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Surface & Coatings Technology 193 (2005) 309 313

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Behavior of carbon in low temperature plasma nitriding


layer of austenitic stainless steel
M. Tsujikawaa,*, N. Yamauchib, N. Uedab, T. Soneb, Y. Hirosec
a

Department of Materials Science, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Sakai-shi, 599-8531, Japan
b
Technology Research Institute of Osaka Prefecture, 7-1, Ayumino 2, Izumi-shi, Osaka 594-1157, Japan
c
Department of Materials Science and Engineering, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan
Available online 28 October 2004

Abstract
Expanded austenite by low temperature plasma nitriding of austenitic stainless steels pushes carbon ahead of the nitrided layer.
Apparently, this phenomenon accompanies uphill carbon diffusion. Clarifying the mechanism of this carbon push-ahead effect is important
for controlling treated-layer microstructure. This investigation is intended to clear the push-ahead effect of specimens treated with a
combination of carburizing and nitriding. Plasma treatments were carried out for 18Cr8Ni steel in 667 Pa at 673 K. We used the
following gas-flow ratios: 80% N220% H2 for nitriding; Ar gas mixed with 5% CH4 for carburizing; and 80% N2 mixed with from 5%
CH4 and balancing H2 for simultaneous carburizing and nitriding. Glow-discharge optical emission spectroscopy (GDOES) indicated an
accumulated carbon layer beyond the nitrogen plateau on the nitrided specimen of pre-carburized sample. Such a carbon accumulation
profile also resulted from simultaneous treatment. Furthermore, carbon accumulated similarly in cases of carburizing after nitriding
treatment. Nitrided specimens of pre-carburized samples have a small carbon peak just under the surface on GDOES profile. This small
carbon peak weakened and disappeared with increasing nitriding time. X-ray diffraction analysis revealed formation of e (Fe23N) phase
just under the surface of the nitrided pre-carburized sample.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Diffusion; Carburizing; Microstructure control; Austenitic stainless steel; Surface improvement

1. Introduction
Low temperature plasma nitriding hardens the surface
of austenitic stainless steel without deterioration of
corrosion resistance [15]. The distribution of dissolved
carbon in austenitic stainless steels changes by low
temperature nitriding. Expanded austenite by low temperature plasma nitriding of austenitic stainless steels pushes
carbon ahead of the nitrided layer. Thereby, the changed
carbon profile shows the carbon accumulation beyond the
front of the nitrided layer. This phenomenon has been
observed widely with a variety of profiling techniques
[58].

* Corresponding author. Tel.: +81 72 254 9317; fax: +81 72 254 9912.
E-mail address: masato@mtl.osakafu-u.ac.jp (M. Tsujikawa).
0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2004.08.179

This phenomenon has been described with a trapping


model, in which nitrogen is trapped in the treated layer,
presumably by chemical binding with chromium [9]. The
carbon is pushed ahead of the incoming nitrogen. This is
qualitatively consistent with trapping and detrapping,
assuming the trap binding energy for carbon to be lower
than that of nitrogen [7,10].
On the other hand, low temperature carburizing similarly
make the expanded austenite phase as hard and corrosionresistant case [11]. Combination of carburizing and nitriding
introduces new structural control of surface modification
layer [12]. It is important for development of the controlled
structure to clarify the behavior of carbon in connection with
nitriding.
This study examines elemental profiles of carbon and
nitrogen of 304 stainless steel after plasma treatment in
various combinations of carburizing and nitriding. In

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Table 1
Plasma treatment and specimen designation
Process

Nitriding
Carburizing
Simultaneous
process
Sequential
process

Symbol

First process

Second process

Temperature
(K)

Gas flow ratio (%)


CH4

N2

H2

Ar

8N
4C
8(C+N)

673
673
673

5
5

80

80

20
15
15

80

8
4
8

4C4N
8C4N
16C4N
24C4N
4C8N
4C16N
4C24N
4N4C
4N4C450

673
673
673
673
673
673
673
673
673

5
5
5
5
5
5
5

80
80

15
15
15
15
15
15
15
20
20

80
80
80
80
80
80
80

4
8
16
24
4
4
4
4
4

673
673
673
673
673
673
673
673
723

addition, it elucidates the formation and change of phases in


treated layers.

Process
time (h)

Temperature
(K)

Gas flow ratio (%)


CH4

Process
time (h)

Total
process
time (h)

N2

H2

Ar

8
4
8

5
5

80
80
80
80
80
80
80

20
20
20
20
20
20
20
15
15

80
80

4
4
4
4
8
16
24
4
4

8
12
20
28
12
20
28
8
8

to identify the crystal structure at the surface of the plasma


treated surface. Glow discharge emission spectrometry
(GDOES) was used to analyze the elemental depth profiling
of treated surfaces.

