Corrosion Science 100 (2015) 121–132

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Study of plasma nitriding and nitrocarburizing for higher corrosion

resistance and hardness of 2205 duplex stainless steel
J. Alphonsa a , V.S. Raja b,∗ , S. Mukherjee a
a
Institute for Plasma Research, Bhat, Gandhinagar, Gujarat 382428, India
b
Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400076, India

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

Article history: 2205 duplex stainless steel despite possessing good corrosion resistance suffers from low hardness. With
Received 29 April 2015 a view to improve hardness and corrosion resistance, plasma nitriding and nitrocarburizing processes
Received in revised form 25 July 2015 were performed at 350, 400, 450 and 500 ◦ C for 4 h. Specimens treated at 400 ◦ C by plasma nitrocar-
Accepted 27 July 2015
burizing exhibits the highest corrosion resistant with a significant raise in surface hardness. At higher
Available online 31 July 2015
temperatures, specimens treated by these processes show poor corrosion resistance. This study high-
lights the difference in plasma nitriding behavior of the ferrite and austenite phases and not so different
Keywords:
behavior of these phases when subjected to plasma nitrocarburizing.
A. Stainless steel
B. EIS © 2015 Elsevier Ltd. All rights reserved.
B. SEM
C. Passivity

1. Introduction nitrocarburized surfaces may be attributed to the super saturation

of nitrogen and carbon [6,7].
Austenitic stainless steels are widely used for applications When compared with austenitic stainless steels, ferritic stain-
where corrosion resistance is a prime concern. These steels have less steels suffer from poor mechanical and corrosion resistance
excellent corrosion resistance due to the presence of chromium, properties due to their relatively soft ferritic matrix and lower
which forms a stable passive layer on the surface. However, these chromium content, thus limiting their practical applications [8].
steels find limited applications where a high wear resistance is Studies on plasma nitriding of ferritic stainless steels to improve
required in addition to corrosion resistance. Plasma nitriding of the wear and corrosion resistance properties have found that the
austenitic stainless steels at typical temperatures above 500 ◦ C diffusion of nitrogen is faster in the ferrite phase than in the austen-
results in improved surface hardness and wear resistance at the ite phase resulting in thick nitrided layers as compared to that of
cost of corrosion resistance [1]. This effect is due to the formation the austenitic stainless steels [9]. It has been observed that the
of chromium nitride (CrN) precipitates. As a result the chromium addition of nitrogen at low temperatures in X6Cr17 ferritic stain-
depleted region of the nitrided layer cannot form a protective pas- less steel produced expanded ferrite and Fe2 N(1−x) iron nitrides
sive film [2,3]. It has been established in earlier studies that when which was responsible for improving the corrosion resistance of
the plasma nitriding temperature is sufficiently low, a nitrogen this steel [10]. Further, Spies et al. also studied gas nitrocarburizing
expanded austenite, also known as ␥N phase is formed which pro- of ferritic stainless steel (X6Cr17) and reported that the nitro-
vides not only a significantly increased surface hardness and wear carburized layers consisted of expanded ferrite with embedded
resistance, but also much improved corrosion resistance [4,5]. Sev- nitrides and cementite when treated below 450 ◦ C [11]. To the
eral studies have also reported that the surface hardness, case author’s knowledge, no corrosion studies have been reported after
depth and corrosion resistant properties of austenitic stainless plasma nitrocarburizing on this steel.
steels can be further increased through plasma nitrocarburizing, Duplex stainless steels having a ferritic-austenitic microstruc-
where a small amount of carbon is introduced during the plasma ture are nowadays being used in a variety of applications within
nitriding. This enhanced corrosion resistance observed on plasma the refining and petrochemical industry, where high corrosion
resistance and mechanical properties are required. However, since
this steel has relatively low hardness and wear resistance, these
properties need to be improved, if they have to be considered
∗ Corresponding author. for use in highly stressed tribological systems [12]. Similar to the
E-mail address: [email protected] (V.S. Raja). studies on plasma nitriding on austenitic and ferritic stainless

http://dx.doi.org/10.1016/j.corsci.2015.07.014
0010-938X/© 2015 Elsevier Ltd. All rights reserved.
122 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132

