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Surface & Coatings Technology 202 (2008) 2577 – 2583

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Improvement of corrosion and wear resistances of AISI 420 martensitic

stainless steel using plasma nitriding at low temperature
Yun-tao Xi ⁎, Dao-xin Liu, Dong Han
Corrosion and Protection Research Lab, Northwestern Polytechnical University, Xi'an 710072, China
Received 10 June 2007; accepted in revised form 18 September 2007
Available online 3 October 2007

Abstract

The influence of low temperature plasma nitriding on the wear and corrosion resistance of AISI 420 martensitic stainless steel was investigated.
Plasma nitriding experiments were carried out with DC-pulsed plasma in 25% N2 + 75% H2 atmosphere at 350 °C, 450 °C and 550 °C for 15 h.
The composition, microstructure and hardness of the nitrided samples were examined. The wear resistances of plasma nitrided samples were
determined with a ball-on-disc wear tester. The corrosion behaviors of plasma nitrided AISI420 stainless steel were evaluated using anodic
polarization tests and salt fog spray tests in the simulated industrial environment.
The results show that plasma nitriding produces a relatively thick nitrided layer consisting of a compound layer and an adjacent nitrogen
diffusion layer on the AISI 420 stainless steel surface. Plasma nitriding not only increases the surface hardness but also improves the wear
resistance of the martensitic stainless steel. Furthermore, the anti-wear property of the steel nitrided at 350 °C is much more excellent than that at
550 °C. In addition, the corrosion resistance of AISI420 martensitic stainless steel is considerably improved by 350 °C low temperature plasma
nitriding. The improved corrosion resistance is considered to be related to the combined effect of the solid solution of Cr and the high chemical
stable phases of ɛ-Fe3N and αN formed on the martensitic stainless steel surface during 350 °C low temperature plasma nitriding. However,
plasma nitriding carried out at 450 °C or 550 °C reduces the corrosion resistance of samples, because of the formation of CrN and leading to the
depletion of Cr in the solid solution phase of the nitrided layer.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Plasma nitriding; Martensitic stainless steel; Wear; Corrosion

1. Introduction
The martensitic stainless steel AISI 420 has been widely
used in manufacturing turbine blades and valve parts for its high
corrosion resistance, shock resistance and high plasticity.
However, low hardness and poor wear resistance sometimes
limit its industrial applications [1–3]. Nitriding as an effective
technique to improve the surface hardness and wear resistance
of steels, including stainless steel, has been developed for many
years. For example, nitriding of austenitic stainless steels at a
temperature above 500 °C can significantly improve the surface
hardness and wear properties. However, corrosion resistance of
the austenitic stainless steel is dramatically reduced after
⁎ Corresponding author. Tel.: +86 29 88491479, +86 29 13572914836.
E-mail addresses: sdxyt1978@mail.nwpu.edu.cn, sdxyt1978@163.com
(Y. Xi).
0257-8972/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.09.036
nitriding due to the formation of CrN and then the depletion
of chromium in the matrix of the nitrided layer [4].
Some later studies show that the formation of chromium
nitride can be avoided if nitriding temperature is lowered to
approximately 400 °C to make the mobility of the chromium to
be restricted. Meanwhile, it is also found that an expanded
austenite called γN or S-phase can be formed simultaneously in
the nitrided layer. Due to the superb properties of the S-phase,
the low temperature nitrided austenitic stainless steel has a very
high surface hardness, a good wear resistance, and more
importantly, an excellent corrosion resistance [4,5]. In recent
years, many studies have been performed to improve the low
temperature plasma nitriding technology for austenitic stainless
steels and to extend its industrial applications.
In contrast, only a few studies have been conducted so far on
the low temperature plasma nitriding of martensitic stainless
steels, especially AISI 420[1,3,6]. Although Kim [7] reported
2578 Y. Xi et al. / Surface & Coatings Technology 202 (2008) 2577–2583
Table 1
Parameters for plasma nitriding treatments
Parameter Sputter cleaning Plasma nitriding
Temperature (°C) 250 350; 450; 550
Voltage (V) 400 600
Current density (mA·cm− 2) 0.8 1.2
Total pressure (Pa) 200 600
Time (h) 1 15
Pulse duration (μs) 50 50–300
Pulse pause (μs) 300 100–500
Treatment gas (vol) 20% H2 + 80% Ar 75% H2 + 25% N2
that the expanded martensite could also be found in the nitrided
layer of such steel at nitriding temperatures around 350 °C–
400 °C, the wear and corrosion properties of them and
especially, the influences of the formed expanded martensitic
have not been reported in publications yet.
