Surface & Coatings Technology 204 (2010) 3087–3090

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Ion nitriding of a superaustenitic stainless steel: Wear and corrosion characterization

F.A.P. Fernandes a,⁎, S.C. Heck a, R.G. Pereira a, C.A. Picon b, P.A.P. Nascente c, L.C. Casteletti a
a
Department of Materials, Aeronautical and Automotive Engineering, São Carlos School of Engineering, University of São Paulo, Av. Trabalhador Sãocarlense,
n. 400, 13566-590, São Carlos, SP, Brazil
b
Department of Physics and Chemistry, Engineering School of Ilha Solteira, Ilha Solteira, SP, Brazil
c
Department of Materials Engineering, Federal University of São Carlos, São Carlos, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Available online 3 March 2010 The superiority of superaustenitic stainless steel (SASS) lies in its good weldability and great resistance to
stress corrosion and pitting, because of its higher chromium, molybdenum, and nitrogen contents, when
Keywords: compared to general stainless steels. However, some of its applications are limited by very poor wear
Superaustenitic stainless steel behavior. Plasma-nitriding is a very effective treatment for producing wear resistant and hard surface layers
Plasma-nitriding
on stainless steels without compromising the corrosion resistance. In this work, UNS S31254 SASS samples
Temperature
were plasma-nitrided at three different temperatures (400, 450, and 500 °C), under a pressure of 500 Pa, for
Wear
Corrosion
5 h, in order to verify the influence of the temperature on the morphology, wear, and corrosion behavior of
the modified surface layers. The plasma-nitrided samples were analyzed by means of optical microscopy,
micro-hardness, X-ray diffraction, wear, and corrosion tests. Wear tests were conducted in a fixed ball micro-
wear machine and corrosion behavior was carried out in natural sea water by means of potentiodynamic
polarization curves. For the sample which was plasma-nitrided at 400 °C, only the expanded austenite phase
was observed, and for the treatments performed at 450 and 500 °C, chromium nitrides (CrN and Cr2N) were
formed in addition to the expanded austenite. Wear volume and Knoop surface hardness increased as the
plasma-nitriding temperature increased. Higher wear rates were observed at high temperatures, probably
due to the increment on layer fragility. The sample modified at 400 °C exhibited the best corrosion behavior
among all the plasma-nitriding conditions.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
The superaustenitic stainless steels (SASS) have been developed
commercially as a result of improved alloying strategies and
manufacturing processes. The term superaustenitic is often used for
stainless steels with a minimum Mo content of 5 wt.% or high values of
the composition based on pitting resistance index (PREN) [1,2]. They
are a group of Fe-based alloys that exhibit good pitting and crevice
corrosion resistances and good mechanical strength [3,4]. These alloys
are specifically designed for the use in highly corrosive environments
at elevated temperatures, and have a PREN number that ranges from
28.3 to 64.3. The high Ni amounts improve the stress–corrosion–
cracking resistance, and the high Mo and N amounts improve the
pitting and crevice corrosion resistances.
All alloying elements are maintained in solid solution, which is
achieved by utilizing the beneficial effect of nitrogen in stabilizing the
austenite phase and suppressing the intermetallic phases [3]. N levels
may reach more than 0.5 wt.% in superaustenitic alloys. The primary
reason for raising the alloy levels in austenitic stainless steels is to
provoke an enhancement in the resistance against pitting and crevice
corrosion under acidic and chloride environments. However, the
application of austenitic stainless steels as a bearing surface is severely
limited by their very poor wear and friction characteristics [5].
Low temperature plasma-nitriding (b500 °C) opens new possibil-
ities for improving greatly the tribological performance of austenitic
stainless steels whilst retaining, or even enhancing, the excellent
corrosion resistance of the untreated material. These benefits have
been reported previously in numerous publications regarding plasma-
nitriding treatments which led to the formation of a hard and wear
resistant layer called expanded austenite (γN) [6–10]. However, there
is very little knowledge about the effects on the tribological properties
of plasma-nitrided SASS samples. In this work, UNS S31254 SASS
samples were plasma-nitrided at three different temperatures (400,
450, and 500 °C), for 5 h, and the resistances of the modified surfaces
against wear and corrosion were investigated.
2. Materials and methods

⁎ Corresponding author.
E-mail addresses: codoico@gmail.com (F.A.P. Fernandes), stenioheck@usp.br
(S.C. Heck), pereira-ricardo@hotmail.com (R.G. Pereira), capicone56@yahoo.com.br
(C.A. Picon), nascente@ufscar.br (P.A.P. Nascente), castelet@sc.usp.br (L.C. Casteletti).
The superaustenitic stainless steel investigated in this work is a
commercially available material, UNS S31254 (ASTM A276), with a
nominal composition given at Table 1.