steels, studies on plasma nitriding under low temperature (below which in turn heats up the specimens. Hence, to get the substrate
450 ◦ C) conditions on duplex stainless steels have also reported temperatures of 350, 400, 450, and 500 ◦ C, the bias voltage was
enhanced wear and corrosion resistant properties. This was adjusted from 400 to 550 V. The temperature of the specimens was
attributed to the presence of expanded austenite phase [13]. In measured by a J-type thermocouple with an accuracy of ±2 ◦ C of
spite of the austenite and ferrite phases being present in duplex the set value. The treatment duration was kept constant in both
stainless steel it was observed by Blawert et al. that after low- the processes for 4 h. After these processes, the bias voltage was
temperature plasma nitriding of duplex stainless steel by plasma reduced to zero and the specimens were cooled down to 180 ◦ C
immersion ion implantation method, the incorporation of nitro- in a nitrogen gas atmosphere to avoid oxidation before removing
gen led to the transformation of ferrite into an expanded austenite them from the vacuum chamber.
phase [14]. Contrary to this observation, Bielawski et al. and Chiu
et al. reported the formation of expanded ferrite and expanded 2.3. Surface and microstructural analysis
austenite in both ferrite and austenite phases of UNS S31803 duplex
stainless steel by gas nitriding and active screen nitriding process The polished specimens were etched with Kallings reagent (5 g
respectively [15,16]. Studies on the effect of carbon on phase tran- of CuCl2 + 100 ml HCl + 100 ml ethanol) to reveal the microstruc-
sition in SAF 2205 duplex stainless steel by gas nitriding, active ture. For studying the layer thickness and the surface morphologies
screen and plasma nitrocarburizing processes have also been done. after the polarization tests, the treated specimens were examined
It was further reported that in the nitrocarburized condition, the by LEO model 40i scanning electron microscopy (SEM). Energy
expanded austenite was supersaturated with nitrogen and carbon dispersive spectrometry (EDS) was used to measure the elemen-
and the duplex stainless showed better corrosion resistance when tal composition on the individual phases after the electrochemical
the treatment temperature was about 400 ◦ C [17–19]. In open liter- tests. Surface roughness was measured with the help of a portable
ature, only one study on plasma nitrocarburizing of duplex stainless Mitutoyo SJ-201 surface roughness tester with a track length of
steel is available [19]. The focus of the present current research 2 cm.
was to increase the hardness of the duplex stainless steel without
compromising with the corrosion resistance for applications which
2.4. Elemental analysis
demand these two properties.
In the present study, an effort was made to develop 2205 duplex
In order to determine the chemical composition of the untreated
stainless steel for high corrosion resistance as well as high hardness
surfaces and the treated cross-sectioned specimens, Jeol make,
by plasma nitriding and nitrocarburizing processes under various
JSM-7600F Field emission electron spectrometer (FESEM) equipped
treatment temperatures.
with wavelength dispersive spectrometer (WDS) was used.

2. Experimental procedures 2.5. X-ray diffraction (XRD)

2.1. Specimen preparation After plasma nitriding and plasma nitrocarburizing, the phases
were identified using a glancing incidence XRD (3000 PTS X-ray
Circular discs of 2205 grade duplex stainless steel having dimen- diffractometer) with Cu-K␣ radiation ( = 1.5406 Å) as the source
sions of 30 mm diameter and 5 mm thickness, cut perpendicular to and scanned from 30 to 90◦ . The 2◦ glancing angle was employed,
the axis of the rod were used as specimens in this study. 2205 grade since the modified layer formed at lower temperatures was too
duplex stainless steel consisted of 0.026% C, 4.60% Ni, 22.06% Cr, thin for the phases to be detected in the Bragg Brentano mode. The
0.69% Si, 1.74% Mn, 0.03% S, 0.045% P, 0.0130 % Ti, and 2.58% Mo, angle resolved GIXRD patterns were obtained using (X’pert PRO)
0.16% N by weight, with Fe being the balance. The samples were Panalytical, make X-ray diffractometer.
mechanically ground with SiC emery papers having a grit size of
240, 320, 400, and 600 followed by polishing with 1 ␮m diamond 2.6. Microhardness evaluation
paste and 0.5 micron alumina paste in order to obtain a final mirror
finish of a mean roughness Ra value better than 0.01 ␮m. Mitutoyo make (HM 200) micro Vickers hardness tester was
used to measure the surface hardness with 10 g load on both
2.2. Plasma nitriding and plasma nitrocarburizing austenite and ferrite phases before and after the treatments. This
load was adequate to obtain the measurements on individual
Both plasma nitriding (PN) and plasma nitrocarburizing (PNC) phases.
processes were conducted in a plasma nitriding setup as described
elsewhere [20]. The specimens were cleaned with acetone before 2.7. Electrochemical corrosion studies
placing them on the sample holder present in the vacuum chamber.
The sample holder acted as a cathode and the vacuum chamber wall Corrosion behavior of untreated, plasma nitrided and plasma
acted as an anode, which was also grounded. Initially, the vacuum nitrocarburized duplex steel specimens were studied using
chamber was evacuated to a base pressure of 8 Pa with the help a potentiodynamic polarization and electrochemical impedance
mechanical rotary pump. Prior to plasma processing, sputter clean- techniques. The setup consisted of Reference 600 Gamry poten-
ing was done using H2 gas at a pressure of 100 Pa and a temperature tiostat driven by software. The electrochemical tests were carried
of 250 ◦ C for 1 h to get rid of the surface oxide layer. For plasma out in a flat electrochemical glass cell having graphite as a counter
nitriding, a gas mixture consisting of 80% N2 and 20% H2 was used. electrode, a saturated calomel electrode (SCE) as a reference elec-
Whereas, for plasma nitrocarburizing, a gas mixture of 78% N2 , 20% trode and the specimen as the working electrode. A specimen area
H2 , and 2% C2 H2 was employed. In both the processes a constant of 2.85 cm2 was exposed to the solution. The electrochemical stud-
pressure of 500 Pa was maintained. During plasma nitriding and ies were carried out at ambient temperature (28 ◦ C). The tests were
plasma nitrocarburizing, under the influence of voltage bias, nitro- performed in freely exposed 3.5 wt.% NaCl solution, which is a very
gen, hydrogen and acetylene gases get ionized and accelerate to common environment for corrosion studies, unlike the deaerated
impinge on the specimens. The kinetic energy of these ions is con- 3.5 wt.% NaCl. After stabilizing the open circuit potential (OCP)
verted into thermal energy during this ion bombardment process, for 30 min, when the drift in the potential became negligible, the
 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132 123

Table 2
Thickness of layers formed after plasma nitriding and plasma nitrocarburizing
treated at different temperatures.