In the present work, an AISI 420 martensitic stainless steel
was DC-pulsed plasma nitrided at different treatment tempera-
tures. The metallurgical structures as well as microhardness
profiles, wear and corrosion behavior of the surface nitrided
layer are evaluated, analyzed and discussed.
2. Experimental procedures
The chemical composition (wt.%) of the substrate material
AISI 420 martensitic stainless steel is as follows: C, 0.19; Si,
0.28; Mn, 0.20; S, 0.007; P, 0.028; Cr, 12.65; Cu, 0.11; Ni, 0.12;
Fe, balance. The material was annealed at 860 °C for 4 h,
followed by oil quenching at 970 °C for 3 h and tempering at
670 °C for 6 h. Disk-type samples of 30 mm in diameter and
10 mm in thickness were cut from a bar. Before nitriding, the
sample surfaces were fine ground using 1200 grit SiC paper and
mechanically polished. Finally, the surfaces were thoroughly
degreased with acetone and ultrasonically cleaned.
The samples were placed on the sample holder of the DC-
pulsed glow discharge plasma nitriding equipment, behaving as
a cathode with respect to the chamber wall. Sputter cleaning
was performed in 80% Ar + 20% H2 atmosphere at about 250 °C
for 1 h, which would remove the oxide layers formed on the
surface of the samples. Then, the AISI 420 martensitic stainless
steel samples were plasma nitrided in 25% N2 + 75% H2
atmosphere at 350 °C, 450 °C and 550 °C for 15 h, and the
chamber pressure was controlled at 600 Pa. The temperature of
plasma nitriding was controlled to an accuracy of ±5 °C, using a
photoelectric thermometer. After the completion of the nitriding,
samples were cooled in the chamber to room temperature under
flowing nitrogen to protect surface from oxidation. The param-
eters used in experiment are given in Table 1.
The cross-sectioned samples were used to examine the
composition and microstructure of the nitrided layers formed
on the AISI 420 martensitic stainless steel at different temper-
atures with a XJL-03 optical microscopy (OM) and a X'pert-
PRO X-ray diffraction (XRD) apparatus. The microhardness of
the nitrided layer was measured using a HV-1000 Knoop micro-
hardness tester with a load of 0.245 N.
Sliding wear test was carried out using a ball-on-disc wear
tester without lubrication. During test, the stainless steel disc
rotated against a stationary Si3N4 ball of 4.75 mm in diameter. A
sliding speed of 6.91 m/min was used in test under 4.985 N
constant load. The wear loss was measured with an analytical
balance (accuracy of 0.1 mg). The wear property was evaluated
by measuring the width of the sliding tracks left on the sample
surface using a HITACHI S-570 scanning electron microscope
(SEM), and the wear morphology was also observed.
A PARSTAT2273 electrochemical measuring system with a
flat cell was used to evaluate the electrochemical behavior of
samples. The flat cell is a three-electrode set-up consisting of a
saturated calomel reference electrode (SCE), a platinum auxiliary
electrode and a working electrode (sample). The scanning poten-
tial was in the range of −0.6 to +0.8 V, and the scanning rate was
0.166 V/s. The test solution (pH = 3) consisted of 5.0 wt.% NaCl
and some H2SO3 maintained at 25 ± 2 °C in order to simulate the
industrial atmosphere environment.
Corrosion test was performed using salt fog spray test in
accordance with ASTM B117. The solution used for salt spray
was the same as the electrochemical test. The salt fog spray test
was conducted continuously, the test temperature was main-
tained at 35 ± 2 °C,and the humidity was maintained at 94 ± 4%.
Samples were placed in testing chamber at an angle of 15° to the
vertical with the unprotected face upwards. During testing
visual inspections were performed once every 24 h. On the basis
of microscopic observation and color metallography, the cor-
rosion resistance of samples was analyzed.
3. Results and discussion
3.1. Microhardness
The microhardness was measured along depth on the cross-
section of samples. As shown in Fig. 1, the microhardness of the
substrate was 289HK0.025, while that of the nitrided layers were
higher than 1000HK0.025, and the lower the nitriding temper-
ature, the higher the microhardness of the nitrided layer. The
microhardness of the 350 °C nitrided layer was about 4.3 times
that of the substrate. In addition, in a certain depth (about
100 μm) underneath the nitrided sample surface, the micro-
hardness of the substrate is reduced gradually with depth. It is
Fig. 1. Microhardness profiles of nitrided samples.
