Surface & Coatings Technology 200 (2005) 507 – 511

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Surface material design of 316 stainless steel by combination of low

temperature carburizing and nitriding
M. Tsujikawaa,T, D. Yoshidab, N. Yamauchic, N. Uedac, T. Sonec, S. Tanakad
a
Graduate School of Engineering, Osaka Prefecture University, Sakai-shi, 599-8531, Japan
b
Osaka Prefecture University, Sakai-shi, 599-8531, Japan
c
Technology Research Institute of Osaka Prefecture, Ayumino, Izumi-shi, 594-1157, Japan
d
SDC LTD. 132, Kannabe-cho 4, Sakai-shi, 590-0053, Japan
Available online 6 April 2005

Abstract

Combinations of carburizing and nitriding were plasma processed both sequentially and simultaneously to AISI 316 substrate at 723
K. All samples treated by combined carburizing and nitrizing show carbon accumulation beyond the nitrided layer. Depth of the
combined treated layer was deeper than that of the nitrided-only specimen. In addition, hardness depth profiles of these samples show
gentle slopes from the surface to substrate. Sequentially carburised then post-nitrided specimen showed corrosion resistance as well as
untreated substrate, however, the corrosion resistance of simultaneously carburized and nitrided specimen was obviously inferior to those
of samples of untreated steel. It was found that the surface design with hardness and corrosion resistance is possible by sequential plasma
process.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Diffusion; Surface improvement; Duplex surface layer; Austenitic stainless steel; Corrosion resistance

1. Introduction substrate as the character of nitriding [5]. These character-

Plasma nitriding is one of the most widely used surface
improvement techniques to increase the surface hardness
and wear resistance of austenitic stainless steels. However,
conventional nitriding at temperature higher than 773 K
degrades the corrosion resistance of the steels by the
chromium nitrides formation which consumes the dissolved
chromium for a passive state.
It has been found that the low temperature nitriding
makes the surface layer of austenitic stainless steel hard and
nitrides free [1]. This surface layer so-called S phase has the
hardness around 1000 HV and keeps good corrosion
resistance of austenitic stainless steel [2–4]. On the other
hand, because of the low temperature diffusion treatment,
the S phase has a thin hardened layer, and a steep drop of
hardness at the border between the hardened layer and
T 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 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.02.051
istic features affect the mechanical properties of treated
austenitic stainless steels.
Low temperature carburizing also forms an S phase like
layer at the surface of austenitic stainless steels. These
carburized layers have a gentle drop of hardness but have a
lower surface hardness than that of nitrided S phase [6,7].
Furthermore, low temperature nitriding of austenitic stain-
less steel shows the push-in effect of dissolved carbon [4,8–
12]. Authors showed that post-nitiriding can propel the
carburized layer into inner space at low temperature. Such a
combination of carburizing and post-nitriding makes the
surface of AISI 304 grade austenitic stainless steel a thick
duplex structure [13].
It has been reported that the precipitation of chromium
carbides or nitrides in 316 steel does not occur at higher
temperature than in 304 steel, and the carburized layer of
316 steel has higher hardness than that of 314 steel. The
duplex surface layer by combined carburizing and nitriding
of 316 steel should be thick and mildly dropping hardness
508 M. Tsujikawa et al. / Surface & Coatings Technology 200 (2005) 507–511

Table 1
Plasma process used in this study
Process Symbol First process Second process
Temp. Gas flow ratio (%) Process Temp. Gas flow ratio (%) Process
(K) CH4 N2 H2 Ar time (h) (K) CH4 N2 H2 Ar time (h)