Process Temperature (◦ C) Layer thickness (␮m)

PN 400 3.2 (F),

450 1.8 (A)
500 4.8 (F),
4.0 (A)
30.0a
PNC 400 3.0a
450 4.6a
500 28.0a
a
Note that there was no variation in thickness in phases (F—ferrite: A—austenite).

measured thickness values of plasma nitrided and plasma nitrocar-

burized layers of the specimens treated at different temperatures
are summarized in Table 2. Since the layer thickness was very small
in case of specimens treated at 350 ◦ C, it was difficult to measure
Fig. 1. SEM micrograph of 2205 grade duplex stainless steel shows dual phases
the thickness of the layers of the individual phases and hence is not
having austenite (␥) and ferrite (␣) phases. mentioned in the Table 2. The table indicates that the thickness of
the modified layers increases with temperature and is marginally
potentiodynamic polarization scan was started, by setting a poten- lower in plasma nitrocarburized specimens compared to that of
tial of 500 mV below the OCP. Each experiment was repeated at the plasma nitrided specimens. A few other variations between the
least three times to check the reproducibility and the scatter in the plasma nitrided and plasma nitrocarburized specimens were also
data are reported. observed.
Electrochemical impedance spectroscopy (EIS) experiments The thickness of the layers over the two phases was found to
were carried out for all the specimens at open circuit potential after be different in the case of plasma nitrided specimens whereas
immersing for 30 min in 3.5 wt.% NaCl solutions. The AC amplitude such a difference was not found in the plasma nitrocarburized
applied for EIS measurement was ±10 mV in the frequency range specimens (Fig. 2a and c). Another point worth mentioning is
of 105 to 10−1 Hz with 10 points per decade. Gamry Echem Analyst that the plasma nitrided specimen treated at 500 ◦ C did not lead
EIS software was used to carry out the tests and to evaluate the to any difference in layer thickness between the two phases. In
impedance data. The frequency values were limited to 0.01 Hz as addition, the ferrite and austenite grains of plasma nitrided and
the system became unstable with further decrease in frequency. nitrocarburized specimens appeared dark as revealed in Fig. 2b
and d.
3. Results With the help of the schematic representations in Fig. 3 an
attempt has been made to explain the behavior of the alloy with
3.1. Characterization of the duplex stainless steel respect to the plasma nitriding and plasma nitrocarburizing on
duplex stainless steel at different temperatures. Fig. 3a show
Typical microstructure of 2205 duplex grade stainless steel thicker layers on the ferrite grains than on the austenite grains.
exhibiting dual phases (austenite and ferrite) is shown in Fig. 1. The same feature has been observed by Bielawski et al. [22]. The
In order to identify the phases, microhardness measurements and reason why ferrite exhibits higher thickness than the austenite can
WDS analysis were performed within the grains. The bright and be explained as follows. It has been reported that the diffusion of
dark grains were found to have hardness values of 370 ± 12 HV0.01 nitrogen in the ferrite phase of the duplex austenitic-ferritic steel
and 338 ± 15 HV0.01 respectively. Compositions of these bright and is higher than in the austenite phase [23]. This is because the BCC
dark regions obtained through WDS are shown in Table 1. Based on structure is more open than the FCC structure and as a consequence
the hardness values and the chemical compositions it can be sug- nitrogen exhibits higher diffusion coefficient in BCC lattice of fer-
gested that the dark phase belongs to ferrite and the bright phase rite than in FCC lattice of austenite phase. Moreover, the chemical
to the austenite phase. These are in conformity with the values potential of nitrogen in ferrite is considered to be lesser than that
reported by Blawert et al. [14]. The ferrite phase is darker than in the austenite phase enabling faster diffusion of nitrogen in the
the austenite phase, indicating its preferential dissolution tendency ferrite [24]. This is further confirmed from the WDS data shown
during etching [21]. in Table 3 which confirms that the nitrogen content in the ferrite
phase (13.09 wt.%, 36 at.%) is much higher than that in the austenite
3.2. Effect of temperature on layer thickness phase (8.56 wt.%, 26 at.%).
As, the temperature increases to 450 ◦ C (Fig. 3b), the tendency
Typical cross-sectional images of 400 and 500 ◦ C plasma nitrided (due to plasma nitriding) for the ferrite to transform to austenite
and plasma nitrocarburized specimens are shown in Fig. 2. The

Table 1 Table 3
Chemical composition in wt.% and microhardness values of the regions in the 2205 WDS analysis in wt.% obtained from different phases of plasma nitrided and plasma
duplex stainless steel. nitrocarburized layers in the cross sectioned specimens treated at 400 ◦ C.

Region Chemical composition in wt.% Hardness Phases inferred Treatment Phases Ni Fe Cr Mo N C

HV0.01
PN Austenite 3.39 66.62 17.39 0.903 8.57 0.94
Cr Ni Mo Ferrite 2.13 61.16 19.91 1.57 13.09 0.92

Bright 20.89 4.68 1.91 370 Austenite PNC Austenite 4.28 64.28 18.73 1.69 4.69 5.70
Dark 22.80 3.79 2.38 338 Ferrite Ferrite 3.77 67.75 21.19 1.98 2.73 2.55
124 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132

Fig. 2. Cross-sectional SEM images of duplex stainless steel, plasma nitrided at (a) 400 ◦ C (b) 500 ◦ C and plasma nitrocarburized at (c) 400 ◦ C and (d) 500 ◦ C.

