends Mr. Arunsinh Zala, Research
Scholar, Facilitation Centre for Industrial Plasma Technologies. We cannot
forget our friend Mr. Romit Tandel, Mr. Aaron Christie, who went through
hard times together cheered me us & celebrated each accomplishment.

Finally, we are grateful to our parents, who provided a carefree environment

for us so that we can concentrate on our study, we deeply thank our parents for
their unconditional trust, timely encouragement & endless patience. It was their
love that raised us up again when we got worried.

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

ABSTRACT

304L A.S.S was Gas Nitrided using different time and temperature in Nitrogen
atmosphere. The gas nitriding process was carried out in horizontal tube furnace at different
temperatures i.e. 400°C, 450°C, 500°C, 550°C, in Nitrogen atmosphere at a flow rate of 280
mbarlit/sec. for 3hr, 4hr, 5hr. Characterization was done by SEM which gives the depth of
Nitrided layer and EDS was carried for elemental analysis. It was observer that at 400°C for
4hr, gas nitriding treatment gives maximum case depth of 19μm. The EDS analysis indicates
conforms of the presets of Nitrogen in Nitrided layer.

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

INDEX

TITLE PAGE………………………………………………..i
CERTIFICATE……………………………………………...ii
DECLARATION……………………………………………iii
ACKNOWLEDGEMENT…………………………………..iv
ABSTRACT………………………………………………...vi
LIST OF FIGURES…………………………………………ix
LIST OF TABLES……………………………………….….xii
LIST OF ABBREVIATIONS…………………………….…xiii
Chapter 1…………………………………………………….01
1.1 Introduction…………………………….……………02
1.2 Aim…………………………………………………..03
1.2.1 Objective………………………………………..03
Chapter 2…………………………………………………….04
2.1 Introduction to Stainless steel………………………05
2.1.1 Type of Stainless steel…………………………05
2.1.2 Austenitic Stainless steel………………………06
2.1.3 Reasons for selecting A.S.S for nitriding……...07
2.1.4 Why only 304L grade for nitriding?...................08
2.1.5 Description about 304L grade………………....09
2.1.6 Effect of nitrogen & Iron-N2 phase diagram…..10
2.2 Surface Hardening……………………………….….11
2.2.1 Types of surface hardening treatment…………12
2.2.2 Nitriding Treatment……………………………13
2.2.3 Gas nitriding treatment….……………………..16
Chapter 3……………………………………………………19
3.1 Literature review…………………………………...20
Chapter 4……………………………………………………22
4.1 Composition of 304L ………………………...……23
4.2 Gas Nitriding process…………………...………….23
vii
CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

4.2.1 Sample preparation for Gas Nitriding sample…..24

4.2.2 Equipments used in Gas Nitriding……...……….26
4.3 Procedure for Gas Nitriding……………………….29
4.4 Characterization ………………….…………………35
4.4.1 SEM and EDS …………………………….….…30
Chapter 5…………………………………………………...…34
5.1 Results and Discussion……………………………....35
5.1.1 Heat treatment cycles of Nitrided samples…..…...35
5.1.2 SEM and EDS results…………………………....39
Chapter 6…………………………………………………..…47
Discussion and Conclusion…………..…………..……48
Chapter 7………………………………………………..……49
References………………………………………..…...50

viii
CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

LIST OF FIGURES

Fig Page
Title
No. No.
2.1 Iron – Nitrogen phase diagram 10
2.2 Schematic structure of nitrided layer 13
2.3 Schematic diagram of gas nitriding 16
2.4 The sketch for the liberation of nascent N 17
4.1 Initial Condition Of Sample 24
4.2 Polishing and grinding machine 24
4.3 Ultrasonic cleaning machine 25
4.4 Laboratory set up of Horizontal Tube furnace 26
4.5 Laboratory set up of vacuum system 27
4.6 (a) Side and (b) Front view of gas dosing valve 27
Schematic view of gas dosing valve with different part
4.7 27
its function
4.8 Experimental setup of nitriding process 28
JEOL scanning electron microscope attached with
4.9 31
EDAX system at FTE, MSU, BARODA
4.10 Schematic diagram of scanning electron microscope 32
Heat treatment cycle of sample no. 1 and appearance
5.01 35
of nitrided sample
Heat treatment cycle of sample no. 2 and appearance
5.02 36
of nitrided sample
Heat treatment cycle of sample no. 3 and appearance
5.03 36
of nitrided sample

ix
CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Heat treatment cycle of sample no. 4 and appearance

5.04 37
of nitrided sample
Heat treatment cycle of sample no. 5 and appearance
5.05 37
of nitrided sample
Heat treatment cycle of sample no. 6 and appearance
5.06 38
of nitrided sample
Heat treatment cycle of sample no. 7 and appearance
5.07 38
of nitrided sample
SEM analysis of Gas nitrided sample at 400°c for
5.08 39
240min at 550x XRD System (Bruker D8 Discover)
SEM analysis of Gas nitrided sample at 400°c for
5.09 40
300min at 550x
SEM analysis of Gas nitrided sample at 450°c for 180
5.10 42
min at 550x
SEM analysis of Gas nitrided sample at 450°c for
5.11 43
240min at 550x

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

LIST OF TABLES

Table Title Page

No. No.
2.1 Details about various phases present in Fe-N phase 10
diagram.
2.2 Typical characteristics of carburizing treatment. 12
2.3 Typical characteristics of Nitriding treatment. 12
2.4 Typical characteristics of Carbonitriding treatment. 13
2.5 Typical characteristics of Boriding treatment. 13
4.1 Details of the Parameters in all Experiments. 30
5.1 Details of the Parameters in all Experiments. 35
5.2 (S 1) composition of nitrided sample surface 40
5.3 (S 2) composition of nitrided sample surface 41
5.4 (S 3) composition of nitrided sample surface 42
5.5 (S 4) composition of nitrided sample surface 44
5.6 (S 5) composition of nitrided sample surface 45
5.7 (S 6) composition of nitrided sample surface 45
5.8 (S 7) composition of nitrided sample surface 46

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CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

LIST OF ABBREVIATIONS

XRD: X-Ray Diffraction

SEM: Scanning Electron Microscope

EDS: Elemental Dispersive Spectroscopy

ASS: austenitic stainless steel

BCC: body-centered cubic

EBSD: electron backscattered diffraction

EDX: energy dispersed x-ray spectroscopy

SS: stainless steel

BHN: Brinell hardness number

EN: Emergency number

ASTM: American society for testing of metal

ʎ: indicate wave length

HRC: Hardness in Rockwell C scale

AISI: American iron and steel institute

SAE: society of automotive engineers

UNS: unified numbering system

xii
 Chapter 1
Introduction
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

1.1 Introduction

For better life and serviceability, many engineering components should be provided
with improved properties in the surface adjacent region of the component, as this is usually
the location of most severe loading. Thus a hard case on a soft core can induce pronouncedly
improved mechanical performance. The outer hard case enhances the wear and fatigue
resistance while the soft core “bulk” retains the toughness to bear the impact loads. Hard
cases can be produced on many steel components for example by thermochemical diffusion
treatments such as nitriding, carburizing, nitrocarburizing and carbonitriding, which are
widely employed in the industry.