2. Experimental procedures
The material used in this work is austenitic stainless,
which satisfies the grade of AISI 304. The chemical
composition of the specimen is Fe18.8 Cr8.3 Ni0.94
Mn0.21 Mo0.31 Cu0.4 Si0.037 P0.003 S0.06 C in
mass%. Roughly cut AISI 304 plates were solution treated
at 1303 K for 2.7 ks. Then they were dry ground slightly to
the specimen shape of 25 mm width, 50 mm length and 5
mm thickness. These preparations gave the specimens a
fully austenitic structure, which was confirmed by X-ray
diffraction analysis [13].
Plasma thermo-chemical treatment was performed with a
laboratory type apparatus with a d.c. power source. Each
specimen attached with a thermo couple was set in the furnace
as cathode. After evacuation up to 1.3310 1 Pa, the
pressure of the mixed gas for each specimen was adjusted
to 6.67102 Pa. All thermo-chemical treatment was performed in this study at 673 K, with the exception of the 4N
4C450 specimen. Its second process was treatment at 723 K.
Table 1 shows details of each plasma treatment with
specimen symbols. For example, the 8N specimen was
plasma treated at 673 K with a mixture of 80% nitrogen gas
and 20% hydrogen gas for 8 h. The 8(C+N) specimen was
treated by plasma carbo-nitriding process for 8 h at 673 K
with a mixture of nitrogen, methane, and hydrogen gases.
Similarly, the 4C4N specimen was first treated by plasma
carburizing for 4 h at 673 K, then followed by plasma
nitriding for 4 h at 673 K. In such sequential processes, gas
mixture changes were made at within 10 s without temperature change. After treatment, the specimens were allowed
to cool in the evacuated furnace.
X-ray diffraction analysis (XRD) using Cu-Ka (40 kV,
150 mA) radiation with a monochrometer, was undertaken

3. Results and discussion


3.1. Push ahead of carburized carbon by nitriding
Elemental depth profiles of carburized only specimen
designated for 4C is shown in Fig. 1(a) and that of

Fig. 1. GDS depth profiles of carburized specimen (a) and nitrided precarburized specimen (b).

M. Tsujikawa et al. / Surface & Coatings Technology 193 (2005) 309313

311

3.2. Competitive diffusion of carbon and nitrogen, and


carbon diffusion through nitrided layer
Fig. 4(a) shows the GDOES depth profile of simultaneous carburizing and nitriding processed specimen
8(C+N). Carbon diffused beyond the nitrided layer; also,
carbon accumulated at the front of the nitrided layer. High
concentration of carbon at the surface decreased sharply in
the nitrided layer. This carbon concentration results from
competition to get trap sites in the austenitic phase. Because

Fig. 2. Microstructure of duplex surface layer formed at surface of


carburized and post-nitrided specimen (4C4N).

carburized and post-nitrided specimen designated for 4C


4N in Fig. 1(b). The plasma treatment condition for
specimen 4C worked successfully to carburize the 304
austenitic stainless steel. The carbon push-ahead effect of
nitrogen is evident when comparing Fig. 1(a) and (b).
However, some carbon remains in the nitrided layer as a
small carbon peak remains in the sub-surface layer. Fig. 2
shows the microstructure of surface layer of the sequentially processed 4C4N specimen. There are obvious
duplex layers as reported by Blawert at simultaneous
processing [12].
The XRD analysis of Fig. 3 indicates that the u 2u
diffraction pattern of 4C4N is fundamentally the sum of
the nitrided specimens and the carburized specimens
patterns. Expanded austenite phase by nitrogen (S(N)) and
by carbon (S(C)) appeared separately, but some chromium
carbides of the 4C specimen disappeared. These results
indicate that movement of the S(C) phase is possible by
applying nitriding process after carburizing.

Fig. 3. Comparison of XRD patterns of nitrided pre-carburized specimen


(4C4N), nitrided specimen (8N) and carburized specimen (4C).

Fig. 4. GDS depth profiles of simultaneous nitriding and carburizing


processed specimen (a: 8(C+N)), nitrided and post-carburized specimen (b:
4N4C) and nitrided and post-carburized at 723 specimen (c: 4N4C450).