Fig. 3. Schematic representation of differing temperature dependence on diffusion of nitrogen in austenite and ferrite phases of duplex stainless steel during plasma nitriding
at (a) 400 ◦ C (b) 450 ◦ C, and (c) 500 ◦ C and nitrogen and carbon during plasma nitrocarburizing at (d) 400 ◦ C (e) 450 ◦ C, and (f) 500 ◦ C (note: A—austenite phase, F—ferrite
phase).

phase increases and so the former acquires the characteristics of an overall increase in plasma nitrided layer thickness values as
the austenite phase with respect to nitrogen diffusion. As a result shown in Table 2. At 500 ◦ C, as seen in Fig. 3c, virtually no difference
the observed thickness difference between the ferrite and austen- between the ferrite and austenite grains was found with respect to
ite phases diminishes. This is attributed to the transformation of the growth kinetics.
ferrite into austenite when its nitrogen content exceeds a certain Contrary to plasma nitriding, plasma nitrocarburizing has
value as nitrogen is an austenite stabilizer [25,26]. At the same yielded a uniform nitrided layer across ferrite and austenite grains
time, the rise in temperature enhances the diffusion kinetics and in specimens treated at all temperatures as shown in Fig. 3d–f.
 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132 125

Fig. 4. (a) GIXRD patterns of plasma nitrided specimens treated at different temperatures (b) angle resolved GIXRD patterns of 400 ◦ C treated plasma nitrided specimens.

One of the possible reasons could be that the diffusion coefficient is interesting to note the position of the peaks corresponding to
of carbon in the austenite phase is higher than that of nitrogen ␥N is shifted toward the higher angles, indicating a drop in lattice
making the plasma nitrocarburized layer to grow faster in the parameter. This can be interpreted as a possible drop in the nitrogen
austenite phase [27]. The WDS analysis summarized in Table 3 content of the nitride layer along the depth.
show that the austenite contains much more carbon than in the fer- GIXRD patterns of plasma nitrocarburized specimens treated
rite phase. This is also true even with respect to nitrogen content. at 350, 400, 450, and 500 ◦ C are shown in Fig. 5a. The patterns
This behavior is in contrast to what was found in plasma nitrided showed a trend different from those of the plasma nitrided spec-
layers. imens as the GIXRD of 350 and 400 ◦ C treated specimens did not
show the presence of austenite peaks. Further, the peaks of plasma
3.3. Phase analysis nitrocarburized specimens are found to be shifted to a much lower
diffraction angle than those of the plasma nitrided specimens. As
Glancing incidence X-ray diffraction (GIXRD) patterns obtained the temperature was increased to 450 and 500 ◦ C, iron nitrides
with an incident angle of 2◦ are shown in Fig. 4a for the untreated along with chromium nitrides peaks were formed. It was difficult to
along with 350, 400, 450, and 500 ◦ C plasma nitrided duplex stain- determine whether the layer consisted of nitrides and/or carboni-
less steel specimens. As expected, the untreated duplex 2205 trides. XRD could not be used to rule out any of these possibilities
stainless steel shows the presence of both austenite and ferrite as the lattice parameters of iron nitrides and carbonitrides were
phases. nearly the same. However, it is reasonable to assume that these
On plasma nitriding at 350 and 400 ◦ C the specimens showed iron nitrides could contain carbon (Fe3 N(C)) as the plasma nitro-
a significant drop in peak intensities for the ferrite phase (Fig. 4a) carburized layer of specimen has been reported to contain carbon
revealing a possible transformation of a significant amount of fer- [30].
rite into austenite phase. New peaks, that are broad in nature Earlier studies reported the presence of bilayers in plasma
positioned at lower angles than the original peaks appeared in the nitrocarburized austenitic stainless steels, where the top and
GIXRD pattern. Such peaks are attributed to expanded austenite ␥N bottom layer consisted of nitrogen expanded austenite and car-
[28]. The position of these peaks of 400 ◦ C treated specimen was bon expanded austenite respectively [31]. Though, the WDS data
found to be at higher angle than specimen treated at 350 ◦ C. At 450 showed the presence of carbon in the plasma nitrocarburized lay-
and 500 ◦ C the peaks corresponding to the austenite phase disap- ers of duplex stainless steel, the metallography studies could not
pear and the peaks corresponding to CrN and Fe3 N phases appear. identify the existence of the bilayers, even after several attempts of
At these temperatures, the expanded austenite decomposes to form etching techniques. A similar observation of absence of dual layer
CrN and Fe3 N phases [29]. Moreover, the extent to which the CrN was also reported by Lee, where the presence of carbon was con-
forms at 500 ◦ C has been found to be higher than that formed at firmed by GDOES analysis [19]. In order to resolve this issue, angle
450 ◦ C. resolved GIXRD studies were carried out for the specimen treated
In the case of plasma nitrided specimens treated at 400 ◦ C, vari- at 400 ◦ C. The GIXRD patterns obtained at different glancing angles
ation in plasma nitriding along the specimen depth was analysed are shown in Fig. 5b. There is presence of carbon expanded austen-
by varying glancing angle as shown in Fig. 4b. As expected, at ite (␥C ) peaks, which are shifted to lower diffraction angles at higher
higher glancing angles, peaks corresponding to ferrite and austen- glancing angles indicative of a carbon rich layer closer to the sub-
ite phases of the substrate appear to be prominent. However, it strate. Thus, XRD confirms the presence of bilayers as has been
126 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132

Fig. 5. GIXRD and angle resolved patterns of plasma nitrocarburized duplex 2205 stainless steel (a) at different temperatures (b) at 400 ◦ C respectively.

reported for the plasma nitrocarburized austenitic stainless steel

[32].