 Y. Xi et al. / Surface & Coatings Technology 202 (2008) 2577–2583
Fig. 2. Optical micrograph of sample nitrided at 450 °C.
considered that this kind of microhardness distribution is related
with nitrogen diffusion layer.
3.2. Microstructure
The metallographic analysis showed that the surface of all
samples nitrided at different temperatures consisted of two
layers: a compound layer at the top and a nitrogen diffusion
layer beneath. The etching examination showed that a clear
boundary existed between the compound layer and the nitrogen
diffusion layer for all the nitrided samples, as shown in Fig. 2. It
is obvious that the compound layer and the nitrogen diffusion
layer are corroded at different rates. The average thicknesses of
the compound layers were measured to be about 90 μm, 105 μm
and 130 μm for the 350 °C, 450 °C and 550 °C nitrided samples
respectively. However, the depth of diffusion zone could not be
measured with SEM since there was no clear boundary between
the diffusion layer and the substrate.
Fig. 3. X-ray diffraction patterns for the untreated and plasma nitrided AISI420 stainless steel.
2579
The phase compositions in the nitrided layer were analyzed
with XRD using Cu-Kα radiation. Fig. 3(a) shows that the
untreated sample has two diffraction peaks of α (110) and α
(200) in the range of 30°–75°. Fig. 3(b) indicates that the
350 °C nitrided surface mainly consists of ɛ-Fe3N iron nitride.
At 42.8° in Fig. 3(b), there was a diffraction peak of super-
saturation solid solution of nitrogen, and this peak could not be
matched with any possible phases including iron, iron nitride
and chromium nitride in the nitrided surface. But it could be
considered as the expanded martensite suggested by Kim [7],
and indicated as αN. Solid solution of nitrogen has expanded the
lattice structure of α-Fe and shifted the (110) peak (44.8°)
toward a lower diffraction angle (42.8°). These αN and ɛ-Fe3N
phases led to the high surface hardness values that can be
observed in Fig. 1. No CrN peak was detected by XRD analysis,
which confirms that 350 °C nitriding prevents the formation of
chromium nitride in the surface layer of AISI 420 stainless steel.
The phase composition in 450 °C nitrided surface layer was
dominantly γ′-Fe4N, and the amount of ɛ-Fe3N was much less
than that in the 350 °C nitrided surface (Fig. 3(c)). Chromium
nitride precipitate was detected in this nitrided surface. The
expanded martensite αN could not be positively determined
since the peaks of αN overlapped with those of CrN or ɛ-Fe3N
phase, even though αN phase could still exist in the 450 °C
nitrided surface [6].
The amount of γ′-Fe4N in 550 °C nitrided surface layer was
further increased, and the amount of ɛ-Fe3N was decreased
apparently. So the peaks of ɛ-Fe3N phase almost disappeared
(Fig. 3(d)). The αN diffraction peak (42.8°) disappeared too and
the CrN was detected in the nitrided layer. It is believed that
nitrogen will react with Cr in the steel to form CrN precipitates
directly during 550 °C nitriding. Therefore, the amount of
nitrogen in solid solution is reduced, and the lattice expansion is
diminished, thus, the XRD peak is shifted back to the position
of α-Fe (44.8°).
2580 Y. Xi et al. / Surface & Coatings Technology 202 (2008) 2577–2583
Fig. 4. Corroded surfaces morphologies of samples after 120 h salt fog corrosion
(a) untreated; (b) 350 °C; (c) 450 °C; (d) 550 °C.
3.3. Salt fog spray tests
The corroded surface morphology of the untreated and
nitrided samples after 120 h salt fog testing is shown in Fig. 4.
The red rust and severe pitting corrosion can be seen on the
450 °C nitrided sample, the 550 °C nitrided sample as well as
Fig. 5. Surface morphologies of the salt spray tested samples after removing
corrosion products (a) untreated; (b) 350 °C nitrided; (c) 450 °C nitrided;
(d) 550 °C nitrided.
Fig. 6. Polarization curves of untreated and plasma nitrided AISI420 in 5%
NaCl + H2SO3 solution (pH = 3).
the substrate sample, and the most severe corrosion occurs on
the 550 °C nitrided sample. However, pitting corrosion behavior
of the AISI 420 stainless steel nitrided at 350 °C is improved
significantly, as seen in Fig. 4(b).