Nitriding 8N 723 – 80 20 – 8 – – – – – –
Carburizing 8C 723 5 – 45 50 8 – – – – – –
Simultaneous process 8(C + N) 723 5 80 15 – 8 – – – – – –
Sequential process 4C–4N 723 5 – 45 50 4 723 – 80 20 – 4
4(C + N)–4N 723 5 80 15 – 4 723 – 80 20 – 4

profile. The purpose of this paper is to design the duplex
layer surface of 316 by various combinations of carburizing
and nitriding.
2. Experimental procedures
The substrate material used in this work was a AISI
316 type austenitic stainless steel with the following
chemical compositions (in mass%): 16.99 Cr, 10.12 Ni,
2.19 Mo, 1.00 Mn, 0.04 C, 0.69 Si, 0.029 P, 0.004 S and
balance Fe. Solution-treated steel bars were cut into 25
S(N)
(a) 8N (b) 8C
S(N)
S(N)
S(C)
mm in width, 50 mm in length and 5 mm in thickness.
The faces of the plates were then ground and polished to
the mirror finish.
Plasma thermochemical treatment was performed with a
laboratory type apparatus with a DC power source. Each
specimen attached with a thermocouple was set in the
furnace as a cathode. After evacuation up to 1.33 d 10 1 Pa,
the mixed gas pressure for each specimen was adjusted to
6.67 d 102 Pa. All plasma thermochemical treatment in this
study was carried out at 723 K. Total respective processing
times were 8 h.
Table 1 shows details of each plasma treatment with the
specimen symbols. For example, 8N specimen was plasma-
treated at 723 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 723 K
S(C) with a mixture of nitrogen, methane, and hydrogen gas. The
4C–4N specimen was processed sequentially, first treated by
plasma carburizing for 4 h at 723 K, then treated by plasma
nitriding for 4 h at 723 K. In such a sequential process, the
gas mixture changes were carried out within 10 s without
temperature change.
Microstructures of treated layers were investigated by X-
ray diffraction analysis (XRD) using Cu-Ka (40 kV, 150
mA) and glow discharge optical emission spectrometry
(GDOES). Tribological properties were evaluated with a
ball on a plate dry slide tribotester using an 8-mm diameter
S(C) ceramic (Si3N4) ball as mated material. The applied load
was constant at 18 N. After 4000 turns of sliding friction,
the specimen plate wear loss was measured by profilometry.
Corrosion resistance of these specimens was estimated by

(c) 8(C+N) (d) 4C-4N

10µm
8N 16.5 µm
S(N) Nitrided layer
8C 14.1 µm Carburized Layer
S(C) 8(C+N) 11.8 µm 8.2 µm
4C-4N 10.6 µm 10.6 µm
4(C+N)-4N 13.5 µm 6.3 µm

0 5 10 15 20 25
(e) 4(C+N)-4N Thickness of layers [ µm ]

Fig. 1. Features of plasma-treated surface layers. Fig. 2. Thickness of treated layers measured from micrographs.
 M. Tsujikawa et al. / Surface & Coatings Technology 200 (2005) 507–511 509

1200
neously carburized and nitrided specimen, 8(C + N), reaches
to 120% that of the nitrided specimen, and the 4C–4N
8N specimen has about 130% deeper layer than that of
1000 4C-4N nitrided-only 8N specimen after being processed for the
8(C+N) same duration.
4(C+N)-4N Fig. 3 shows these five specimens’ hardness depth
800 profiles. The 8C specimen has the maximum hardness of
8C
about 770 HK, which is far lower than the hardness of other
specimens of about 1050 HK. Comparison of the hardness
600 profile of the 8C specimen with that of the 8N shows that
the nitrided layer of the 8N specimen has a hard layer with
an abrupt layer–core interface, while the carburizing
400 produces a gradually decreased hardness profile.
Three combined carburized and nitrided specimens,
8(C + N), 4C–4N and 4(C + N)–4N, show a similar
200 tendency to bulge in hardness profiles at inner carburized
layer as shown in Fig. 1(c), (d) and (e) as S(C) definition.
The most gradual decrease in hardness from 1050 HK
0 level to substrate hardness was displayed by the 4C–4N
0 10 20 30 40 50 specimen. The hard surface layer thickness of the 4C–4N
Distance from surface [µ] specimen was about 70% of that of nitrided-only specimen
Fig. 3. Depth profiles of Knoop hardness. 8N, because of the half nitiriding duration. However, the
largest bulging of hardness at the inner layer was
saltwater immersion testing at room temperature with 10% achieved.
NaCl solution.
3.2. Elemental profiles of carbon and nitrogen