Nitriding is the most widely employed thermochemical surface treatment whereby Nitrogen
is introduced into the surface of the solid metal by holding the metal at moderate or high
temperature to enhance the mechanical (fatigue and wear) and chemical (corrosion)
properties of ferritic steel components but here it is performed on Austenitic Stainless Steel
components for study purpose which obtained the positive results. At the usual nitriding
temperatures (450°C-580°C; below the Ac1 temperature of steel) no phase transformations,
such as austenite-ferrite and austenite-martensite, can occur in the bulk of the steel
components. Due to the absence of these bulk phase transformations, which involve large
volume changes, good dimensional tolerance can be achieved, upon nitriding, which avoids
the need of post-machining and/or post-heat treatments.

This is a distinct advantage of the nitriding process over other surface heat treatments, like,
carburizing and carbonitriding. Several nitriding methods are available such as gas nitriding,
salt bath nitriding, plasma nitriding and laser nitriding. Among these nitriding methods,
gaseous nitriding is the only method which can be thermodynamically controlled due to the
possibility of precise control of the chemical potential of nitrogen in the gas atmosphere.

Owing to their good corrosion resistance, mechanical strength, heat resistance and high
formability, austenitic steels have found application in many branches of industry. In the
initial state, these steels exhibit, however, low hardness and abrasive wear resistance.
However, the modification of the surface of austenitic steels is, as a rule, difficult, as the
dense and tight Cr2O3 oxide film formed on the steel surface prevents other elements from
penetrating into the material.

2
Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

The range of the employed nitriding duration and temperature was adopted based on
preliminary tests of short-duration (3 - 5 h) and low-temperature (450 - 550°C) nitriding of
austenitic steels.

1.2 Aim

To carry out Gas Nitriding Treatment on 304L Austenitic Stainless Steel to observe
the case depth by varying time and temperature.

1.2.1 Objective

Formation of CrN / Cr2N coating on 304 L to improve wear resistance, & corrosion
resistance without degradation of other mechanical properties by Gas Nitriding
Treatment.
To observe the depth of compound layer and its composition by advanced
characterization techniques like EDS & SEM.

3
Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
Chapter 2
Theory
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

2.1 Introduction to Stainless steel

Steel which contains more than 12% Chromium will form a thin passive
oxide film which consists high corrosion resistance called Stainless Steel.
Stainless steel are high alloy steels and possess excellent corrosion and oxidation
resistance. Due to this characteristics, these steels find numerous application in nuclear
plants, power generating units, paper and pulp manufacturing plants, food processing unit,
and petrochemical units.[1]

2.1.1 Type of Stainless steel

There are mainly five types of Stainless Steels based on their microstructures. They are,[2]

1. Ferritic Stainless Steel

Standard ferritic grades contain mainly Cr (11 - 19%) as alloying element,
with little or no Ni. This allows the cost connected to raw materials to be stable and low,
comparable to that of carbon steels but with significantly improved corrosion resistance.
Their microstructure is ferritic and they therefore are magnetic. To prevent the formation
of Cr-rich carbides/nitrides at the grain boundaries during welding it is possible to add
small amounts of Nb and/or Ti having higher affinity to C/N than Cr. As ferrite
stabilizers, Nb and Ti can also be used to prevent formation of brittle martensite. The
field of application usually ranges from room to high temperature, especially in Sulphur-
containing atmospheres. Generally, ferritic stainless steels are not used at cryogenic
temperature due to high brittleness in the low temperature range.

2. Martensitic Stainless Steel

Martensitic grades contain similar amount of Cr to that of ferritic SS, but in order
to increase the austenite stability range at high temperature, necessary for heat treatment,
this requires addition of Ni, N or C. The martensitic stainless steels are magnetic and
heat-treatable, following the same procedure as for conventional carbon steels
(austenitizing, quenching, tempering). Stainless steels belonging to this grade are the
least corrosion resistant and are normally employed in similar application fields as the
corresponding martensitic steels, including surgical equipment, razors, cutlery, bearings,
etc.

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Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

3. Precipitation hardening Stainless Steel

Precipitation hardening stainless steel is a highly specialized class of materials,
mainly used when higher strength at high temperature is desired, although the corrosion
resistance is not superior to that of more conventional ferritic stainless alloys. They can
be further classified as martensitic, austenitic or semi-austenitic, depending on the nature
of the main constituting phase. Most precipitation hardening stainless steels contain Ti,
Al, Cu, Nb and Mo for strengthening purposes.

4. Duplex Stainless steel

Duplex stainless steel grades have a multiphase microstructure, typically ferritic-
austenitic. High Cr content (17 - 30%), with rather low Ni content (1 - 7%) produces
almost equi-proportional balance of phases (ferrite and austenite) following heat-
treatment in the two phase region. Other common alloying elements are Mo and N to
improve strength, corrosion resistance against pitting and to balance the microstructure.
Duplex stainless steels usually take advantage of both characteristics of ferritic and
austenitic steels, with an additional advantage of the cost prospective thanks to the
limited use of Ni.

5. Austenitic Stainless steel

Austenitic Stainless steels possess optimum combination of strength, ductility
and toughness. Hence, they are the most widely used of all varieties of stainless steels.
There is no phase transformation in these type of S.S. For these reasons they are not
subjected to heat treatment operation in order to improve the properties. Cold working
is the only strengthening mechanism for these and it suffers from sigma-phase
embrittlement.

2.1.2 Austenitic Stainless steel

Addition of Ni to stainless steels can increase their ability to passivate in

sulphuric acid, significantly improve corrosion resistance in hydrochloric acid of all
concentrations at room temperature, and increase corrosion resistance in aqueous and
molten sodium hydroxide. Nickel also improves toughness, cold formability and
resistance of welds to certain agents. [2][3]

6
Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Progressive addition of Ni displace delta ferrite zero to higher

temperatures and increase the amount of austenite formed at higher temperatures. The
stability of the austenite phase is also increased by Ni so that at approximately 8% Ni an
austenitic structure persists at room temperature.
The parents of the austenitic stainless steel class are 302 (0.15% c) and
304 (0.08% c) which have approximately 18% chromium and 8% nickel. Therefore,
Austenitic stainless steel is commonly known as 18-8 stainless steel. Based on 302 and
304 steels, a series of 3xx austenitic stainless steels have been developed by adjusting the
chromium and nickel content or by addition of small amounts of other alloying elements.
The most common austenitic stainless steels ae (a) the basic 18-8 stainless
steels (17-19% Cr, 8-10% Ni), 302 and 304; (b) the higher nickel content 305 (10-13%
Ni) to reduce the rate of work hardening and improve deep drawing; (c) the highly
corrosion resistant molybdenum-bearing 316 (2-3% Mo) and 317 (3-4% Mo); (d) the
stabilized grade 321 (about 0.4% Ti); (e) the extra low carbon (0.03% c) grades,304L and
316L; (f) the oxidation resistant grades, 308 (19-21% Cr,10-12% Ni), 309 (22-24% Cr,
12-15%Ni), 310 (24-26% Cr, 19-22% Ni).