Fig. 5 shows the surfaces morphology of the untreated and
nitrided samples after salt spray tests and followed by removing
corrosion products. As is the case for Fig. 4, the 550 °C nitrided
sample corrodes most severely, and a lot of large and deep
corrosion pits can be seen on the surface. The corrosion pits on
the 450 °C nitrided samples are smaller in size, and more
extensive in distribution. The untreated samples and 350 °C
nitrided samples also suffer pitting corrosion, however, the
corrosion pits on the 350 °C nitrided samples are smaller and
less than those on the untreated sample.
It is well known that both Cr and N alloy elements, which are
added to stainless steel, are effective to enhance the resistance to
localized corrosion [4]. The chromium can combine with
oxygen to form a dense and continuous protective oxide film on
the surface, and mitigate the corrosion attack to a certain extent.
The nitrogen will dissolve during corrosion process and react
with H+ in solution to form the NH4+ [8]. Owing to the cathodic
reaction ([N] + 4H+ + 3e− → NH4+), the local pH increase allows
to facilitate the re-passivation. However, the beneficial effect of
both nitrogen and chromium can be taken only when they are in
solid solution and the concentration is high enough, or at least in
single phase. Once CrN forms, the nitrogen and chromium in
the solid solution of the nitrided layer will be depleted, which
prevents the formation of passivating films on the surface and
then deteriorates the corrosion resistance of the stainless steel [9].
The 450 °C and 550 °C nitriding decrease the corrosion resistance
of AISI 420 steel samples only because of the formation of
chromium nitride and the depletion of Cr in the solid solution of
the nitrided layers. However, the 350 °C plasma nitriding treat-
ment prohibits the formation of CrN, promotes the formation of
high chemical stable phases of ɛ-Fe3N and αN on the nitrided
surface, therefore, improves the corrosion resistance of the AISI
420 steel significantly.
 Y. Xi et al. / Surface & Coatings Technology 202 (2008) 2577–2583
Fig. 7. Corrosion morphologies of samples after electrochemical behavior tests in
5.0 wt.% NaCl + H2SO3 solution (pH = 3) (a) untreated; (b) 350 °C; (c) 550 °C.
3.4. Electrochemical behavior tests
Fig. 6 shows the anodic polarization curves for untreated and
plasma nitrided AISI 420 martensitic stainless steel samples in
5.0 wt.% NaCl + H2SO3 solution (pH = 3). From Fig. 6, it can be
seen that the untreated sample does not have an evident
Fig. 8. Wear morphologies of the untreated and nitrided samples (a)(b) untreated; (c)(d) 350 °C nitrided;(e)(f) 550 °C nitrided.
2581
passivation region, and the corrosion potential (Ecorr) is −0.58 V.
The 550 °C nitrided sample does not have a passivation region
either due to the formation of CrN and the depletion of Cr in the
solid solution of the nitrided layer, and is accompanied by
localized corrosion. However, for the 350 °C nitrided sample the
corrosion potential (Ecorr) is −0.52 V, and the polarization curve
shows an evident passivation region. The polarization curves in
Fig. 6 indicates that the pitting potential is −0.05 V for the 350 °C
nitrided sample, much higher than −0.58 V for the untreated steel
and −0.55 V for the 550 °C nitrided sample.
The corrosion morphologies of samples after electrochemical
behavior tests are compared in Fig. 7. The visual and microscopic
examinations of the corroded surface of different samples reveal
that the untreated sample is severely damaged by pitting corrosion
during electrochemical behavior test. The corrosion pits of
various sizes and shapes can be clearly seen, as shown in Fig. 7(a).
The surface of 550 °C nitrided sample is damaged more severely
than the surface of untreated sample, and in corroded region a
wide and deep groove is formed (Fig. 7(c)). Fig. 7(b) shows that
the corrosion pits on the 350 °C nitrided sample surface are
smaller and less than those on other samples. Consequently, the
pitting corrosion resistance of AISI 420 martensitic stainless steel
is evidently improved using 350 °C low temperature plasma
nitriding. The results of the electrochemical behavior test are in
accord with the results of salt fog spray tests.
3.5. Sliding wear tests
As mentioned above, the sliding wear behaviors of the un-
treated and nitrided samples are evaluated using a ball-on-disc
2582 Y. Xi et al. / Surface & Coatings Technology 202 (2008) 2577–2583
wear tester. The width of the wear scar and the loss of weight of
samples were measured using SEM and the analytical balance
separately after testing at a load of 4.985 N for 30 min. The
weight loss after 30 min wear test are 4.33 mg, 0.13 mg and
0.21 mg for the untreated sample, the 350 °C and 550 °C
nitrided samples respectively. The wear scar width of the
untreated samples is 0.55 mm, it is 3.1 times that of the 350 °C
nitrided sample and 2.9 times that of the 550 °C nitrided sample.