3. Results and discussion
3.1. Layer morphology and hardness profile
Fig. 1 shows the morphological appearance of the
processed 316 steel specimens. The three combined
processed specimens, 8(C + N), 4C–4N and 4(C + N)–4N,
have duplex layers irrespective of whether they were
processed sequentially or simultaneously.
Fig. 2 indicates layer thickness measured from micro-
scopic observations. The nitrided specimen, 8N, has a
deeper layer than the carburized specimen, 8C. Further-
more, combined processed specimens have deeper layers
than the nitrided-only specimen. The depth of the simulta-
Fig. 4 shows the elemental depth profiles of plasma-
processed specimens for carbon and nitrogen. The carbon
push-ahead effect of incoming nitrogen [14] is shown
clearly in Fig. 4(c), (d) and (e). Even in Fig. 4(a),
dissolved carbon is accumulated at the front of the nitrided
layer. A large amount of carburized carbon accumulated
beyond the nitrided layer in the combined process.
However, some carbon remains in the nitrided layer of
4C–4N. A small peak of carbon is at the sub-surface layer.
This small peak in Fig. 4(d) is due to the dissolved carbon
in e-phase (Fe2–3N) [13].
Simultaneously carburized and nitrided specimen
8(C + N) in Fig. 4(c) shows accumulation of carbon beyond
the nitrided layer as in Fig. 4(d), but carbon concentration at

Fig. 4. GDOES depth profiles of nitrogen and carbon for plasma-treated 316 samples.
510 M. Tsujikawa et al. / Surface & Coatings Technology 200 (2005) 507–511

AISI 316
8N
8C
8(C+N)
4C-4N
4(C+N)-4N

0 2 4 6
Wear loss [10-13m3]

Fig. 6. Wear under dry sliding condition.

specimen exceeded the value of 8N specimen even though

Fig. 5. Comparison of XRD patterns of treated specimens. the peak hardness is as high as the 8N specimen. A
hardness drop at the very surface is suspected. The
the surface is also observed. coefficient of friction of the 8(C + N) specimen was 0.4
Fig. 5 shows XRD patterns of plasma-processed speci- in the early stage of friction under 150 turns. Other
mens. The carburized specimen and nitrided specimen show specimens including untreated 316 showed the coefficient
a typical S phase by carbon and nitrogen. The h 2h of friction to be 0.7.
diffraction pattern of 4C–4N is fundamentally the sum of
the nitrided specimen’s and the carburized specimen’s
patterns. However, in the pattern of 8(C + N), the peaks that 4. Conclusions
were inferred to indicate S phase do not show the separated
manner of S(N) and S(C). They are positioned between S(N) The surface structure of AISI 316 austenitic steel was
and S(C) in the 8(C + N) pattern. Some chromium carbides contriled by combinations of low temperature plasma
were suspected in the 8(C + N) specimens. nitriding and plasma carburizing. A plasma-carburized layer
of carbon was pushed ahead by post-plasma-nitriding. It
3.3. Corrosion resistance accumulated in the front of the nitrided layer. This formed
duplex surface layers with different hardness. The duplex
Table 2 shows results of saltwater immersion testing. The structure by sequential carburizing and nitriding has excel-
nitrided-only specimen has excellent corrosion resistance, lent corrosion resistance in saltwater immersion tests.
just as untreated 316 steel. The saltwater immersion test However, the simultaneously carburized and nitrided speci-
indicated a clear distinction between simultaneous process- men has the poorest corrosion resistance of all. The
ing and sequential processing. Simultaneously carburized possibility of surface material design has been extended by
and nitrided specimens, 8(C + N), began to form reddish the control of the location of carbon-S phase by the
brown rust within 8 h. This could be attributed to the combined carburizing and nitriding at low temperature.
formation of chromium carbides. In contrast, sequentially
post-nitrided specimens, 4C–4N and 4(C + N)–4N, never
developed the rust.
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