2.1.3 Reasons for selecting A.S.S ( Austenitic stainless steel ) for nitriding
Austenitic stainless steels of the 300 series are the most difficult to
nitride; nevertheless, types 301, 302, 303, 304, 308, 309, 316, 321, and 347 have been
successfully nitrided. These nonmagnetic alloys cannot be hardened by heat treating;
consequently, core material remains relatively soft, and the nitrided surface is limited as
to the loads it can support. This is equally true of the nonhardenable ferritic stainless
steels. Alloys in this group that have been satisfactorily nitrided include types 430 and
446. With proper prior treatment, these alloys are somewhat easier to nitride than the 300
series alloys. so, It is a known fact that A.S.S. is difficult to Case harden as it contains
Cr2O3 film which is generally hardtop remove. This experiment was generally based on
research work for obtaining a thin case on the surface of 304L SS by varying the Time &
Temperature. As the Corrosion resistance of ASS is better, wear resistance is made to
increase by Nitriding without degradation of other mechanical properties. The grain
refinement of ASS is also much difficult because it consist of a single phase system. Also
304L ASS is susceptible to sensitization which is carried out when >0.03%c is their for
these reason carburizing is not carried out on it so mainly nitriding process is carried out

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Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

for surface hardening but, Due to certain reasons specified above, it was a challenging
role to carryout Nitriding on 304L Stainless Steel.

2.1.4 Why only 304L grade for nitriding?

Type 304L stainless steel, also known as ASTM/AISI/SAE
304L, UNS S30403, A2 stainless steel or EN 1.4307, is the most versatile and widely
used steel available in the market. It is an “all purpose” grade characterized by good
corrosion resistance, excellent formability and weldability. Additionally it is among the
cheapest grades of stainless steels, making it the favorite choice of industry. It is
particularly suitable for large structures such as food and beverages containers,
pharmaceutical industry, kitchenware, construction material (screws, bolts, etc.) as well
as for exhaust systems within automotive industry. As other ASS, 304L is non-magnetic,
even though some δ-ferrite (0-5%) is commonly found in the form of stringers.
Controversial results have been reported regarding the effects of δ-ferrite, including
resistance to stress-corrosion cracking and tendency to cracking during cold work.
Applying Angel’s equation, it infers that deformation induced martensite can form at
room temperature in 304L. This was experimentally demonstrated by several researchers
in a number of experiments including uniaxial tensile tests and cold working. In our
studies we also observed the formation of deformation induced martensite due to
mechanical polishing through XRD and EBSD measurements

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Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

2.1.5 Description about 304L grade

Composition of 304L stainless steel

Components Wt.%
C 0.03max.
Cr 18-20
Mn 2 max
Ni 8-12
P 0.045 max
S 0.03 max
Si 1.0 max

Properties of 304L stainless steel

 Density 8 gm/cc
 Melting point 1450 °c
 Hardness 158 BHN
 Tensile strength 564 MPA
 Yield strength 210 MPA
 Elongation % 58 %
 Modulas of elasticity 200 GPA
 Charpy impact 216 j

Application of 304L stainless steel

 In chemical plant for making tank and pipe
 In medical device and in food industries
 In building construction
 Interior decoration
 Kitchen furniture
 In windows frame etc.

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Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

2.1.6 Effect of nitrogen & Iron-N2 phase diagram

Iron-nitrogen equilibrium diagram can be used to study the nitriding process. At
the commonly used nitriding temperature (below 590°), nitrogen dissolves in α-iron up to
only 0.1% (called nitrogenous ferrite). When the nitrogen dissolved in a-iron exceeds 0.1%,
next phase stable at the temperature, i.e. γ’- nitride (a solid solution) is formed. When nitrogen
content exceeds about 6%, ε-nitride (a solid solution) is formed.

Fig: 2.1 Iron – Nitrogen phase diagram

If the temperature of nitriding is below 500°C, further increase of nitrogen results in the
formation of ζ-nitride which has nitrogen content of about 11%. Normally, temperatures are
higher, and thus the nitrided layer has on the surface, ε-nitride, richest in nitrogen, and
somewhat inside the steel, it has γ’- and then α-ferrite. Below Table given these intermediate
phases with chemical formula.

Table: 2.1 Details about various phases present in Fe-N phase diagram

Phase Ccompo Wt % of N Interstitial atop Bravais

-sition per 100 Fe atom lattice
Ferrite α Fe 0.10 - B.C.C

Austenite γ Fe 2.8 12.4 F.C.C

Martensite α Fe 2.6 11.1 B.C.tetrag.

γ Fe2N 5.9 25 Cubic

Fe2N2 4.5-11 22-49.3 Hexagonal

ζ Fe2N 11.4 50 Orthorohmbic

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Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Thus, after cooling, the phases in nitrided case are in the order from surface towards the
case:
Thus, plain carbon steels which don’t contain any strong nitride forming elements, when
nitrided in an atmosphere of high nitrogen activity, the iron nitrides are formed. The iron
nitride case thus formed is generally brittle and does not have high hardness. But steels
containing strong nitride forming elements like Al, Mo, Cr, Ti, V etc. interact with diffusing-
in nitrogen during nitriding and internal precipitation of their nitrides takes place resulting in
high surface hardness.

2.2 Surface Hardening

Surface hardening, a process which includes a wide variety of techniques, is
used to improve the wear resistance of parts without affecting the more soft, tough interior of
the part. This combination of hard surface and resistance to breakage upon impact is useful
in parts such as a cam or ring gear that must have a very hard surface to resist wear, along
with a tough interior to resist the impact that occurs during operation. Further, the surface
hardening of steel has an advantage over through hardening because less expensive low-
carbon and medium-carbon steels can be surface hardened without the problems of distortion
and cracking associated with the through hardening of thick sections.
Surface hardening include wide varieties of technique.[4]

Diffusion method Coating method Applied energy method

Carburizing Hard chromium plating Flame hardening
Nitriding Electroless nickel plating Induction hardening
Nitrocarburizing Thermal spraying Laser beam hardening
Carbonitriding Weld hard facing Electro beam hardening
Boriding Chemical vapor deposition
Thermal diffusion process Ion implantation
Laser surface processing

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

2.2.1 Types of surface hardening treatment [5]

Below tables shows different process with them parameter.
Carburizing process
Table: 2.2 Typical characteristics of carburizing treatment.
Process Nature of Process Typical Case Typical base Process characteristics
case temperature, Case hardne metals
in °c depth ss,
HRC
Pack Diffused 815-1090 125 μm- 50-63 Low-carbon Low equipment costs,
carburizing carbon 1.5 mm steels, low- difficult to control case depth
carbon alloy accurately
stee
Gas Diffused 815-980 75 μm- 50-63 Low-carbon Good control of case depth,
carburizing carbon 1.5 mm steels, low- suitable for continuous
carbon alloy operation, good gas controls
stee required, can be dangerous
Liquid Diffused 815-980 50 μm- 50-65 Low-carbon Faster than pack and gas
carburizing carbon 1.5 mm steels, low- processes, can pose salt
and possibly carbon alloy disposal problem, salt baths
nitrogen stee require frequent maintenance
Vaccum Diffused 815-1090 75 μm- 50-63 Low-carbon Excellent process control,
carburizing carbon 1.5 mm steels, low- bright parts, faster than gas
carbon alloy carburizing, high equipment
stee costs