0257-8972/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2010.02.064
3088 F.A.P. Fernandes et al. / Surface & Coatings Technology 204 (2010) 3087–3090
Table 1
Nominal chemical composition (wt.%) of the UNS S31254 steel.
C Mn P S Si Cr Ni Mo N Cu
0.020 1.00 0.03 0.01 0.8 19.5– 17.5– 6.0– 0.18–
20.5 18.5 6.5 0.22
UNS S31254 SASS samples were prepared according to conven-
tional metallographic techniques, which result in a surface roughness
of about 0.08 µm (Ra), and then were plasma-nitrided. The samples
were cleaned inside the plasma chamber by argon sputtering under a
pressure of 500 Pa, at a temperature 50 °C lower than the plasma-
nitriding temperature, for 30 min. The plasma treatments were done
using the direct current method with the following conditions: a gas
mixture of 80 vol.% H2 and 20 vol.% N2, a pressure of 500 Pa,
temperatures of 400, 450 and 500 °C, and time period of 5 h. The
plasma-nitriding temperature was obtained by a thermocouple
attached to the sample holder.
The plasma-nitrided SASS samples were characterized by optical
microscopy, micro-hardness measurements, X-ray diffraction analy-
sis, and wear and corrosion tests. The microstructural analysis was
carried out with a Zeiss Axiotech optical microscope using the
interference contrast technique after etching the samples with
nitromuriatic acid. The measurements of Vickers and Knoop micro-
hardness were performed using a Buehler digital equipment with a
load of 25 gf and applied time of 10 s. Also a Brinell indentation test
was carried out on the nitrided samples in order to evaluate the
resultant crack network aspect. The indentation was performed with
15.625 kg using a 2.5 mm steel sphere applying the load for 10 s.
The X-ray diffraction patterns were obtained on the surface of the
samples using Rigaku Gergerflex equipment with scanning angles
ranging from 30 to 100°. The analyses were performed using copper
Kα radiation and continuous scanning with a speed of 2°/min.
Micro-wear tests were performed in a fixed ball machine without
the use of abrasive using a 52100 steel sphere of 25.4 mm in diameter.
The rotation speed and load were 500 rpm and 245 g (2.45 N),
respectively. Consecutive wear scars were produced with test times of
5, 10, 15, and 20 min in order to obtain the volume loss curve. The
removed volume (V) of each wear crater and its depth (h) were
calculated according to the following equations:
π⋅d4
V≈ ; for dbbR
64⋅R
rffiffiffiffiffiffiffiffi
V prevented the acquisition of the micro-hardness profiles for this
h≈ ; for hbbR
π⋅R
where d is the scar diameter and R the sphere radius.
Corrosion tests were performed employing an electrochemical cell
in order to obtain the potentiodynamic polarization curves. The cell
contains a reference electrode of saturated calomel (SCE) and a
Fig. 1. Cross-section optical micrographs of the SASS samples which were plasma-nitrided at (a) 400 °C, (b) 450 °C, and (c) 500 °C for 5 h.
platinum auxiliary electrode. The electrolyte employed was natural
sea water (pH 8). For monitoring the potential and current, a VGSTAT-
302 Autolab potentiostat was used. The polarization curves of the
samples were obtained with a scanning speed of 1 mV/s in the range
0.50–
1.00 of − 0.8 to 1.5 V.
3. Results and discussion
Fig. 1 presents the cross-section optical micrographs of the
samples which were plasma-nitrided at 400, 450, and 500 °C for 5 h.
In all these micrographs, the white layer is shown, and it can be
observed that increasing the temperature causes an increase in the
layer thickness. For the plasma-nitriding temperatures of 400 and
450 °C (Fig. 1a and b), the formation of a white layer only is observed,
possibly the nitrogen expanded austenite, and for the plasma-
nitriding temperature of 500 °C, the formation of a dark layer is also
detected, possibly chromium nitrides, on top of the white layer.
Observing this peculiarity, it may be suggested that the white layer is
replaced by the dark layer by a mechanism of nitrogen saturation, due
to a high concentration of this element at that temperature. So this
secondary layer is formed later onto the white layer.
On Fig. 2 the X-ray diffraction patterns of the SASS substrate and
the plasma-nitrided samples at different temperatures are presented.
The untreated SASS contains diffraction peaks related to the gamma
(γ) iron phase, which is characteristic of austenitic stainless steels.
Nitriding at 400 °C yielded the appearance of some diffraction peaks
shifted to the left, which is a characteristic of a nitrogen expanded
austenite (γN) phase. At this temperature the layer is thin and the
diffraction peaks of the substrate also appear. X-ray diffraction
confirms the existence only of the nitrogen expanded austenite on
the sample nitrided at 400 °C (Fig. 1a). With an increase in nitriding
temperature (450 °C) the diffraction peaks of the substrate disappear
due to the increase of the layer thickness. Although the optical
micrograph on Fig. 1b shows that only a white layer is present, X-ray
diffraction indicates that chromium nitrides are also present.
Moreover, the expanded austenite is also detected. Further increase
in nitriding temperature (500 °C) causes the expanded austenite
diffraction peaks to diminish, and more CrN and Cr2N peaks are
detected, which clearly indicates the precipitation of these nitrides.
This confirms that the dark layer formed onto the white expanded
austenite is a mixture of chromium nitrides.
Fig. 3 shows the micro-hardness profiles for the SASS samples
ð1Þ
which were plasma-nitrided at 450 and 500 °C. The low thickness of
the layer formed on the SASS sample treated at 400 °C (Fig. 1a)
ð2Þ sample.
The sample which was nitrided at 450 °C presented a hardness
value around 1400 HV, near the surface region, and reached the
substrate hardness value at a depth of approximately 10 µm. Some
researchers reported that the chromium nitride layers formed on top
of the expanded austenite in austenitic stainless steels (AISI 304 and
 F.A.P. Fernandes et al. / Surface & Coatings Technology 204 (2010) 3087–3090 3089