The micrographs of the wear tracks on the surfaces of the
untreated and nitrided samples are shown in Fig. 8. The
characteristic of the worn surfaces reveals quite different wear
behaviors between untreated and nitrided samples. The
untreated sample suffers severe wear. Metallic wear debris
and heavily scored surfaces are observed from the very
beginning of the test. A mixture of adhesion, abrasion and
plastic deformation is observed in both the wear track and its
adjacent area. The parallel grooves and scratches on the surface,
typical damages for a plough wear mechanism, are shown in
Fig. 8(b). On the contrary, a basically smooth appearance with
very mild abrasive wear can be seen on the worn surfaces of the
350 °C and 550 °C nitrided samples, as shown in Fig. 8(d) and
Fig. 8(f). Little metallic wear debris can be observed in both the
wear track and the adjacent region. That is to say, the severe
metallic wear behavior is replaced by a much milder abrasive
wear behavior through plasma nitriding.
Typical friction coefficient versus wear time curves for
untreated and nitrided samples during sliding against a
stationary Si3N4 ball are given in Fig. 9. In steady wear states,
the values for the friction coefficient are 0.6 and 0.72
respectively for the 350 °C and 550 °C nitrided samples, and
about 0.8 for the untreated samples.
Compared with the untreated sample, both nitrided samples
exhibited a lower friction coefficient and a lower wear rate.
The improvement of tribological properties for plasma nitrided
AISI 420 steels is considered as a result of the combined
effects of the microstructure, the high surface hardness and
the high compressive residual stress in the nitrided layer. The
high surface hardness can resist the plastic deformation. The
super-saturated nitrogen in nitrided layer can introduce high
compressive residual stresses, which will tend to close the
formed microcracks or impede their formation during wear
[5,10].
Fig. 9. Friction coefficient of the untreated and nitrided samples.
4. Conclusions
(1) The microhardness of the AISI 420 steel is 289HK0.025,
while those of all nitrided layers are higher than
1000HK0.025. And increasing nitriding temperature can
increase the effective case depth but slightly decrease the
hardness of the nitrided case.
(2) The plasma nitriding can improve the wear resistance of
the AISI 420 steel. The anti-wear property of the steel
nitrided at 350 °C is much more excellent than that at
550 °C. The weight loss after 30 min wear test is 4.33 mg
for the untreated sample, while those for the 350 °C and
550 °C nitrided samples are only 0.13 mg and 0.21 mg
respectively. In steady wear states, the values for the
friction coefficient are 0.6 and 0.72 respectively for the
350 °C and 550 °C nitrided samples, and about 0.8 for the
untreated samples. The micrographs of the wear tracks on
the surfaces of samples show the severe metallic wear
behavior is replaced by a much milder abrasive wear
behavior through plasma nitriding. The improvement of
wear resistance is considered as the effects of microstruc-
ture, high surface hardness and high compressive residual
stresses of the nitrided layer. The high surface hardness
can resist the plastic deformation, and the high compres-
sive residual stresses can tend to close the formed micro-
cracks or impede their formation during wear.
(3) The corrosion resistance of AISI 420 martensitic stainless
steel can be improved using plasma nitriding at low
temperature. The pitting potential is −0.05 V for the 350 °C
nitrided sample, much higher than −0.58 V for the
untreated steel and −0.55 V for the 550 °C nitrided sample.
The corrosion pits on the 350 °C nitrided samples are
smaller and less than those on the untreated sample after
120 h salt fog spry testing. The improved corrosion
resistance is considered to be related to the combined effect
of the solid solution of Cr and the high chemical stable
phases of e-Fe3N and αN formed on the martensitic
stainless steel surface during 350 °C low plasma nitriding.
The Cr solid solution without Cr depletion can form a dense
and continuous protective oxide film on the surface to
protect from the corrosion of the environment. The αN
phase can promote the reaction of [N] → NH4+ and increase
the local pH to facilitate the re-passivation. When the
plasma nitriding temperature is 450 °C and 550 °C, the αN
phase decreases or disappears and the CrN is formed, which
results in the depletion of Cr in the solid solution phase of
the nitrided layer and then prevent the formation of a dense
and continuous oxide film on the surface. Therefore the
corrosion resistance of AISI 420 stainless steel decreases as
the nitriding temperature increases from 350 °C to 550 °C.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (no 50671085) and the National High-
Tech Research and Development Program of China (“863”
Program, 2007AA03Z521).
 Y. Xi et al. / Surface & Coatings Technology 202 (2008) 2577–2583
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