1

Chapter 1
INTRODUCTION
The effect of nitrogen on the surface properties of steel have been the subject of
interest since 1920s and it was first studied in Europe and America. Initially the
process didnt get much attention but after 1940 there were some avid responses in
this field. With the passage of time, nitriding became one of the most significant case
hardening process for steels. Nitriding doesnt involve any rapid cooling and other
key point to notice in nitriding is that it is not accompanied by any phase
transformation [1]. Nitriding is carried out by keeping the work piece at an elevated
temperature which is characteristic to the work piece material. As time passes,
nitrogen starts diffusing into the work piece surface and hence a solid solution is
formed. If the concentration of nitrogen is beyond a particular limit then it may lead to
precipitation of nitrides. These two processes combined together lead to case
hardening through two different mechanisms namely solid solution hardening and
precipitation hardening. Figure 1.1 represents the microhardness profile of AISI
420 stainless austenitic steel.
Fig 1.1 : Microhardness profile of the longitudinal section of sample treated at 435C
for 20 minutes [1].
The alloying elements present in steel helps in the precipitation of nitrides as they
form nitrides which are stable at nitriding temperature. These elements include
aluminium, chromium, vanadium, and molybdenum. Molybdenum also reduces the
risk of embrittlement at nitriding temperature. Nitriding scores over other case
hardening methods in a few aspects like nitriding can be carried out at relatively low
temperature and it causes little distortion as compared to other case hardening
methods [1].
Depending on the medium in which process is carried out, nitriding can be
divided into three subcategories.
Gas nitriding
Salt bath nitriding
Plasma nitriding

2

Generally, gas nitriding is carried out in an ammonia rich environment where
ammonia dissociates to give nitrogen and hydrogen when it comes in contact with
heated specimen.
Reaction involved : N
2
+ 3H
2
= 2NH
3

In salt bath nitriding, nitrogen is given by a nitrogen containing salt e.g. cyanide
salt.
Reactions involved : 2NaCN + O
2
= 2NaCNO
4NaCNO = Na
2
CO
3
+ 2NaCN + CO + 2N
Plasma nitriding is a method where an electric discharge i.e. plasma is produced at
or in the vicinity of the work piece surface. This plasma contains electrons, ions, and
nascent atoms of the elements which constitute electrolyte. If we use aqueous
solution of a proper electrolyte then these nascent atoms can diffuse into the work
piece and lead to case hardening [10].
Advantages of Plasma nitriding over other nitriding methods:
Smaller process time as compared to other nitridng processes
Low process temperature
Minimal distortion
Faster nitrogen penetration
Low energy use

When nitriding of AISI 420 stainless martensitic steel using a DC pulse is done in
75% H
2
and 25% N
2
at different temperatures, it is found that the wear resistance of
the sample is better at low temperature nitridng. This phenomenon is observed due
to the combined effect of high surface hardness and high residual stress of the
nitride layer because compressive stresses are quite instrumental in closing
microcracks and also avoid the formation of microcracks during wear. Also at low
temperatures Cr forms solid solution with highly stable phases of Fe
3
N and
N
during
plasma nitriding and this solid solution forms a protective oxide layer on the surface
of the sample thus protecting it from being corroded. But as temperature is increased
the volume fraction of
N
decreases and hence CrN is formed which results in the
depletion of CrN in the solid solution. Hence, no oxide layer is formed on the surface
and it leads to a decrease in the corrosion resistance of the sample. Since mobility of
Cr is diminished at low temperature therefore no CrN is formed at low temperatures
[3]. It was observed that when we keep on increasing the applied voltage while
carrying out a normal electrolysis a point reaches where normal electrolysis (NE)
suddenly changes to Contact Glow Discharge Electrolysis (CGDE). This
phenomenon can be observed at low voltage value if the temperature of the
electrolyte is increased or the surface tension of the electrolyte is decreased by
adding some surfactants. After a systematic study it was found that this happens
because of the vaporisation of the solvent near the electrodes due to the heat
generated because of Joule effect. Onset of hydrodynamic instability in local solvent
vaporisation is also a major reason for this phenomenon [4].The mechanism of
breakdown of NE is that initially vaporisation of local solvent near the anode starts
due to joule heating which is followed up by a stable counterflow between vapour
bubbles and anolyte. As heating increases, the speed of escaping vapour bubbles
increase beyond a critical value which leads to their coalesce and hence they
obstruct the flow of anolyte liquid to the anode surface. This leads to the formation of
a continuous and unstable vapour plasma envelope on the anode, which later