Fig. 2. X-ray diffraction patterns of the non-nitrided and plasma-nitrided SASS samples.
Fig. 4. Volume lost as a function of sliding distance.

316) possess higher hardness values than those measured for the γN increasing traveled distance for all plasma-nitriding conditions. Also,
phase [11,12]. However, in this work it was observed that the the wear rate, for nitrided samples, increased as the surface Knoop
chromium nitride layer formed on the SASS sample which was hardness increased.
plasma-nitrided at 500 °C presented lower hardness values than that
of the expanded austenite (Fig. 3).
The Knoop micro-hardness indentations, performed on the top of
each nitrided sample, increased as the temperature was increased
from 400 to 500 °C. Nitriding at 400 °C showed an average surface
Knoop hardness of 873 ± 73HK, at 450 °C the hardness was 1553 ±
76HK and for 500 °C, 1717 ± 182.
Fig. 4 presents the wear volume loss curves which were obtained
during the tribological characterization in dry sliding for all plasma-
nitrided SASS samples and the substrate itself. The worn volumes
were calculated based on Eq. (1) with the crater diameters. A decrease
in wear values for all plasma-nitrided SASS samples in comparison
with the substrate value is observed. The lower wear rate value was
obtained for the sample which was plasma-nitrided at 400 °C; the
second value was associated to the sample treated at 450 °C. The
higher wear rate value was measured for the sample treated at 500 °C,
and this could be due to a greater fragility detected for this sample, as
can be observed in Fig. 5, which depicts Brinell indentations on the
SASS samples that were plasma-nitrided at 400 and 500 °C. The worn
volume values shown in Fig. 4 indicate a tendency of stabilization with