Nitriding process
Table: 2.3 Typical characteristics of Nitriding treatment.
Process Nature of Process Typical Case Typical base Process characteristics
case temperatur Case depth hardnes metals
e, in °c s,
HRC
Gas Diffused 480-590 125 μm- 50-70 Alloy steels, Hardest cases from
nitriding nitrogen, 0.75 mm nitriding steels, nitriding
nitrogen stainless steels steels, quenching not
compounds required, low distortion,
process is slow, is usually a
batch process
Salt Diffused 510-565 2.5 μm- 50-70 Most ferrous Usually used for thin hard
nitriding nitrogen, 0.75 mm metals cases <25 μm (1 mil), no
nitrogen including cast white layer, most are
compounds irons proprietary processes
Ion Diffused 340-565 75 μm- 50-70 Alloy steels, Faster than gas nitriding no
nitriding nitrogen, 0.75 mm nitriding, white layer, high equipment
nitrogen stainless steels costs, close case control
compounds

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Carbonitriding process
Table: 2.4 Typical characteristics of Carbonitriding treatment.
Process Nature of Process Typical Case Typical base Process characteristics
case temperatu Case hardnes metals
re, in °c depth s,
HRC
Gas Diffused 760-870 75 μm- 50-65 Low-carbon Lower temperature than
carbonitriding carbon 0.75 mm steels, low- carburizing (less distortion),
and carbon alloy slightly harder case than
nitrogen steels, carburizing gas control
stainless critical
stee
Liquid Diffused 760-870 2.5-125 50-65 Low-carbon Good for thin cases on
carbonitriding carbon μm steels noncritical parts, batch
and process, salt disposal
nitrogen problems
Ferritic Diffused 565-675 2.5-25 40-60 Low-carbon Low-distortion process for
carbonitriding carbon μm steels thin case on low-carbon
and steel,
nitrogen most processes are
proprietary

Boriding process
Table: 2.5 Typical characteristics of Boriding treatment
Process Nature Process Typical Case Typical Process characteristics
of case temperature, Case hardness, base metals
in °c depth HRC
Boriding Diffused 400-1150 12.5-50 40->70 Alloy steels, Produces a hard compound layer, mostly
boron, tool steels, applied over hardened tool steels, high
μm
boron, cobalt & ni process temperature can cause distortion
compound alloy

2.2.2 Nitriding Treatment

Nitriding is a conventional surface engineering method which relies on nitride formation
within a metal matrix. Among the various thermochemical treatments it is the one
requiring the lowest temperature (from 315°C to 540°C). Alloys containing significant
amount of nitride formers such as Al, Cr, Ti, Mo are also called “nitriding alloys” and are

rteryhersryerryeFig.: 2.2 Schematic structure of nitrided layer

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

specifically designed to benefit from such processes. The typical structure of a nitrided layer
includes a gradient of nitride compounds with decreasing stoichiometry, followed by an
interstitial diffusion layer and finally the bulk, as shown in below Fig.[7][8]

The composition and proportion of the compounds present within the layer is highly
dependent on both the process parameters and the alloy composition (ε-Fe 3-2 N, γ´-Fe 4 N,
CrN in stainless steel). Higher temperatures and longer treatment times lead to an increase
in thickness of the compound layer, while more alloyed steels show a thinner layer compared
to low alloyed steels. [9]

Nitriding of austenitic stainless steel is mainly performed either through gas nitriding
or plasma nitriding. Gas nitriding relies on the use of ammonia or ammonia-hydrogen
mixtures (eq. 1). but first it requires removal of the protective oxide layer. This can be
performed ex situ by electrochemical treatment of the steel, which leads to dissolution of the
Cr-rich oxide and subsequent plating of a thin Ni or Fe layer to prevent re-passivation.

NH3 [N] + 3/2H2………………………………..eq (1)

Nickel and Fe also act as catalysts for the decomposition reaction of ammonia during the
heat treatment. After the atomic nitrogen diffusion, the catalyst layer is successively
removed by acid and passivation can be restored. One advantage of this method is the
possibility to store oxide stripped components before heat treatment. Moreover, the
compound layer formed during nitriding can easily be removed in the post-treatment process
using acids. The disadvantage resides in the number of steps required in this procedure.
Alternatively, de-passivation can be performed in situ, within the heat-treatment furnace.
The procedure involves flushing with halogen-based compounds (e.g. HCl, NF 3) prior to
nitriding 12 process. However, these compounds are aggressive to the furnace. Addition of
NO to NH 3 has been proven to be a possible alternative for activation of SS surfaces.

The reasons of high surface hardness of around 1100 VPN in nitrided cases
of these steels are:

1. Small closely—spaced nitride particles (size 5-15 nm) block the motion of dislocations.
2. As dislocations are generated, there is high density of dislocations, at least 1010 cm-2 as in
heavily cold-worked metals, which increases the hardness.

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

3. High concentration of N atoms forming Cottrell-type atmospheres with dislocations and

also with Fe-alloy nitride interfaces.
Thus, normally the steels containing strong nitride-forming elements are case-hardened by
nitriding.

Main Reasons for Nitriding:

1. To obtain high surface hardness, wear resistance and antigalling properties. Hardness
obtained is higher than obtained by carburising. Hardness HRC 62-67 or even 71 can be
obtained.
2. To improve fatigue properties.
3. To improve corrosion resistance in atmosphere, water, steam, etc. (except stainless steels).
4. To have good high temperature (up to nitriding temperature ≈ 550°C) properties. As the
case has high resistance to tempering, it retains high hardness at high temperatures.
5. No dangers of quench cracks and distortion i.e., high dimensional stability. No other heat
treatment is required after nitriding.

But, nitriding is an expensive process:

1. As low temperatures are used in nitriding, much more time is required to develop the
requisite case depth. It takes 48 to 96 hours of nitriding to develop a case depth of around 1
mm.
2. Expensive gas ammonia is used in nitriding.
3. Expensive alloy steels can only be nitrided and are used.
Thus, as a case-hardening process, nitriding is more expensive as compared to carburising
or carbonitriding. But now with the use of glow-discharge nitriding (ion nitriding)
considerable reduction in total nitriding time (one-half or two-third) is possible.

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Operations before Nitriding:

Normally several operations are done before nitriding:

1. Hardening and Tempering:
Nitriding steels are invariably hardened and tempered at high temperature to increase the
strength and toughness of the core. The tempering temperature is at least 30° higher than the
nitriding temperature, normally 600-675°C. Steel now has sorbitic structure which is also
good for machining.

2. Final Machining:
All the machining operations are done which give the final size to the component, keeping
a close tolerance of 0.03 mm to .05 mm on all areas as parts grow during nitriding. Sharp
corners if possible should be rounded off. If heavy machining had been done, the parts may
be stress-relieved by heating at 550-570°C for 2-4 hours. Final finish machining may be
done then. No machining is done after nitriding.

