Effects of various gas mixtures on plasma nitriding

behavior of AISI 5140 steel

Mehmet Karakan
*
, Akgun Alsaran, Ayhan C elik
Department of Mechanical Engineering, Ataturk University, 25240 Erzurum, Turkey
Received 21 October 2002; accepted 9 January 2003
Abstract
AISI 5140 steel was plasma nitrided at various gas mixtures of nitrogen, hydrogen, and argon to investigate the
actions of hydrogen and argon on plasma nitriding. The structural and mechanical properties of ion-nitrided AISI
5140 steel have been assessed by evaluating composition of phases, surface hardness, compound layer thickness,
and case depth by using X-ray diffraction (XRD), microhardness tests, and scanning electron microscopy (SEM).
It was found that the growth of compound layer can be controlled and the diffusion improved when the gas
mixture includes H
2
gas. Additionally, it was determined that the amount of Ar in dual gas mixture must be at 20%
minimum to obtain distinctive surface hardness and compound layer thickness.
D 2003 Elsevier Science Inc. All rights reserved.
Keywords: Ion nitriding; Gas mixture
1. Introduction
Plasma nitriding is one of the most effective meth-
ods for increasing wear resistance, fatigue strength,
surface hardness, and for protecting the surface of
materials from corrosion. This method has been com-
monly used in industry for the last two decades [13].
Hydrogen and nitrogen gas mixtures are widely
used to enhance the rate of nitriding in the plasma
nitriding process [47]. To investigate alternatives to
these gas mixtures, several studies on mixtures such
as nitrogen and argon [811] and nitrogen and neon
[12] were performed. However, it remains uncertain
as to the importance of any gas additions other than
nitrogen to plasma nitriding. For example, hydrogen
enhances case depth and surface hardness by remov-
ing surface oxide. The presence of argon improves
surface hardness and it may be beneficial either alone
or in combination with hydrogen.
This study primarily deals with the effect of
various gas mixtures on plasma nitriding to improve
surface hardness, composition and thickness of com-
pound layer, and case depth. Therefore, AISI 5140
low-alloy steel was plasma nitrided under various gas
mixtures such as nitrogen + argon, nitrogen + hydro-
gen, and nitrogen + hydrogen +argon, for a constant
time of 4 h and a temperature of 450 C at a working
pressure of 5 mbar. The structural and mechanical
properties of plasma nitrided AISI 5140 are inves-
tigated using X-ray diffraction (XRD), scanning elec-
tron microscopy (SEM), optical microscopy, and
microhardness tests.
2. Experimental procedure
A schematic diagram of the ion nitriding system is
shown in Fig. 1. It consists of a glass bell jar in which
1044-5803/03/$ see front matter D 2003 Elsevier Science Inc. All rights reserved.
doi:10.1016/S1044-5803(03)00010-X
* Corresponding author. Tel.: +90442-231-4860; fax:
+90442-236-0957.
E-mail address: mkarakan@atauni.edu.tr (M. Karakan).
Materials Characterization 49 (2003) 241246
an insulated central electrode is situated, which holds
specimens. A cylindrical anode at earth potential
surrounds it. The cathode has a nest on which the
specimen is located. A thermocouple is connected to
the specimen through the cathode and the nest to
monitor the specimen temperature.
A series of experiments has been carried out to
investigate the ion-nitriding response of AISI 5140
low alloy. The chemical composition of AISI 5140
steel is listed in Table 1. The specimens were nor-
malized at 850 C for 30 min, and then cooled in air.
After cleaning in alcohol, the specimens were placed
into the plasma-nitriding chamber and the chamber
was evacuated to 2.5 10
2
mbar. Prior to ion
nitriding, the specimens were subjected to cleaning
by hydrogen sputtering for 15 min under a voltage of
500 V and a pressure of 5 mbar to remove surface
contaminates.
After ion nitriding, the specimens had a thin
compound layer that was removed before they were
polished through 0.05 mm alumina. This was fol-
lowed by metallographic examination and hardness
testing. The case depth and the surface hardness were
measured by using a Buchler 16004980T at a load
of 50 gf and a dwell time of 15 s. The maximum
surface hardness at 25 mm depth was chosen for
comparison so that any possible effects from a
compound layer would be negligible. A Rigaku
diffractometer was used for XRD analysis. The X-
ray diffractomer was operated at 30 kV and 30 mA
with CuK
a
radiation. The compound layer thickness
was also investigated by using SEM.
3. Results and discussion
Figs. 24 show XRD results for ion-nitrided AISI
5140 low-alloy steel as a function of various gas
mixtures. As seen in the figures, polyphase (g and e)
iron nitrides occur on the surface of low-alloy steel.
Fig. 1. The schematic diagram of ion nitriding system.
Table 1
Chemical composition of AISI 5140 low-alloy steel (%)
Element (wt.%)
C Mn Si Cr Ni Mo V S Cu P
0.426 0.77 0.287 0.845 0.134 0.054 0.0287 0.064 0.0154 0.019
M. Karakan et al. / Materials Characterization 49 (2003) 241246 242
Fig. 2 shows the XRD results of the ion-nitrided
specimens at gas mixtures of 10% H
