Influence of process parameters in pulse

plasma nitriding of plain carbon steel

Z. urisic*, A. Kunosic and J. Trifunovic
Glow discharge nitriding is widely used to improve the mechanical characteristics of steel
components. This treatment produces a modified surface layer, consisting of an outer compound
zone and an inner diffusion zone. The compound zone (white layer) is the first zone and therefore,
is the contact surface layer. It is of particular interest for establishing the exploitation features of
engineering components exposed to the wear and corrosion. It is important to analyse the
mechanical and tribological features of this layer. With the aim of optimising the nitriding process
and gaining an insight for further research, experimental studies of the pulsed plasma nitriding of
plain carbon steel grade DIN C45 (AISI C1043) were carried out, using a pulsed direct current
glow discharge. The influence of gas composition, temperature, treatment time, duty cycle and
frequency on compound layer thickness and microhardness has been investigated. Five
experiments were performed. In each experiment, one of the process parameters was varied
while the others were kept constant. The characteristics of the nitride surface layers were studied
by optical metallography, Vickers microhardness measurement as well as specially modified Calo
test method. The results obtained could be useful in optimising of the nitriding process and
computer process control.
Keywords: Pulsed plasma nitriding, Process parameters, Compound layer depth, Surface microhardness

Introduction
Glow discharge nitriding is widely used to improve the
wear, fatigue and corrosion resistance of steel components.1 This treatment produces an outer compound
layer and an underlying diffusion layer. In the compound zone, iron nitrides, c9-Fe4N and e-Fe23N, and
alloy element nitrides are present while diffusion zone
consists of iron and alloy nitride of alloy elements
dispersed in nitrogen enriched metal matrix.2,3 The
characteristics of these layers, phase composition,
thickness and hardness, can be easily changed by
varying the process parameters.2,4,5 A single c9-Fe4N
phase layer is tougher and shows better wear and fatigue
properties under severe loading conditions while an eFe23N phase layer increases anti-scuffing properties and
is suitable for applications which are relatively free of
shock loading or high localised stresses.1,2 However, the
formation of a brittle and porous compound zone
affects the wear and corrosion resistance, and restricts
the applications of this technique.3 This problem occurs
when compound zone with mixed c9-Fe4N and e-Fe23N
phases is produced. Such a nitrided phase structure is
known to be detrimental to the tribological properties,
particularly under impact loading conditions, owing to

Faculty of Electrical Engineering, University of Belgrade, Bulevar Kralja

Aleksandra 73, PO Box 35-54, 11120 Belgrade, Serbia and Montenegro
*Corresponding author, email djurisic@etf.bg.ac.yu

2006 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 28 September 2004; accepted 27 October 2005
DOI 10.1179/174329406X98485

the inherently high internal stresses arising from the

c9-Fe4N and e-Fe23N phase boundaries (lattice
mismatch).4,5
Pulsed plasma generators with the power supply in
unipolar and bipolar operational mode,6 with changeable voltage level up to 1000 V (Ref. 5) and pulse
frequency 0100 kHz, are widely used in surface
engineering by diffusion processes, synthesis and deposition of new materials.7,8 The development of insulated
gate bipolar transistors (IGBTs) with high power
conductivity, which are used as basic switching elements
in modern pulsed plasma generators, has contributed a
great deal to the spread of the above techniques.9 Unlike
thyristors, IGBTs enable efficient and simple switching
off of power supply when gas discharge instability in
pulsed plasma appears.10
Compared with the other techniques for surface
engineering, pulsed plasma processes have several
advantages, including a better control of the surface
layer architecture, chemical composition and functional
characteristics, and unlike the other techniques, it is
environment friendly.1 These advantages are especially
noticeable in plasma assisted chemical vapour deposition (CVD) and physical vapour deposition (PVD), but
are also significant in thermochemical diffusion processes, e.g. nitriding. Use of a pulsed plasma provides
the stabilisation of the nitriding process and therefore
the scope for its full automation. The main advantage of
pulsed plasma utilisation in plasma nitriding technology,
compared with classic usage of direct current plasma

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Influence of process parameters in pulse plasma nitriding