3. Selective Nitriding:
The areas not to be nitrided are coated with a thin layer of tin (0.01-0.15 mm thick), copper
or nickel or water glass. Surface tension keeps the molten tin sticking to the parts while
being nitrided. Copper (electrolytically deposited) is also used quite often.

4. Then, nitriding is done as required.

5. Finish-lapping is done.

2.2.3 Gas Nitriding Treatment

Fig.: 2.3 schematic diagram of gas nitriding [10]

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Gas nitriding is based on a heterogeneous reaction between an ammonia gas atmosphere

and a steel surface at temperatures between 500 and 580°C. Residence times for the steel
components to be treated are between 2 to 20 hours. Ammonia content, furnace temperature
and residence time control the process result with respect to the hard layer morphology.
Usually the hard layer can be divided into a "white layer" and a compound layer consisting
of metal nitrides of thickness 20 um or less, and a diffusion layer below, containing nitride
precipitation at grain boundaries and dissolved atomic nitrogen in the ά-iron lattice of some
mm thickness.[11] As seen in the figure given below, the reaction is the typical
heterogeneous reaction between a gas and the steel's surface. As ammonia is not
thermodynamically stable at nitriding conditions with respect to the formation of nitrogen
and hydrogen, the reaction is kinetically controlled. Several chemical reactions that control
the overall reaction rate and thus, the growth rate of the hard layer:

 The molecular transport of ammonia

 The adsorption of ammonia molecules
 The stepwise dissociation into atomic N and H
 The combination of H and N atoms to form H2 and N2 , and/or, in competition
with the combination reactions
 The removal of atomic nitrogen from the surface owing to the formation of the
interstitial solution representing the diffusion layer and at higher nitrogen content.
 The removal of H 2 (and N2 if present) by desorption and molecular transport into
the bulk gas phase.

Fig.: 2.4 the sketch for the liberation of nascent N [12]

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

The results are a compound layer at the surface consisting of iron nitrides, as well as a
diffusion layer beneath the compound layer. The compound layer is responsible for excellent
wear and corrosion resistance and the diffusion layer for the increased surface hardness. In the
compound layer, nitrogen concentration can reach values of 20 at% and more. In the diffusion
layer, nitrogen concentration is below 8 at%. [13]

The overall reaction is slow and demands long furnace residence times of up to 20
hours. The performance of this process depends on the material, on surface shape and
condition, and on the pre-treatment of the work-piece, as well as the nitriding process
parameters. Each step of the process can be hindered by surface contamination from prior
manufacturing steps.[14]

Advantages and Disadvantages of Gas Nitriding

Advantages:-
1. Medium term process cycle involved in gas nitriding.
2. Reasonable equipment investment.
3. Possible to have variations in process.
4. Most widely used process of today’s generation.
5. Greater depth obtained than Salt Bath Nitriding.
6. Gas-nitriding is more clean job than salt bath nitriding.

Disadvantages:-
1. Difficult process control.
2. Low development potential.
3. Needs problematic consumables (ammonia).
4. Reasonably high energy and gas consumptions.
5. Limited in applications.
6. Takes much longer time than salt bath nitriding.

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 Chapter 3
Literature review
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

3.1 Literature review

Wendi Liu., in Nov’2008, studied the effects of contaminants on Gas Nitriding of

Nitralloy-135. Surface contamination during the heat treatment process can greatly affect
the quality of the heat treated parts. Although cleaning the post-heat treated parts is
considered a value added process in heat treatment, cleaning parts prior to heat treatment is
also important and can influence the outcome of subsequent processes. The samples were
contaminated with a variety of contaminants, including rust preventive oil, cutting fluid and
rust. The contaminated samples were cleaned using either acid or alkaline cleaner. Both
cleaned and contaminated samples were nitride in the furnace. To determine the effect of
contaminants on gas nitriding, weight gain and the surface hardness were measured.

Zaidao Yang, Windsor, Ontario, Canada, 2012, researched on nitriding to enhance

the wear resistance of austempered ductile iron (ADI), ductile iron (DI), and gray iron (GI),
and 4140 steel. Three gas nitriding processes, namely “Gas nitriding + nitrogen cooled down
to 800°F (Blue)”, “Gas nitriding + cooled down to 300oF (Gray)”, and “Gas nitriding + oil
quenched (Oil)” were used for the cast irons. This study was carried out through optical
metallography, roughness measurements, microhardness, and SEM. The ball-on-disc wear
tests were conducted under lubricated conditions.

Sule Yildiz Sirin, and Erdinc Kaluc, researched on AISI4340 steel. It was ion nitrided
using different time and temperature and the gathered properties were assessed by evaluating
hardness profile, compound layer thickness, case depth and surface roughness by using
microhardness tester, optical microscopy, and X-ray diffraction. It has been found that the
thickness of the compound layer increases with increasing treatment time and temperature.
The surface roughness, the surface hardness, the hardness profile, the case depth, the
compound layer thickness, and phase content of the compound layer depends on nitriding
parameters such as treatment time and temperature.

N.E. Vives Dı´az, R.E. Schacherl, L.F. Zagonel, E.J. Mittemeijer,. Different iron–
chromium alloys (4, 8, 13 and 20 wt.%Cr) were nitrided in a NH3/H2 gas mixture at 580°C
for various times. The nitrided microstructure was characterized by X-ray diffraction, light

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

microscopy and hardness measurements. Composition depth profiles of the nitrided zone
were determined by electron-probe microanalysis.

Xiaoyun Yuan, Yang Zhao, Xing Li and Liqing Chen, The effects of gas nitriding
temperature on the cross section morphology, element nitrogen distribution, and surface
layer compositions of a cold rolled and pre-strained high manganese austenitic TWIP steel
25Mn-3Cr-3Al-0.3C-0.01N and the corresponding anti-corrosion ability have been studied.
The results show that, depending on nitriding temperature, the distribution of element
nitrogen and main phase compositions are significantly different in the nitriding layers. At
a temperature lower than 500 _C, the main composition in the modified layer is S-phase and
the nitrogen concentration linearly decreases from the surface to the center, while Fe4N
forms with S-phase and a step-like distribution of nitrogen content is present at nitriding
temperature of 600°C. Caused by the increasing of modified layer thickness and the
formation of S-phase and Fe4N, the surface hardness was obviously enhanced.

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 Chapter 4
Experiment Work
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

The 304L SS samples were Gas Nitrided at different temperature 400°C, 450°C ,
500°C, 550°C for different time 3hr, 4hr, 5hr.

4.1 Composition of 304L

Components Wt.%
C 0.03max.
Cr 18-20
Mn 2 max
Ni 8-12
P 0.045 max
S 0.03 max
Si 1.0 max

4.2 Gas Nitriding process

Fig. shows the flowchart for gas nitriding process of 304L Austenitic
stainless steel.

Sample :- 304 L
Size :- 2 x 1 cm

With emery paper and Ultrasonic Polishing and Cleaning of sample

stirring with acetone

-2
Create vacuum 10 torr.
N purging.
2
Set heat treatment cycle in furnace. GAS NITRIDING
Heating of sample at specific temperature.
Holding for specific period of time.
Cooling of specimen up to 150ºc in N2 atm. .