Fig. 5. Brinell indentations on the SASS samples which were plasma-nitrided at (a) 400 °C
Fig. 3. Micro-hardness profiles for the plasma-nitrided SASS samples. and (b) 500 °C.
3090 F.A.P. Fernandes et al. / Surface & Coatings Technology 204 (2010) 3087–3090
Table 2
Scar depth (h) values obtained after 20 min of wear testing and nitriding layer
thicknesses (e).
Sample h (µm) — 20 min
SASS 31 ± 1
(400 °C/5 h) 9±1
(450 °C/5 h) 11.4 ± 0.5
(500 °C/5 h) 21.8 ± 0.9
The sample which was plasma-nitrided at 400 °C shows a larger
Brinell indentation than that which was treated at 500 °C. This
indicates a lower surface hardness, although no visible cracks are
observed around the impression carried out on the sample which was
plasma-nitrided at 400 °C. Analyzing the Brinell indentation per-
formed on the SASS sample which was plasma-nitrided at 500 °C, the
formation of a crack network can be observed, shown by the arrows in
Fig. 5b. According to the wear volume tendency, observed in Fig. 4,
and the Brinell indentations, displayed in Fig. 5, there is an indicative
higher fragility for the layer produced at 500 °C.
Table 2 lists the wear scar depth values and the layer thickness (e)
values obtained after 20 min (800 m) of wear testing for the
untreated SASS sample, for comparison, and the SASS samples
which were plasma-nitrided at 400, 450, and 500 °C for 5 h. The
h values were obtained using Eq. (2).
Based on these calculations, it should be noticed that after the
wear tests were done, all the plasma-nitrided layers had been
perforated. Despite the layer disruption during the sliding, the wear
depth values for the SASS samples which were plasma-nitrided at 400,
450, and 500 °C are 3.4, 2.8, and 1.4 times less than the substrate's
depth, respectively. This shows that for all plasma-nitriding condi-
tions there is an increase in wear resistance, and even after
perforation of the modified layers, the layer/substrate entirety
maintains its wear resistance.
Fig. 6 displays the potentiodynamic polarization curves obtained
under natural sea water immersion of the untreated SASS sample and
the samples which were plasma-nitrided at 400, 450, and 500 °C for
5 h. The results obtained by analyzing these polarization curves are
presented at Table 3.
The comparison of the tabulated data shows that the corrosion
potentials are smaller for the plasma-nitrided samples as compared to
the substrate (untreated sample). Increasing plasma-nitriding tem-
perature causes an increase in the corrosion potentials and corrosion
currents. The SASS sample treated at 400 °C presents the lowest
corrosion current. The corrosion rates calculated using the Tafel
Fig. 6. Potentiodynamic polarization curves of the untreated and plasma-nitrided SASS
samples.
Table 3
Corrosion parameters obtained by analyzing the polarization curves.
Sample Ecor (mV) Icor (A) Vcorr (mm/year)
e (µm)
SASS − 463 5.12 × 10− 7 7.36 × 10− 3
– (400 °C/5 h) − 298 5.44 × 10− 8 7.82 × 10− 4
4.5 ± 0.3 (450 °C/5 h) − 266 6.27 × 10− 7 3.15 × 10− 3
10 ± 1 (500 °C/5 h) − 265 1.54 × 10− 6 2.21 × 10− 2
22 ± 2
parameters indicate that the corrosion rate increases with increasing
temperature. Thus the sample which was plasma-nitrided at 400 °C
for 5 h presents the highest corrosion resistance for immersion into
natural seawater.
4. Conclusions
Plasma-nitriding of UNS S31254 superaustenitic stainless steel
samples produced continuous and homogeneous layers composed of
mainly expanded austenite (γN), for nitriding temperature of 400 °C,
and chromium nitrides and expanded austenite, for the nitriding
temperatures of 450 and 500 °C. This outermost chromium nitride
layer (obtained after nitriding at 500 °C) forms on top of the γN layers.
The rise of nitriding temperature produced an increase in surface
Knoop hardness, which in turn causes an increase in wear rate. The
SASS sample which was plasma-nitrided at 400 °C presents the best
tribological behavior among all nitriding conditions. The improve-
ment on the wear behavior occurs probably due to the increase in
layer fragility for temperatures from 400 to 500 °C. Although the
samples treated at 450 and 500 °C present higher corrosion potentials,
the corrosion rate increases with increasing temperature; thus, the
sample treated at 400 °C presents the highest corrosion resistance for
immersion into natural seawater.
Acknowledgements
The authors would like to thank CAPES, for the scholarships
granted to F.A.P. Fernandes and S.C. Heck, and to CNPq, for a research
grant (process PDS 150799/2008-0).
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