2 Voltage waveform on output of pulsed plasma generator in unipolar operation mode: T entire pulse duration, Ton pulse-on time (active pulse duration) and Toff
pulse-off time (pause duration)

1 Schematic diagram of pulsed plasma nitriding system

used in experiments

generators, is the almost complete overcoming of such

problems as local overheating of treated samples and
plasma instabilities.11 Application of pulsed plasma
technologies also enables almost full control of the so
called hollow cathode effect, which makes possible the
efficient nitriding of treated specimens with complex
geometry.12 In addition, pulsed plasma processes are
characterised by a greater number of parameters, which
enable the formation of surface structures with diverse
characteristics and chemical composition2,4 and therefore provide for functional characteristics.13
The aim of the present work was to investigate and to
present the basic parameters of pulsed plasma nitriding
which influence the process especially regarding the
compound zone thickness and microhardness of treated
specimens made from plain carbon steel grade DIN C45.
The influence of gas composition, temperature, treatment time, duty cycle and pulse frequency on compound
zone thickness and microhardness was studied through a
series of experiments.

Experimental procedure
Cylinder shaped specimens made of plain carbon steel
grade DIN C45 were treated in a nitrogenhydrogen
pulsed plasma with various process parameters. Before
nitriding, the specimens were normalised and then a
plane surface of specimens (cylinder basis) was ground
and polished to a constant level of roughness.
Five experiments were performed. In each experiment,
one of the process parameters was varied while the
others were kept constant at fixed values:
(i) temperature t5500uC
(ii) duty cycle dc595%
(iii) frequency f55 kHz
(iv) treatment time t54 h
(v) gas composition: 25%N2, 75%H2.

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All the process parameters refer to the stationary pulsed

plasma nitriding process. It should be mentioned that the
processes of cleaning, heating to the defined temperature
and cooling of the specimens in all experiments were
performed in the same way. This programme of experiments enabled the separation of significant process
parameters relating to the specific characteristics of the
surface structure with minimum number of experiments.
The experiments were performed in a 20 kVA pulse
plasma nitriding unit JONPULS-MK with vacuum
chamber of w3006700 mm, developed by the Faculty
of Electrical Engineering in Belgrade.14 The pulsed
plasma power supply generates the voltage pulses in the
frequency range of 90 Hz16.7 kHz and with a duty
cycle of 595%. A vacuum chamber with cold walls
(water cooling), without thermal shields, was used in the
experiments (Fig. 1).
A pulsed plasma generator in the unipolar operational
mode was used as the system power supply. The voltage
U waveform on the output of the pulsed plasma
generator is shown in Fig. 2.
Characteristic periods of the pulse power supply are
marked in Fig. 2. It is possible to use various relations of
the pulse and pause durations for the same power supply
pulse frequency (f51/T), and therefore this relation
appears as a new parameter in the pulsed plasma
processes. This parameter is called duty cycle and is
defined by the relative duration of active pulse15
dc(%)~

Ton
Ton
100~
100
Ton zToff
T

(1)

considering that infrared heaters are not included in the

vacuum chamber with cold walls, warming of treated
specimens is performed exclusively by the ion bombardment and therefore, it is necessary to provide the
constant effective power of the gas discharge to keep
the constant temperature t of treated specimens on
desired level. This conclusion can be defined by the
following equation
T
i(t)u(t) dt~constant

(t~constant)

(2)

where i(t) and u(t) are instantaneous values of current

and voltage respectively, and t is the time.
Keeping the pulse period T and specimen treatment
temperature t constant during the duty cycle variation
demands the adjustment of the voltage amplitude (and
therefore the current amplitude) of the power supply to
meet the conditions in equation (2). The conclusion is
that the voltage and duty cycle are correlated parameters
in the pulsed plasma nitriding process with constant

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3 Micrograph of specimens surface with calotte formed by microabraser (left) and mathematic equivalent for compound
layer thickness calculation (right)

temperature. By changing the duty cycle dc and therefore the power supply voltage amplitude, the electric
field changes also. That causes changes in the physical
and chemical processes in the plasma and accordingly,
affects the surface structure characteristics of the treated
specimens. It can be concluded that the duty cycle dc
must be recognised as the parameter which not only has
an influence on the process stability during pulse plasma
nitriding, but also affects the characteristics of the
surface structure obtained.7,16