3

achieves stability underneath the liquid [5]. Figure 1.2 shows the breakdown of NE at
two different temperatures.
Fig 1.2 Current-time (I-t) characteristics of 0.05 M K
2
SO
4
solution at 100V for transition to
anodic CGDE between Pt-wire electrodes(length 5 mm and diameter 0.35 mm) at two
different temperature(--) 452C and (--) 752C [4]

While studying the effect of preset voltage on hardening of the surface it was
observed that for same case depth, the minimum heating time in case of pulse
conditions were less than that in the case of DC conditions. Pulse conditions were
found to have around 25% increase in heating efficiency when the average preset
voltage under pulse conditions was 260V and under DC condition was 300V. And to
add more to the advantages of pulse conditions it has been seen that the operating
voltage in pulse conditions are smaller as compared to that in DC conditions which
implies safer operations and lower energy consumption [6]. However, if the average
preset voltage in pulse condition and in DC condition is kept same then the heating
efficiency of pulse condition 425% greater than that of DC condition [7].
In my sixth semester I did a course in electrochemistry under Prof. Rajiv
Shekhar. I found that course really intriguing and hence I decided to do my project in
fields related to electrochemistry. What I want to do in my project is to understand
the mechanism of plasma nitriding and study the effect of various parameters like
duty cycle, temperature, peak current and voltage on the nitriding behaviour.







4

Chapter 2
EXPERIMENTAL
The experimental set up which I will be using for my work has been schematically
shown in Fig. 2.1.
Fig 2.1 : Schematic diagram of experimental set up of aqueous electrolyte plasma
nitriding
2.1 Anode : Material, dimension and geometry
I will be using a disc of stainless steel as anode with a thickness of about 2 mm and
radius around 100 mm. It will be places inside the electrolyte in such a manner that
the inter electrode gap will be around 50 mm with cathode being partially submerged
in the electrolyte.
2.2 Cathode : Material, dimension and geometry
A cylinder of austenitic stainless steel of 50 mm in length and varying diameter will
be used as cathode on which the nitriding effect has to be studied. For measuring
the temperature, the specimen will be drilled upto 47.8 mm from the top and the hole
diameter will be 5 mm so that thermocouple can be housed in that. Specimens must
be annealed at 550C for 45 minutes and then it will be polished upto 5 m diamond
surface finish using metallographic techniques. Then specimen will be dried after
cleaning it with alcohol [1].
2.3 Electrolyte Used in Aqueous Electrolyte Plasma Nitriding
The electrolyte which I will be using in my experiment will be aqueous solution of
ammonium carbonate. Concentration of the electrolyte was decided after carrying
out the conductivity test for different wt % of ammonium carbonate with distilled
water as the solvent. After studying the effect of electrolyte concentration on the
behaviour of nitiding, it was found that 10 wt % solution would be good for carrying
out the experiment [1].
2.4 Power Supply specifications
A high power pulse rectifier with following features :
(a) Inputs : (1) Voltage : 3 phase, 50 Hz, 380 V (2) Current : 0-60 A

5

(b) Outputs : Direct Current, Voltage : 0-300 V (adjustable) (2) Current : 0-3- A
(adjustable)
(c) Pulse Current : (1)On time : 0.001s 1s (adjustable) (2) ON:OFF ratio 9:1 to
1:9 (adjustable) (3) Peak Current : 0-60 A (4) Peak Voltage : 0-300 V
(adjustable) (5) Heating Time : 0-99s (adjustable) [2].
2.5 Measurement of Temperature, Voltage, and Current
To measure the temperature a chromel-alumel thermocouple will be connected to
the specimen at a distance of 3 mm from the treated surface and to record
temperature a K-type digital thermometer and data logger will be used. I will use a
data acquisition system interfaced with a computer will be used to get the voltage
and current reading [1].



