3.4. Surface roughness and microhardness

After plasma nitriding and plasma nitrocarburizing at 350, 400,

450, and 500 ◦ C, a change in surface roughness of the specimens
was observed. Fig. 6a brings out the effect of temperature on the
roughness and reveals an increment in surface roughness with
increasing temperatures. This can be attributed to the sputtering
due to ion bombardment and the phases formed during the pro-
cesses [33]. There was no significant change in surface roughness
at and below 400 ◦ C due to precipitate free surfaces. However, at
450 and 500 ◦ C the surface roughness was high in plasma nitrided
specimens due to the presence of chromium and iron nitrides and
higher in plasma nitrocarburized specimens due to the presence of
iron carbonitrides.
The microhardness values of individual phases of plasma nitrid-
ing and plasma nitrocarburizing specimens are shown in Fig. 6b.
The 350 ◦ C treated specimen did not show any significant rise in
hardness in relation to the base alloy. This could be attributed to
the thin layer formed in this case and the consequent effect of
the substrate. On all the treated specimens an increase in hard-
ness with temperature was found. Between the two treatments
plasma nitrocarburizing has yielded a higher hardness values at all
these temperatures mainly due the carbon and nitrogen saturated
expanded austenite at 400 ◦ C and the presence of carbonitrides
above 400 ◦ C [34]. It was interesting to note that the microhard-
ness of ferrite phase was harder than the austenite phase despite
the fact that ferrite phase of the untreated specimen was softer than
the austenite phase. Similar reports were reported by Bielawski
et al. on gas nitrided 2205 duplex stainless steel [35]. This increase
is attributed to the high amount of nitrogen in the ferrite phase as
described above.

3.5. Corrosion studies

Fig. 6. (a) Surface roughness (The dashed line indicates that the initial surface
roughness). (b) Microhardness values obtained on austenite and ferrite phases after
Fig. 7a and b compares the open circuit potential and dynamic plasma nitriding and plasma nitrocarburizing treated at different temperatures.
polarization curves respectively of untreated and plasma nitrided
 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132 127

Table 4
Summary of Ecorr , icorr , ipass , ˇc , and Etrans /Epit for plasma nitrided and plasma nitrocarburized duplex stainless steel obtained in 3.5 wt.% NaCl. Standard deviation in the data
is shown.

Process Temperature (◦ C) Ecorr (mV vs. SCE) icorr (␮A cm−2 ) ipass (␮A cm−2 )(at 500 mV vs. SCE) ˇc (mV decade−1 ) Etrans /Epit (mV vs. SCE)

Untreated – −154 ± 3 0.25 ± 0.20 7.90 ± 0.30 −84.30 ± 20 996 ± 15

PN 350 −74 ± 4 0.01 ± 0.02 1.70 ± 0.2 −114.90 ± 6 1122 ± 20

400 42 ± 4 0.36 ± 0.03 2.80 ± 0.2 −140.0 ± 5 1153 ± 08
450 −288 ± 5 2.51 ± 1.10 164 ± 2 −90.00 ± 10 829 ± 30
500 −288 ± 3 4.06 ± 0.90 4301 ± 20 −105.90 ± 20 –

PNC 350 −68 ± 2 0.11 ± 0.90 5.51 ± 0.30 −64.50 ± 10 998 ± 30

400 280 ± 3 0.88 ± 0.30 1.38 ± 0.30 −181.00 ± 20 1093 ± 20
450 −312 ± 6 2.09 ± 0.90 325 ± 20 −146.00 ± 30 –
500 −392 ± 4 36.80 ± 2.00 4348 ± 150 −396.80 ± 30 –

lost its ability spontaneously due to 450 ◦ C treatment as inferred

from the active-passive transition of the anodic curve. The passive
current density of the alloy has significantly gone up. At 500 ◦ C the
alloy seems to have lost its passivation tendency quite significantly.
The above observations are in close agreement with the OCP data.
The effect of plasma nitriding on the anodic dissolution tendency of
the alloy was analysed by comparing its anodic current density val-
ues at different anodic potentials as no stable passive region were
found. Table 5 compares the anodic current densities of the alloy at
different anodic potentials for all the treatment conditions.
Subsequent to the polarization tests, the plasma nitrided spec-
imens were examined using SEM. In order to know if the pitting
occurred randomly or in preference at austenite or ferrite grains,
the specimens were lightly etched before examination. The SEM
images showed deeper and wider pits in the untreated specimen
than in treated specimens (Fig. 8a and b). The EDS analysis showed
that the pitting occurred preferentially within the austenite grains
(Cr: 20.36; Ni: 4.27; Mo: 1.63; Fe: 64.6; Mn: 2.49 and Si: 0.71 in
wt.%). In contrast to the above, the 500 ◦ C treated specimens suf-
fered extensive dissolution which is uniform in nature as shown in
Fig. 8c.
Fig. 9a and b show Nyquist and Bode plots of the untreated and
the plasma nitrided 2205 duplex stainless steel specimens respec-
tively. The Nyquist plots are characterized by a single capacitive
loop in all the cases. However the Bode phase angle plot for 500 ◦ C
treated specimen shows two phase angle maxima. So, two equiva-
lent circuits with single and two time constants were employed to
fit to the data (Fig. 10). In all the cases the chi- squared (2 ) values
were found to be in the range of 10−2 . However, the impedance data
of 450 ◦ C treated specimen fitted equally well for both the circuits.
For the reasons explained in the discussion sections, the model of
two time constants was fitted to the experimental data. The data so
obtained are summarized in Table 6 and the plots of Fig. 9a show
the fitment.
Fig. 11a and b compares the OCP the cathodic and anodic
polarization curves respectively of 2205 duplex stainless steel in
all the plasma nitrocarburized conditions. Except for the case of
Fig. 7. (a) Open circuit potential (OCP) as a function of time and (b) Potentiodynamic 400 ◦ C treatment, plasma nitrocarburizing does not seem to pro-
curves of untreated and plasma nitrided duplex stainless steels treated at different vide any additional resistance to either corrosion or pitting for the
temperatures in 3.5 wt.% NaCl solution. duplex stainless steel compared to the untreated specimen. The
anodic and the cathodic kinetics were analysed similar to that done
2205 duplex stainless steel specimens. Table 4 summarizes the for the plasma nitrided specimens. Table 4 summarizes the data.
electrochemical corrosion parameters such as corrosion potential Microscopy study of the polarized specimens revealed a similar
(Ecorr ), corrosion current density (icorr ), passivation current density trend of corrosive attack except that they showed lesser density of
(ipass ), and cathodic Tafel slope (ˇc ), transpassive potential/pitting pits than the plasma nitrided specimens (Fig. 12).
potential (Epit/trans ). The icorr values were obtained merely using Nyquist and Bode plots of untreated and plasma nitrocar-
cathodic Tafel region as uncertainties existed in the anodic polar- burized 2205 duplex stainless steel specimens along with the
ization curves. fitment, based on the equivalent circuits are shown respectively
Examination of the anodic curves showed that plasma nitrid- in Fig. 13a and b. As 450 and 500 ◦ C treated specimens showed
ing at 350 and 400 ◦ C has marginally improved the passivity of the two phase angle maxima the data corresponding to them were
alloy and at 450 and 500 ◦ C a significant loss in passivity. The alloy fitted for a two time constant equivalent circuit and the speci-
128 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132