Surface microhardness and compound zone

thickness measurements
The surface microhardness of plasma nitrided specimens
was determined by the Vickers method with a standard
diamond pyramid. The measurements were performed
with the F50.5 N load. This low force provided
relatively shallow penetration of the pyramid peak into
surface layer. Compound zone thickness measurements
showed that in all the Vickers microhardness measurements, the pyramid peak penetrated deep enough, but
not too deep into compound layer and did not reach the
diffusion zone. Consequently, the results of surface
microhardness measurements can be considered to be
compound layer microhardness measurements.
The compound layer thickness measurements of
treated specimens were performed by a specially
modified Calo test method.17,18 Wear scars were formed
on specimen surfaces by a rotating abrasive ball. These
were later chemically treated to create conditions for the
visual detection of compound zone borders and its
thickness with an optical microscope. A micrograph of a
specimen surface with the wear scar formed by the
microabraser is shown in Fig. 3 (left) and the mathematic equivalent for the compound layer thickness
calculation in Fig. 3 (right).
The compound layer thickness h is calculated on the
basis of a mathematical equivalent (Fig. 3, right)
according to the following equation
h~

a2 {b2 (azb) (a{b) 1

~
2
2 2R
8R

(3)

where R (R512.5 mm&a,b) is the abrasive ball radius.

Radii a and b are measured by two optical microscopes
with magnifications of 632, 656 and 696.

Results and discussion

In the pulsed plasma nitriding processes, various
architecture and characteristics of the surface layers
can be achieved. A micrograph of the modified surface
layers on a pulsed plasma nitrided specimen with typical
architecture of the surface zones is shown in Fig. 4.
The compound (white) zone can be seen first and this
is therefore the contact surface layer. In the design of
machine elements exposed to wear and corrosion, it is of
particular interest to analyse the mechanical and
tribological features of this zone.
As a result of the experiments, the influence of each
process parameter on the surface microhardness and
compound zone thickness of the treated specimens could
be established. The results of the measurements are
presented diagramatically in Figs. 59.
At higher working temperatures, a relatively thick
compound zone is formed in the treated specimens

4 Micrograph of modified surface

plasma nitrided specimen

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5 Compound layer thickness (left) and surface microhardness (right) as function of specimen temperature

6 Compound layer thickness (left) and surface microhardness (right) as function of square of nitriding treatment time

7 Compound layer thickness (left) and surface microhardness (right) as function of nitrogen percentage in gas mixture

8 Compound layer thickness (left) and surface microhardness (right) as function of duty cycle

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9 Compound layer thickness (left) and surface microhardness (right) as function of power supply pulse frequency

(Fig. 5) and its thickness, in the analysed range, is

approximately an exponential function of temperature.
However, the surface microhardness for analysed steel
achieves the highest value for nitriding temperature
around 500uC. This behaviour can be explained with the
fact that by increasing the process temperature, the
number of chemical reactions between steel and nitrogen
atoms on the surface of nitrided specimen is increased.
Accordingly, the growth of compound zone thickness is
more intensive. On the other hand, the phase composition of the compound zone can vary as a function of the
nitriding temperature. The c9-Fe4N phase appears at
lower temperatures and with increasing of temperature,
e-Fe23N phase appears also.1,19 That is the most
probable reason for decreased superficial microhardness
after increasing the nitriding temperature over 500uC.
It can be concluded, based on Fig. 6, that with the
increasing nitriding treatment time, the compound zone
growth achieves saturation. For nitriding times up to
t<4 h, the compound layer thickness increases rapidly at
an approximate linear function of t1/2. For treatment time
t.4 h, the growth of compound zone thickness is
negligible. Similar behaviour of the surface microhardness
as a square root function of nitriding time was observed.
These observations are in agreement with the literature.4,20
Compound zone thickness and surface microhardness
were not uniform functions of the nitrogen levels in the
N2H2 gas mixture (Fig. 7). Very low and very high
percentages of nitrogen have a negative influence on the
compound layer thickness and surface microhardness. It
can also be noticed with a nitrogen level in the range of
4060% the compound layer thickness is practically
constant. A thin compound zone and surface microhardness at nitrogen percentages is to be expected owing
to a lower number of nitrogen atoms that are involved in
the chemical reaction with the specimen surface. With
very high nitrogen percentages, there is a high number of
active nitrogen species, but the compound layer thickness and surface microhardness remain low. This could
be due to the low energy of the ions deposited on the
cathode when low levels of hydrogen are present in the
gas mixture. This too was observed in Ref. 2.
The influence of duty cycle on surface microhardness,
noticed in the experimental results, agrees with theoretical expectations. For low values of dc, the voltage has
to be relatively high according to equation (2).
Therefore, the ion kinetic energy is also relatively high
and causes an increase in the cathode sputtering effect.
As a result, the weaker surface structures are sputtered