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M. Tsujikawa et al. / Surface & Coatings Technology 193 (2005) 309313

of the weak affinity of carbon to trap site [9], carbon must


remain in the diffusion site [10]. Thereby carbon at diffusion
sites diffused to inner spaces according to the concentration
gradient of interstitial atoms.
Similar diffusion of carbon on nitrided layer occurred at
nitrided and post-carburized specimen 4N4C. Fig. 4(b)
shows diffusion of carbon through a pre-nitrided layer.
Slight accumulation of carbon occurs at the front of nitrided
layer.
Fig. 5 shows that these two specimens have similar
XRD peaks. Separation of S(N) peaks and S(C) peaks are
vague in comparison with the pattern of 4C4N that
appears in Fig. 3 and the CrN peak is shown in the
8(C+N) specimen [12].
Although the 4N4C450 specimen has a huge accumulation of carbon beyond the nitrided layer shown in Fig.
4(c), the circumstance of the carbon diffusion was quite
different from the 4N4C. S(N) phase was decomposed to
CrN and ferritic iron (a-Fe) by secondary process at 723 K
[14] as shown in Fig. 5. The concentration of nitrogen in
Fig. 4(c) displays not the interstitial nitrogen but the
nitrogen in CrN.
3.3. Formation of E -nitride at sequential processing
Fig. 6 shows GDOES profiles for carburized and postnitrided specimens with various carburizing time before
nitriding for 4 h. Intensities of elemental concentration vary
in each measurement. In Fig. 6, there are iron (Fe)
concentration profiles of each specimen as an intensity
index. The Fe content of substrates showed good consistency for carbon and nitrogen concentration comparison.
The concentration and the depth of accumulated carbon
increase with the pre-carburizing time. The peak at the subsurface also increased.
The height of the peaks increases with carburizing time.
However, the positions of the peaks are almost at the same
depth. Equally, the concentration of nitrogen decreases with
carburizing time.

Fig. 5. XRD analysis of combined processed specimens.

Fig. 6. Influence of carburized time on GDS depth profiles after nitriding


(nitriding time: 4 h).

Fig. 7 shows the set of GDOES profiles of 4CxN (x=4,


8, 16, 24) specimens. The accumulation of carbon at the
front of nitrided layer moves with the nitriding front.
However, the small sub-surface peak of carbon did not
move into a deeper position. Furthermore, weakening of the
sub-surface peak is apparent with increasing nitriding time.
On the 4C24N specimen, the carbon sub-surface peak
almost disappeared.
Fig. 8 shows XRD patterns of 4CxN specimens. On
the 4C4N specimen, as mentioned before, the S(C) peak
can be recognized. However, S(C) peaks no longer appear
on 4C8N specimen because the carbon accumulation
moves to a deeper position. On the other hand, the E-Fe23N
peaks and S(N) peaks are clarified with increasing nitriding
time. Especially, the XRD peaks of e phase seem to

Fig. 7. Effect of post nitriding time on GDS depth profiles of carburized


specimens (carburizing time: 4 h).

M. Tsujikawa et al. / Surface & Coatings Technology 193 (2005) 309313

(2)

(3)

(4)
Fig. 8. XRD patterns for nitrided pre-carburized specimens with various
nitriding times.

correspond to the sub-surface peak of carbon in GDOES


analysis. They are shown clearly with increasing nitriding
time.
These results suggest that formation of E-Fe23N phase
occurs in pre carburized specimens at the sub-surface when
nitriding starts because of the presence of super saturated
carbon released from trap sites by incoming nitrogen. At
this position, trapping of nitrogen by affinity with
chromium [7] renders the formation of chromium carbides
or chromium nitrides difficult. Through the help of supersaturated carbon, E-Fe23N may be formed at the subsurface layer. Further nitriding dilutes the dissolved carbon
in E phase.

A series of nitriding and carburizing by plasma processing at relatively low temperature qualitatively clarified the
behavior of carbon in nitriding as followings:
(1)

Movement of S(C) phase is possible by post nitriding.


Carburized layer was pushed ahead by incoming
nitrogen. With such sequential carburizing and nitrid-

ing the duplex surface layer was formed at austenitic


304 stainless steel.
Accumulation of carbon at the front of nitrided
layer also occurred in both simultaneous carburizing
and nitriding process and in the carburizing pre
nitrided process. The carbon accumulation at the
front of nitrided layer also occurred in both
simultaneous carburizing and nitriding process and
in the nitriding and post-carburizing process. However, chromium carbide was detected by XRD in
these specimens.
E-Fe23N phase is formed at the sub surface of
sequentially carburized and post-nitrided specimens,
but no chromium compounds were detected by
XRD.
Carbon concentration of the sub surface E-Fe23N
phase decreased with increasing post-nitriding time.

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