2
+ 90% N
2
and
10% Ar + 90% N
2
. a-Fe phase was clearly observed
with Ar N
2
mixtures, because the intensity of e phase
was not high. A thin compound layer occurred at a gas
mixture of 10% Ar + 90% N
2
. This is because the
amount of Ar in the gas mixture was insufficient to
create diffusion. The experiments showed that the
amount of Ar in dual gas mixture should be a minimum
of 20% to form a compound layer and to increase
surface hardness. However, the compound layer was
observed with a 10% H
2
gas mixture because the
ionization energy of H
2
is lower than that of Ar.
Fig. 3 illustrates the XRDresults of the ion-nitrided
specimens for gas mixtures of 90% H
2
+ 10% N
2
and
90% Ar + 10% N
2
. While the intensity of e decreased
Fig. 2. XRD patterns of plasma nitrided AISI 5140 steel for gas mixtures of 10% H
2
+90% N
2
(a) and 10% Ar + 90% N
2
(b).
Fig. 3. XRD patterns of plasma nitrided AISI 5140 steel for gas mixtures of 90% Ar + 10% N
2
(a) and 90% H
2
+ 10% N
2
(b).
M. Karakan et al. / Materials Characterization 49 (2003) 241246 243
for Ar N
2
mixtures, the intensity of g increased for
H
2
N
2
mixtures.
The 2q angles of phases were higher at large
angles when the amount of N
2
in the tripartite gas
mixture was high (Fig. 4). When Ar gas amount in
the mixture was increased, the intensity of the phases
occurring compound layer increased.
The compound layer thickness, case depth, and
surface hardness of the ion-nitrided AISI 5140 steel
depending on the gas mixtures are given in Table 2.
The minimum case depth, compound layer thickness,
and surface hardness were obtained at the gas mix-
tures of 10% Ar + 90% N
2
and at 450 C for 4 h.
These results showed that ion nitriding did not
completely occur. When these results are considered
together with XRD results (Fig. 2), it can be con-
cluded that the compound layer (Fe
23
N and Fe
4
N)
was not observed. The compound layer provides
materials with good physical properties against wear
and corrosion. However, the case is very hard and
brittle, and for an application subjected to stresses,
the compound layer should be thin or absent. Addi-
tion of H
2
gas into the gas mixture prevented from
undesirable effects by stopping the rapid growth of
compound layer.
The surface hardness of ion-nitrided AISI 5140
increased up to two to three times for gas mixtures
including H
2
. Furthermore, the maximum case depth
was also observed for the 10% N
2
+90% H
2
gas
mixture. The hardness profiles and SEM photograph
of microhardness indentations of the ion-nitrided
specimens are given in Fig. 5. The increase in indent
dimension is a sign of decreasing hardness. In addi-
tion, the hardness decreases from surface to core
because the concentration of metal nitrides decreased
toward the core.
Fig. 4. XRD patterns of plasma nitrided AISI 5140 steel for gas mixtures of 10% Ar +10% H
2
+ 80% N
2
(a), 80% Ar + 10%
H
2
+10% N
2
(b), and 10% Ar + 80% H
2
+10% N
2
(c).
Table 2
The change of the compound layer thickness, the case depth, and surface hardness with the gas mixtures
Plasma nitriding parameters Compound Case depth Surface
Time (h) Temperature (C) Gas mixture
layer (mm) (mm) hardness (HV)
4 450 90% N
2
+ 10% H
2
45 160190 540550
4 450 10% N
2
+ 90% H
2
22.5 210240 760770
4 450 90% N
2
+ 10% Ar 3565 290300
4 450 10% N
2
+ 90% Ar 810 6090 470480
4 450 80% N
2
+ 10% H
2
+ 10% Ar 56 110140 470480
4 450 10% N
2
+ 10% H
2
+ 80% Ar 5.56.5 90120 500510
4 450 10% N
2
+ 80% H
2
+ 10% Ar 23 185215 700710
M. Karakan et al. / Materials Characterization 49 (2003) 241246 244
Fig. 6 shows SEM micrographs of ion-nitrided
AISI 5140 at different gas mixtures. The thickness of
the compound layer is 22.5 mm at 90% H
2
(Fig. 6a)
and 9 mm at 90% Ar (Fig. 6b). A lot of voids were
observed in the compound layer, as seen in Fig. 6b.
The porous shows one of the undesirable features of
the compound layer.
4. Conclusions
The following main conclusions can be derived
from the above results and discussions:

The hardness profiles of the ion-nitrided speci-

mens exhibited maximum hardness in the range of
760770 HV
0.05
for the 10% N
2
+ 90% H
2
gas
mixture. It was observed that the compound layer
thickness and case depth can be controlled and the
good surface hardness can be obtained with an
increase in the amount of H
2
gas in the gas
mixture.

The compound layer of the ion-nitrided speci-

mens consists of e phase and g phase. The
intensity of e phase is not high for the 10%
N
2
+ 90% Ar gas mixtures. Ar in the gas mixture
causes the rapid growth of compound layer but
the case depth is not as deep with Ar in the gas
mixtures.

The amount of Ar in dual gas mixture must be a

minimum of 20% to obtain distinctive surface
hardness and compound layer thickness.
Fig. 5. (a) The hardness profiles of ion-nitrided specimens as gas mixtures, (b) SEM micrograph of specimen ion nitrided at gas
mixtures of 80% N
2
+ 10% H
2
+ 10% Ar.
Fig. 6. SEM micrographs of plasma nitrided AISI 5140 for 90% H
2
+ 10% N
2
(a) and 90% Ar + 10% N
2
(b).
M. Karakan et al. / Materials Characterization 49 (2003) 241246 245
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