away while the stronger compact structures are held on

the surface, resulting in surface microhardness increase.
Indeed in these experiments, it has been shown that the
surface microhardness is approximately a linear function
of the duty cycle (Fig. 8, right). The duty cycle of the
pulsed plasma process also affects the compound zone
thickness. At low dc values and, accordingly, relatively
high voltages, the high strength electric field (during the
Ton period) leads to the creation of a relatively high
number of charge carriers in plasma. This stimulates the
compound zone growth which is, on the other hand,
limited to a certain degree by the sputtering effect.
Which one of these two effects that will be dominant,
depends on the other process parameters and character
of the nitrided material.2 The intensity of surface ion
bombardment and corresponding temperature probably
have a local influence on the phase composition of the
nitrided surface structure. This is reflected in the high
surface microhardness at the lowest values of the
compound zone thickness (Fig. 8).
According to the diagrams in Fig. 9, it can be
concluded that the frequency, as a process parameter,
has a greater influence on compound layer thickness
than on the surface microhardness. In fact, differences in
the surface microhardness measurement results for
various frequencies get into the range of unacceptable
measurement errors, therefore it is hard to conclude how
the pulse frequency affects the microhardness of the
treated specimens. To observe the influence of this
parameter on surface structure, it would be necessary to
perform measurements for pulse frequencies of
.20 kHz. The frequency influence on compound zone
thickness can be explained by the fact that charge
carriers in the plasma exist in excited states for a certain
time during the source voltage absence (pulse-off time
Toff). Pulse-off time proportionally decreases with
increasing frequency. This statistically decreases the
time unexcited particles exist and positively affects the
compound layer growth. However, for higher frequencies, pulse-on time Ton is getting shorter and the particle
energy received during that period is insufficient to
ionise or excite them to any significant level. Also,
discharge ignition can be slow and the time for the
discharge current to reach saturation can be as high as
100 ms.6 For high frequencies, the discharge current
might not reach the saturation value during the pulse-on
time Ton. Therefore, for higher frequencies, lower
number of charge carriers are created, which causes a
decrease in the compound zone growth rate.

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After reviewing the results of the compound layer

thickness and surface microhardness measurements, it
can be concluded that all the analysed process parameters have a significant influence on the compound
layer thickness and surface microhardness of treated
specimens made of plain carbon steel grade DIN C45.

Summary
With the aim of optimising the nitriding process and
gaining directions for further research, experimental
studies of the pulsed plasma nitriding of plain carbon
steel grade DIN C45 were carried out, using a pulsed
direct current glow discharge. The influence of gas
composition, temperature, treatment time, duty cycle
and frequency on the compound layer thickness and
microhardness is of particular interest. Five experiments
were performed. In each experiment, one of the process
parameters was varied while the others were kept at
defined constant values. The characteristics of nitrided
surface layers were studied by optical metallography,
Vickers microhardness measurement and a specially
modified Calo test method. According to the set
programme of experiments and the measurement
methodology, the influence of each process parameter
on the surface microhardness and compound layer
thickness of treated specimens were obtained. It has
been found that the lack of the pulsed plasma process
parameters studied affects the surface microhardness
and compound layer thickness of treated specimens
made of plain carbon steel grade DIN C45. These results
should be of value in the optimisation of the nitriding
process and facilitate its computerised process control.

Acknowledgement
This research was partially supported by the Ministry of
Science, Technology and Development of Serbia,
Project NAPIP, and by the European Commission,
RISE Project FP6-INC02-S09161.

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