Table 5
Polarization data showing ipass values taken at different potentials for the untreated, plasma nitrided and plasma nitrocarburized duplex stainless steel specimens treated at
different temperatures.
o
Process Temperature ( C) ipass (␮A cm−2 ) (at 100 mV vs. SCE) ipass (␮A cm−2 ) (at 300 mV vs. SCE) ipass (␮A cm−2 ) (at 500 mV vs. SCE)

Untreated – 0.22 1.11 7.90

PN 350 0.17 0.57 1.7

400 0.53 1.15 2.8
450 570 127 165
500 3648 5978 4300

PNC 350 1.2 2.74 5.51

400 – 0.33 1.38
450 62 163 342
500 4627 5164 4146

Table 6
Summary of electrochemical impedance spectroscopy parameters of untreated, plasma nitrided and plasma nitrocarburized duplex stainless specimens derived from the EIS
plots obtained after 30 min of exposure in 3.5 wt.% NaCl solution at OCP.

Process Temperature(◦ C) Qf (␮F cm−2 ) nf Rf (k cm2 ) Qdl (␮F cm−2 ) ndl Rp (k cm2 )

Untreated – – – – 109.5 0.91 46.0

PN 350 – – – 65.5 0.94 140.0

400 – – – 65.8 0.90 100.0
450 68.6 0.83 8.3 68.6 1.00 4.9
500 68.7 0.83 0.1 59.5 0.87 3.9

PNC 350 – – – 93.0 0.93 141.0

400 – – – 105.1 0.85 168.0
450 661 0.73 0.9 99.7 1.00 4.7
500 364 0.80 0.03 545.0 0.83 1.3

mens treated at lower temperatures (below and at 400 ◦ C) for a less steel indicate the possibility of the occurrence of these two
single time constant equivalent circuit. The data is summarized in reactions [38]. Because the tranpassive region corresponds to pit-
Table 6. ting, oxygen evolution and oxidation of Cr3+ to Cr6+ , the potential
corresponding to the inflection point is refereed as Epit/trans .
4. Discussion Plasma nitriding at 350 and 400 ◦ C has led to notable increase
in Ecorr and OCP values, but at 450 and 500 ◦ C it caused reduction
The main purpose of this study was to develop 2205 duplex in both these parameters. The above observations are reflected in
stainless steel having high corrosion resistance as well as high the anodic kinetics of the duplex stainless steel under these plasma
hardness through plasma nitriding and nitrocarburizing, as spe- nitriding conditions (Fig. 7a and b). Excepting a small increase in
cial applications demand this alloy having these two properties. ipass values, close to the Ecorr for 400 ◦ C treated specimens, both
As a consequence of plasma nitriding and nitrocarburizing, various 350 and 400 ◦ C treated specimens showed marginal improvement
phases are formed in the stainless steel, making the steel either in passivity over the entire range of anodic potentials (Table 5) in
prone to passivity or corrosion. Hence, there is a need to under- relation to the untreated specimen. These specimens show smaller
stand the relation between the phase formations, role of processing pits (∼2 ␮m) as compared to the untreated specimen (∼8 ␮m)
parameters and corrosion in this steel. This aspect is discussed in thus indicating that they possess better pitting resistance than
this section. the untreated specimen (Fig. 8a and b). In contrast, the specimen
treated at 500 ◦ C lost its passivity completely, while in the case
of 450 ◦ C treated specimen the spontaneous passivity is lost as
4.1. Plasma nitriding revealed by the active-passive transition of its anodic curve. The
alloy also shows secondary passivation corresponding to oxidation
The untreated 2205 duplex stainless steel specimen shows two of Cr3+ to Cr6+ [39]. The EIS data complements the alloy dissolution
inflection points at 438 mV (vs. SCE) and 962 mV (vs. SCE) in the kinetics as revealed by the anodic polarization curves (Table 6).
anodic polarization curve (Fig. 7b), Similar to those reported by Thus the Rp values of untreated, 350 and 400 ◦ C specimens were
Hussain et al. [36]. According to the authors, the first inflection point found to be 46, 140, and 100 k cm2 respectively. In contrast, the
corresponds to pitting in the austenite grains while the second to Rp values of 450 and 500 ◦ C specimens were 13.2 and 4.0 k cm2
pitting of the ferritic grains. However, our studies show that only respectively. From the Fig. 9 and Table 6, for 450 ◦ C treated speci-
the austenite phase suffered pitting even after completion of the mens though the bode phase angle revealed single phase maxima,
polarization test when the duplex stainless steel was subjected to an equivalent circuit of two time constant was used to fit the data
potentials beyond the second inflection points (Fig. 8a). The rea- as their ipass values were a two magnitude higher and impedance
son why the ferrite phase did not pit can be attributed to the fact values lower than that of the untreated specimens.
that it is rich in Cr and Mo (Table 1). Our observation that ferrite The loss in passivity and the consequent increase in icorr can be
is resistance to pitting is also supported by Mesquita et al. [37] in understood when the phases formed in the specimens are analysed.
a similar study on this steel. Since, the “so called” pitting poten- GIXRD results (Fig. 4a) show that 350 and 400 ◦ C treated speci-
tial 962 mV (vs. SCE) lies above the water decomposition potential mens contain only ␥N (an expanded austenite phase) and that of
at pH 7 (which is 572 mV (vs. SCE)), oxygen evolution as per the 450 and 500 ◦ C treated specimen show Fe3 N and CrN phases. As a
reaction 2H2 → 4H+ + 4e− + O2 is expected to occur. In addition, the consequence, the matrix has not been depleted of chromium in the
potential is sufficiently positive enough, for oxidation of Cr3+ to case of the 350 and 400 ◦ C plasma nitrided specimens [40–42]. In
Cr6+ . The shallow and small pits found on the surface of the stain-
 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132 129