Scanning electron microscope ( SEM ) Characterisation of nitrided

Energy Dispersive Spectroscopy samples

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

4.2.1 304L Sample Preparation for Gas Nitriding

 Sample Details

Sample grade :- 304L A.S.S

Size of sample :- 2 x 1 cm
Fabrication technique :- Rolling (Plate)
Composition of specimen :- C-0.03%, Cr-18-20%,
Ni-8-12%, P-0.045%,
Mn-2%, Si-0.75%,
S-0.03%, Fe-Balance
Fig.: 4.1 Initial Condition
of Sample
 Specimen preparation for nitriding
o Grinding and Polishing

GRINDING removes saw marks and levels and cleans the specimen surface. Polishing
removes the artifacts of grinding but very little stock. Grinding uses fixed abrasives—the
abrasive particles are bonded to the paper or platen—for fast stock removal. Polishing uses
free abrasives on a cloth; that is, the abrasive particles are suspended in a lubricant and can
roll or slide across the cloth and specimen. The term lapping to mean grinding or coarse
polishing with an abrasive slurry against a hard metal platen. Grinding is done by manually
or mechanically but manual grinding allows better control of grinding depth than automatic

Fig.: 4.2 polishing and grinding machine

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

grinding. For improve surface smoothness first rough grinding is carried out then fine
grinding i.e 1-4 emery no. After the finest grinding step and subsequent cleaning, manually
polish the specimen on napless polishing cloths loaded with lubricant and Alumina paste.
[15]
o Ultrasonic cleaning

Ultrasonic cleaning is the rapid and complete removal of contaminants from

objects which are immersed in a tank of liquid that is flooded with high frequency sounds
waves. These non-audible sound waves create a gentle scrubbing action within the fluid,
removing contaminants from all surface areas the fluid comes into contact with. The process
is brought about by high frequency electrical energy that is converted by a transducer into
high frequency sound waves – ultrasonic energy. Ultrasonic energy enters the liquid within
the tank or bath, this causes the rapid formation and collapse of minute bubbles; a
phenomenon known as cavitation. These bubbles travel at high speed within the tank,
causing them to implode against the surface of any immersed object with an enormous
release of energy. As the bubbles implode and cavitation occurs, the cleaning solution rushes
into the gap left behind by the bubbles, gently lifting any contaminants, dirt and tarnishing
from both the surface and innermost recesses of intricately shaped parts. [16]

Fig.: 4.3 Ultrasonic cleaning machine

But in our case the cleaning is carried out with water and acetone where the samples
are kept in the beaker consisting samples completely dipped in acetone. The beaker is then
kept in the cleaning chamber which is filled with water and the arrangement is such that
water and acetone doesn’t come in contact with each other. Required time for cleaning set
in the programmer.(generally 15 – 20 min in our case).

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

4.2.2 Equipment used in Gas Nitriding

The main component of Gas Nitriding setup are as follows

1. Horizontal Tube Furnace
2. Vacuum system
3. Gas dosing Valve
4. N2 Cylinder
1. Horizontal Tube furnace
Figure shows the horizontal Tube furnace, MTI corporation make model No.
GSL1100x
Connection Connection with
with cylinder vacuum system

Fig.: 4.4 Laboratory set up of Horizontal Tube furnace

The furnace has Quartz tube having internal diameter 5cm. the hot zone of the
furnace is about 15cm. the maximum temperature which can be achieved is 1100°C.
the furnace has arrangement for creating vaccum and facility for gas purging during
heating the furnace can be operated under controlled condition by PID controller
where temperature, heating rate, holding time and cooling can be controlled. Figure
shows the photograph of Horizontal Tube furnace
2. Vacuum system
Figure shows the vaccum system supplied by HIND HIVAC model no. VS
65D. it consists of rotary pump to achieve a pressure of maximum 10-3torr and
a different pump to attain 10-6torr vaccum. The pressure gauge is Pirani
Gauge(10-3torr) and Penning Gauge(10-6torr), measures the vaccum level
inside the furnace. The vaccum system was connected using bellow at one end
of the furnace.

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Connection Pressure
with Gauge
furnace

Rotary
pump Regulating
Fig.: 4.5 Laboratory set up of vacuum system valves

The Rotary pump creates a vacuum of 10-3torr prior to purging Nitrogen gas inside the
furnace.

3. Gas dosing Valve

(a)

(b)

Fig.: 4.7 schematic view of

gas dosing valve with
Fig.: 4.6 (a) Side and (b) Front view different part its
of gas dosing valve function

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Once the vaccum of 10-3torr is achieved, the Nitrogen flow inside the furnace is
controlled by Gas Dosing Valve. Figure shows the schematic view of Gas dosing valve
provided from M/S fifer pvt, ltd., model No.(EVM 116), the gas flow is controlled such
that pressure inside the furnace during Nitrogen purging is at 1mbar.

Figure shows the experimental setup for Gas Nitriding process consisting of Nitrogen Gas
cylinder, Gas dosing valve, horizontal tube furnace and vaccum system.

N2 cylinder
Gas Horizontal Tube
dosing Quartz Tube
Furnace Pressure Gauge
Valve

Fig.: 4.8 Experimental setup of Rotary

nitriding PROCESS pump

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

4.3 Procedure for Gas Nitriding:-

1. Clean the furnace using Acetone to remove dust particle from the
furnace.
2. A Quartz boat was used as a sample holder. Samples were placed in
Quartz boat and treated in the Hot zone of the furnace.
3. Both the ends of furnace are closed. At one end the furnace was
connected to the vacuum system and at the other end it is connected to
Gas Dosing Valve to Nitrogen cylinder

Now the set-up is ready for Gas Nitriding process.

4. Initially using the Rotary pump, a vacuum of 10-3 torr is connected inside
the furnace.
5. Nitrogen Gas was then purged through gas dosing valve and flow rate is
controlled such that pressure 1mbar is created inside the furnace.
6. The furnace is switched on and the experiment was carried out as per the
program set in PID display.
7. Table 4.1 gives the detailed parameter of Gas Nitrided experiments.
8. Once the program is over, the samples are cooled in furnace in Nitrogen
atmosphere upto 150°C.
9. The samples are removed next day for characterization (SEM, EDS).

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Table: 4.1 Details of the Parameters in all Experiments.

Sample Base pressure Time to Temperature Heating Holding

no. (mbar) reach at (in °c) atm. time (in
temp. min)
(min)
S-1 0.02 40 400 N2 240
S-2 0.02 40 400 N2 300
S-3 0.02 45 450 N2 180
S-4 0.02 45 450 N2 240
S-5 0.02 45 450 N2 300
S-6 0.02 50 500 N2 180
S-7 0.02 55 550 N2 240

4.4 Characterization
The characterization tests are necessary to confirm the phase of the material, its
stoichiometry and composition formed. Characterization techniques such as scanning
electron microscopy (SEM) and elemental analysis using energy dispersive spectroscopy
(EDS) were performed on Gas nitrided samples. The cross-sectional microscopy of the
samples was carried out in a Scanning electron microscope at various magnifications while
the elemental composition was determined using Energy dispersive spectroscopy.