6

Chapter 3
CONCLUSION
Nitrding has been an extensively studied area. It has been observed that
nitriding significantly improves the physical properties of the substrate as it
hardens the surface of the material used.
Nitriding can be done by various methods including gas nitriding, salt bath
nitriding, and plasma nitriding.
Plasma nitridng has many advantages over other methods because it
consumes less energy, process time is less, and it is nature friendly. The
various parameter on which the properties of the substrate depend are
applied voltage, nitriding time, specimen geometry, temperature, electrolyte
concentration e.t.c.
Many works have already been done on the optimization of above mentioned
parameters to achieve better physical properties of the substrate nitrided via
plasma nitriding.
But it is still to be discovered that what comprises the plasma layer, near the
electrodes, formed during the plasma nitriding process.
So in my work I will try to figure out the composition of the plasma layer.
Apart from that I will also focus on the effect of pulse DC on the behaviour of
nitriding .












7

REFERENCES
1. M.Tech thesis by Amritendu Roy, Aqueous electrolyte plasma nitriding of AISI
stainless austenitic steel ; Department of Materials and Metallurgical Engineering,
IIT Kanpur, December 2006.

2. S.F. Luk, T.P. Leung, W.S. Miu, Ian Pashby, Heating performance of electrolytic
heat-treatment in aqueous solution by pulse current ; Journals Of materials
Processing Technology 63 (1997) 833-838.

3. Yun-tao Xi, Dong Han, Doa-xin Liu, Improvement of corrosion and wear resistances
of AISI 420 stainless martensitic steel using plasma nitidng at low temperature ;
Surface & Coatings Technology 202 (2008) 25772583

4. Susanta K. Sengupta, Ashok K. Sfivastava, Rajeshwar Singh, Contact glow
discharge electrolysis: a study on its origin in the fight ofthe theory of hydrodynamic
instabilities in local solvent vaporisation by Joule heating during electrolysis ; Journal
of Electroanalytical Chemistry 427 (1997) 23-27

5. Urvashi Gangal, Monika Srivastava, and Susanta K. Sen Gupta, Mechanism of the
Breakdown of Normal Electrolysis and the Transition to Contact Glow Discharge
Electrolysis ; Journal of The Electrochemical Society, 156 (10) (2009) F131-F136

6. S.F. Luk, T.P. Leung, W.S. Miu, and I. Pashby, A Study of the Effect of Average
Preset Voltage on Effective Case Depth During Electrolytic Surface-Hardening ;
Materials Characterization Volume 42, Issues 2-3, February 1999, Pages 65-71

7. S.F. Luk a, T.P. Leung , W.S. Miu , I. Pashby, A study of the effect of average preset
voltage on hardness during electrolytic surface-hardening in aqueous solution ;
Journal of Materials Processing Technology 91 (1999) 245249

8. B. Cullity, Elements of X-Ray Diffraction, Prentice hall

9. J. Garcia Sole, D. Jaque, L.E.Bausa, An Introduction to Optical Spectroscopy of
Inorganic Solids, John Wiley & Sons, Ltd

10. Ruth Chatterjee-Fischer - Wrmebehandlung von Eisenwerkstoffen: Nitrieren und
Nitrocarburieren [Heat treatment of ferrous materials: nitriding and nitrocarburising]
1995 2nd Edition, Expert Verlag ISBN 3-8159-1092