Fig. 9. (a) Nyquist plots (inset: enlarged view) (b) Bode magnitude (top) and phase
angle (bottom) plots of untreated and plasma nitrided 2205 duplex stainless steel
specimens treated at different temperatures. Note the solid line refer to fitting.

Fig. 8. SEM images obtained after the polarization tests for (a) untreated (b) plasma
nitrided at 400 ◦ C (c) plasma nitrided at 500 ◦ C. The inset shows the location and
size of the pit.

other words, chromium remained evenly distributed at micro and

nano level in these two cases. The formation of CrN in the 450 and
500 ◦ C treated duplex stainless steel specimens causes Cr depletion
at micro and nano level depending on the size of the precipitates. Fig. 10. Electrical equivalent circuit models chosen for analysis of EIS spectra (where
While Fe3 N and CrN per se may not suffer higher dissolution than Rs is solution resistance, Rp is the polarization resistance associated with the charge
the untreated specimen, the chromium depleted regions of these transfer behavior, Qdl is the constant phase element of the double layer capacitance,
specimens can suffer extensive dissolution (Fig. 8c). Needless to Rf is the resistance provided by the active sites, Qf is the constant phase elements of
the active sites).
emphasize the fact that the extent of dissolution at these regions
130 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132

Fig. 11. (a) OCP plots and (b) potentiodynamic curves of untreated and plasma nitro-
carburized duplex stainless steels treated at various temperatures in 3.5 wt.% NaCl
solution.

Fig. 13. EIS plots of untreated and plasma nitrocarburized specimens treated at
different temperatures (a) Nyquist plots (inset: enlarged view) (b) Bode magnitude
(top) and phase angle (bottom) plots. Note the solid line refer to fitting.

depend on the amount of Cr depletion which in turn depends on

the volume fraction of CrN phase present in the specimen.
The EIS data of 450 and 500 ◦ C treated plasma nitrided speci-
mens is in agreement to the above preposition due to the fact they
can be fitted to two time constants, one belonging to the depleted
(Rf ) and the other to the chromium rich region (Rp ). Between 450
Fig. 12. SEM micrograph of 400 ◦ C treated plasma nitrocarburized specimen after
and 500 ◦ C treatment the latter caused larger volume fraction of
potentiodynamic tests. The inset SEM image shows the location and the size of the CrN in the alloy (Fig. 4a) and more Cr depletion in the matrix than
pit. the former. As a consequence, 500 ◦ C treated specimen showed low
Rf and Rp values.
 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132 131