4.4.1 SEM and EDS

Surface Morphological and Chemical Analysis:

The SEM imaging of cross section of the samples for determining the film
thickness was carried out with the help of a SEM-EDAX machine; model – JSM
5610LV, and make – JEOL scanning electron microscope at Faculty of Technology
and Engineering, The Maharaja Sayajirao University of Baroda, Vadodara, Gujarat.

A typical SEM instrument, showing the electron column, sample chamber,

EDS detector, electronics console, and visual display monitors. The above following
Fig shows the view of SEM instrumentation.
The scanning electron microscope (SEM) uses a focused beam of high-
energy electrons to generate a variety of signals at the surface of solid specimens. The
signals that derive from electron-sample interactions reveal information about the

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

sample including external morphology (texture), chemical composition, and

crystalline structure and orientation of materials making up the sample. In most
applications, data are collected over a selected area of the surface of the sample, and
a 2-dimensional image is generated that displays spatial variations in these properties.
Areas ranging from approximately 1 cm to 5 microns in width can be imaged in a
scanning mode using conventional SEM techniques (magnification ranging from 20X
to approximately 30,000X, spatial resolution of 50 to 100 nm). The SEM is also
capable of performing analyses of selected point locations on the sample; this
approach is especially useful in qualitatively or semi-quantitatively determining
chemical compositions (using EDS), crystalline structure, and crystal orientations
(using EBSD).

Fig.: 4.9 JEOL scanning electron microscope attached with EDAX system at
FTE, MSU, BARODA

FUNDAMENTAL PRINCIPLES OF SEM

Accelerated electrons in an SEM carry significant amounts of kinetic energy, and this energy
is dissipated as a variety of signals produced by electron-sample interactions when the
incident electrons are decelerated in the solid sample. These signals include secondary
electrons (that produce SEM images), backscattered electrons (BSE), diffracted
backscattered electrons (EBSD that are used to determine crystal structures and orientations
of minerals), photons (characteristic X-rays that are used for elemental analysis and
continuum X-rays), visible light (cathodoluminescent), and heat. Secondary electrons and

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

backscattered electrons are commonly used for imaging samples: secondary electrons are
most valuable for showing morphology and

Fig.: 4.10 Schematic diagram of scanning electron microscope [20][19]

topography on samples and backscattered electrons are most valuable for illustrating
contrasts in composition in multiphase samples (i.e. for rapid phase discrimination). X-
ray generation is produced by inelastic collisions of the incident electrons with electrons
in discrete orbitals (shells) of atoms in the sample. As the excited electrons return to
lower energy states, they yield X-rays that are of a fixed wavelength (that is related to
the difference in energy levels of electrons in different shells for a given element). Thus,
characteristic X-rays are produced for each element in a mineral that is "excited" by the
electron beam. SEM analysis is considered to be "non-destructive"; that is, x-rays
generated by electron interactions do not lead to volume loss of the sample, so it is
possible to analyze the same materials repeatedly.[19]

APPLICATIONS

The SEM is routinely used to generate high-resolution images of shapes of objects

(SEI) and to show spatial variations in chemical compositions: 1) acquiring elemental
maps or spot chemical analyses using EDS, 2)discrimination of phases based on mean atomic

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

number (commonly related to relative density) using BSE, and 3) compositional maps based
on differences in trace element "activators" (typically transition metal and Rare Earth
elements) using CL. The SEM is also widely used to identify phases based on qualitative
chemical analysis and/or crystalline structure. Precise measurement of very small features
and objects down to 50 nm in size is also accomplished using the SEM. Backscattered
electron images (BSE) can be used for rapid discrimination of phases in multiphase samples.
SEMs equipped with diffracted backscattered electron detectors (EBSD) can be used to
examine micro fabric and crystallographic orientation in many materials.[19]

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 Chapter 5
Results & Discussion
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

5.1 Results & Discussion

Table: 5.1 Details of the Parameters in all Experiments.

Time to
Holding
Sample Base pressure reach at Temperature Heating
time (in
no. (mbar) temp. (in °c) atm.
min)
(min)
S-1 0.02 40 400 N2 240
S-2 0.02 40 400 N2 300
S-3 0.02 45 450 N2 180
S-4 0.02 45 450 N2 240
S-5 0.02 45 450 N2 300
S-6 0.02 50 500 N2 180
S-7 0.02 55 550 N2 240

5.1.1 Heat treatment cycles of nitrided samples

1. Sample no. 1 (S-1) :-

Fig.: 5.01 Heat treatment cycle of sample no. 1 and appearance of nitrided
sample

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

2. Sample no. 2 (S-2) :-

Fig.: 5.02 Heat treatment cycle of sample no. 2 and appearance of nitrided
sample

3. Sample no. 3 (S-3) :-

Fig.: 5.03 Heat treatment cycle of sample no. 3 and appearance of nitrided
sample

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

4. Sample no. 4 (S-4) :-

Fig.: 5.04 Heat treatment cycle of sample no. 4 and appearance of nitrided
sample

5. Sample no. 5 (S-5) :-

Fig.: 5.05 Heat treatment cycle of sample no. 5 and appearance of nitrided
sample

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

6. Sample no.6 (S-6) :-

Fig.: 5.06 Heat treatment cycle of sample no. 6 and appearance of nitrided
sample

7. Sample no.7 (S-7) :-

Fig.: 5.07 Heat treatment cycle of sample no. 7 and appearance of nitrided
sample

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

5.1.2 Scanning Electron Microscope and EDS results

Surface Morphology studies using SEM: Surface morphology observations by

SEM have been an effective tool to qualify the phase of nitrogen compound present on the
sample surface. In order to match the XRD data, the surface morphology observations were
conducted by SEM. Nitrided samples contain nitrogen compound like (chromium nitride,
iron nitride etc.) in the harden layer. Hence, all samples were gas nitrided for different time
and temperature they are subjected to analysis of its nitrided layer. The observed
morphologies of nitrided layer are as discussed below.

1. Sample no.1 (S-1):- Fig. indicates the SEM micro photographs of Gas
Nitrided sample S1 treated at 400°C for 240min. It is observed that two
continuous thin layers are formed with an average thickness of 17μm and
11μm on the surface of the specimen..

Fig.: 5.08 SEM analysis of Gas nitrided sample at 400°c for 240min at 550x

Sample no :- S1 Base pressure :- 0.02 mbar

Nitriding temp. :- 400°C Magnification :- 550X
Nitriding time :- 240 min

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Table: 5.2 (S 1) composition of nitrided sample surface

The Table shows the EDS analysis of the sample S1 Nitrided at 400°C for
240min.the micrograph shows the region where EDS is carried out. The
Nitrogen content in the gas nitrided sample is 2.06% along with the presence
of Cr 17.08 wt% and Fe 63.56 wt%.

2. Sample no.2 (S-2):- Fig. indicates the SEM micro photographs of Gas
Nitrided sample S1 treated at 400°C for 300min. It is observed that a
continuous thin layer is formed with an average thickness of 14-15μm on
the surface of the specimen.

Fig.: 5.09 SEM analysis of Gas nitrided sample at 400°c for 300min at
550x

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Sample no :- S2 Base pressure :- 0.02 mbar

Nitriding temp. :- 400°C Magnification :- 550X
Nitriding time :- 300 min

Table: 5.3 (S 2) composition of nitrided sample surface

The Table shows the EDS analysis of the sample S1 Nitrided at 400°C for
300min.the micrograph shows the region where EDS is carried out. The
Nitrogen content in the gas nitrided sample is 3.40% along with the presence of
Cr 6.10 wt% and Fe 19.44 wt%

3. Sample no.3 (S-3):- Fig. indicates the SEM micro photographs of Gas
Nitrided sample S1 treated at 450°C for 180min.different layers present, may
be of Cr-N or Fe-N.

Sample no :- S3 Base pressure :- 0.02 mbar

Nitriding temp. :- 450°C Magnification :- 200X
Nitriding time :- 180 min

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Fig.: 5.10 SEM analysis of Gas nitrided sample at 450°c for 180 min at 550x

Table: 5.4 (S 3) composition of nitrided sample surface

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

The Table shows the EDS analysis of the sample S1 Nitrided at 450°C for
180min.the micrograph shows the region where EDS is carried out. Nitrogen
was not found in this gas nitrided sample is % along with the presence of Cr
16.25 wt% and Fe 59.60 wt%

4. Sample no.4 (S-4):-

Fig.: 5.11 SEM analysis of Gas nitrided sample at 450°c for 240min at 550x
Sample no :- S4 Base pressure :- 0.02 mbar
Nitriding temp. :- 450°C Magnification :- 550X
Nitriding time :- 240 mi

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Table: 5.5 (S 4) composition of nitrided sample

surface

Fig. indicates the SEM micro photographs of Gas Nitrided sample S1 treated
at 450°C for 240min. It is observed that a very thin continuous layer formed
with an average thickness of 9μm the surface of the specimen.
The Table shows the EDS analysis of the sample S1 Nitrided at 450°C for 240
min. the micrograph shows the region where EDS is carried out. Nitrogen was
not found in this gas nitrided sample. The presence of Cr 16.25 wt% and Fe
59.60 wt% can be seen.

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

EDS results of nitrided sample

1. Sample no.5 (S-5) :-
The Table shows the EDS analysis of the sample S1 Nitrided at 450°C for 300
min. The micrograph shows the region where EDS is carried out. Nitrogen was
not found in this gas nitrided sample. The presence of Cr 16.98 wt% and Fe
62.09 wt% can be seen.

Table: 5.6 (S 5) composition of nitrided

sample surface

2. Sample no.6 (S-6) :-

Table: 5.7 (S 6) composition of nitrided

sample surface

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

The Table shows the EDS analysis of the sample S1 Nitrided at 500°C for
180 min. The micrograph shows the region where EDS is carried out.
Nitrogen was not found in this gas nitrided sample. The presence of Cr 17.59
wt% and Fe 63.79 wt% can be seen.

3. Sample no.7 (S-7) :-

Table: 5.8 (S 7) composition of nitrided sample

surface

The Table shows the EDS analysis of the sample S1 Nitrided at 550°C for
240min.the micrograph shows the region where EDS is carried out. The Nitrogen
content in the gas nitrided sample is 0.48% along with the presence of Cr 16.99
wt% and Fe 63.10 wt%.

46
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 Chapter 6
Discussion &
Conclusion
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

6.1 Discussion and Conclusion

304 L S.S. samples are gas nitrided using nitrogen gas at 1 mbar
pressure for 4 different temperature and 4 different time. The SEM and
EDS analysis indicates the formation of nitrided layer on 304 L S.S.
a.) S1 400°C for 240 min N2 % is 2.06 %.
b) S2 400°C for 300 min N2 %is 3.40 %.
c) S4 450°C for 240 min N2 % is 0.16 %.
d) S7 550°C for 240 min N2 % is 0.48 %.
The 304 L sample gas nitrided at 400°c temperature and 240 min time
shows max. thickness of 19 μm.

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

Chapter 7
References

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Faculty of Tech. and Engg., The Maharaja Sayajirao University of Baroda, Vadodara
 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

1) T.V. Rajan & C.P. Sharma, Heat Treatment- Principles and

Techniques
2) Giulio Maistro, 2015. Microstructural Characterization of Expanded
Austenite in 304L and 904L Austenitic Stainless Steels
3) Xinyang Li, Microstructural characterisation of nitrogen implanted and plasma
nitrided austenitic stainless steel
4) surface hardening of steels, understanding the basics, edited
by,j.r.devis, ASM internatioional 2002
5) S. Lampman, ASM Internationa, Introduction to Surface Hardening of
Steels
6) P. Weymer, “Principles of Gas Nitriding,” Heat Treat. Prog., no.
July/August, pp. 12– 13, 2009
7) K.G. Budinski, Surface Engineering for Wear Resistance, Prentice-
Hall, 1988
8) P. Weymer, “Principles of Gas Nitriding,” Heat Treat. Prog., no.
July/August, pp. 12– 13, 2009
9) T. Christiansen and M. A. J. Somers, “Characterisation of low
temperature surface hardened stainless steel,” Struers J. Mater., no. 9,
pp. 1–17, 2006
10) https://www.slideshare.net/morphinssquad/gas-nitriding
11) F. Hoffmann and P. Mayer: in ASM Handbook, Vol.3, p122-123,
Materials Park,OH, 1992
12) J. Darbellay, Gas nitriding: An Industrial Perspective, MSE 701 –
March 22,2006

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 CHARACTERIZATION OF GAS NITRIDED 304L STAINLESS STEEL

13) K. Jack, Nitriding, Proceedings of the Metal Society, Heat Treatment,

London,1973
14) B. Haase, J. Dong and J. Heinlein. Surface oxidation of steels at low
pressures and elevated temperature, Impact on Gas nitriding, 2000,
p263-268
15) ch-4,grinding and polishing © 2002 ASM International. All Rights
Reserved. Ceramography: Preparation and Analysis of Ceramic
Microstructures (#06958G)
16) F. John Fuchs Blackstone Ultrasonics P.O. Box 220 - 9 N. Main
Street Jamestown, NY 14702-0220,Ultrasonic Cleaning Fundamental
Theory and Application
17) http://serc.carleton.edu/research_education/geochemsheets/techniqu
es/XRD.html
18) https://www.slideshare.net/muffafa/2-components-of-xray-machine)
19) http://serc.carleton.edu/research_education/geochemsheets/techniqu
es/SEM.html
20) https://www.google.co.in/search?q=schematic+diagram+of+scannin
g+electron+microscope&source=lnms&tbm=isch&sa=X&ved=0ahU
KEwiElcPCrvaAhUYR48KHRhuBfkQ_AUICigB&biw=1366&bih=
700#imgdii=iW1cuAVpZ5y2IM:&imgrc=ZP7TuU00rBtXaM

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