4.2. Plasma nitrocarburizing The increase in the pitting resistance after plasma nitriding has
been attributed to nitrogen by many researchers and several mech-
Surface hardness measurements of plasma nitrided and plasma anisms have been proposed [48–53]. However, in our case it has
nitrocarburized duplex stainless steel show that the latter offer been observed that there is only a marginal increase in the pit-
higher hardness than the former under identical treatment con- ting resistance after plasma nitriding and plasma nitrocarburizing.
ditions (Fig. 6b). Nevertheless, it is essential to understand how Though, earlier studies on plasma nitriding of duplex stainless steel
plasma nitrocarburized specimens behave in relation to corro- also reported a marginal increase in pitting resistance, not much
sion vis-a-vis plasma nitrided duplex stainless steel, for it to be data is available on the improvement of corrosion resistance after
successfully employed in applications demanding both corrosion plasma nitrocarburizing [54,18]. Since, this steel showed better pit-
and wear resistance. ting resistance even in the as-received condition, it was found that
Broadly, with respect to the treatment temperatures, plasma increasing the nitrogen content to (8 wt.% N in austenite and 13 wt.%
nitrocarburizing influences the corrosion behavior of the alloy N in ferrite) by plasma nitriding and (5.70 wt.% C in austenite and
in a similar way as plasma nitriding did. Thus, 350 and 400 ◦ C 2.55 wt.% C in the ferrite phase) by plasma nitrocarburizing in this
treatments were found to be beneficial, whereas 450 and 500 ◦ C study, did not elevate the pitting potentials to more higher values
treatments were detrimental to corrosion resistance. However, which may indicate that there can be no further increase in the pit-
differences existed between the two types of surface treatments. ting resistance in this steel with further addition of nitrogen as it
Notable differences were found in the Ecorr values of the spec- may lead to formation to nitrides.
imen treated at 400 and 500 ◦ C. In the former case, the Ecorr The beneficial effects of plasma nitrocarburizing over plasma
value of the plasma nitrocarburized specimen moved to a much nitriding process steams from the fact that it has not only given rise
nobler potential and in the latter to a more active potential in to better corrosion resistance than the plasma nitrided specimens,
relation to the plasma nitrided specimens (Fig. 11). Furthermore, but also higher hardness. Thus at 400 ◦ C, plasma nitrocarbur-
the 400 ◦ C treated plasma nitrocarburized specimen distinctly izing has given a hardness of 1010HV0.01 as against 699HV0.01
showed better passivity than the 400 ◦ C treated plasma nitrided obtained after plasma nitriding. Also, the 400 ◦ C plasma nitrocar-
specimen indicating that for plasma nitrocarburizing 400 ◦ C is an burized duplex steel showed an ipass of 1.38 ␮A cm−2 compared to
optimal temperature to obtain the highest passivity and corrosion 2.80 ␮A cm−2 obtained from plasma nitrided specimen.
resistance. In addition, among the entire plasma nitrocarburized Hence, from the perspective of having high hardness and cor-
specimens, the 400 ◦ C treated specimen in the post polarized con- rosion resistance, the results show the fact that 400 ◦ C plasma
dition showed the smallest and least number of pits (Fig. 12). nitrocarburized treatment exhibited the maximum hardness val-
Another difference that exists between the plasma nitrocarburized ues along with better corrosion resistance compared to the bare
and plasma nitrided specimens is that the 450 ◦ C treated plasma duplex stainless steel. However, as plasma nitrocarburizing pro-
nitrocarburized specimen lost its passivity completely, while the vides higher hardness than plasma nitriding, the former is better
plasma nitrided specimens had the tendency to passivate, despite suited to duplex stainless steel for applications requiring a combi-
having a large critical current density (20 mA cm−2 ). nation of higher hardness and higher corrosion resistance.
The EIS data of the plasma nitrocarburized specimens is in
agreement with its anodic polarization data wherein the highest 5. Conclusions
(168 k cm2 ) and lowest (1.33 k cm2 ) Rp values were observed for
400 ◦ C for 500 ◦ C treated specimens, respectively (Table 6). Based Plasma nitriding and plasma nitrocarburizing processes were
on the polarization and EIS results, it can be inferred that the 400 ◦ C carried out at 350, 400, 450, and 500 ◦ C on 2205 duplex stainless
and 500 ◦ C plasma nitrocarburized specimens showed the highest steel for 4 h. The following are the salient conclusions.
and the lowest corrosion resistance properties respectively among
all the treatments. 1. Plasma nitriding and plasma nitrocarburizing processes treated
The improvement in the passivity and corrosion resistance of at 400 ◦ C, exhibited higher surface hardness without compro-
400 ◦ C plasma nitrocarburized specimen can be correlated with the mising with corrosion resistance as seen from marginal rise in
phases formed in the GIXRD patterns (Fig. 5a). The GIXRD pattern pitting potential, and a reduction in passive current density in
reveal the presence of ␥N , an expanded austenite phase supersat- comparison to the untreated specimens. However, with further
urated with nitrogen and carbon, which has been confirmed by increase in the treatment temperatures loss of passivity and pit-
the WDS analysis (Table 3). Without going into the mechanisms ting resistance occurred.
of the role of nitrogen and carbon on the passivity and pitting, it 2. The pitting resistance of 400 ◦ C treated plasma nitrided and
can be said that as long as nitrogen and carbon is in solid solution, nitrocarburized specimens were mainly due to the presence of
they enhance the passivity and pitting resistance [43–46], so it is nitrogen and carbon as solid solution in the austenite phase (fer-
expected that 400 ◦ C plasma nitrocarburized alloy acquires these rite transformed into the austenite phase), whereas the loss of
properties. On the other hand the formation of chromium nitrides passivity of specimens treated above 400 ◦ C is due to chromium
in the alloy at 450 and 500 ◦ C has led to Cr depletion in the matrix depletion caused by precipitation of CrN.
leading to loss of passivity. Unlike the plasma nitrided specimens, 3. The post polarization micrographs of the duplex stainless steel
the plasma nitrocarburized treatments formed larger volume frac- in all cases showed pits only on the austenite grains. This is
tion of CrN in the alloy treated at 450 ◦ C and 500 ◦ C leading to poor attributed to the lower chromium and molybdenum content
corrosion resistance of this alloy as reflected from the lower Rf and than that present in the ferrite grains. In addition, the presence
Rp values. Since it is reported that the surface roughness strongly of nitrogen and carbon during plasma nitriding and nitrocarbur-
influences the passive film formation and pitting of stainless steel izing aided passivation by lowering the density and size of the
[47], the enhanced surface roughness of the plasma nitrocarbur- pits.
ized specimens treated at 450 ◦ C and 500 ◦ C temperatures could 4. The thickness of the layers over the two phases was found to
also contribute to the loss of passivity of the duplex stainless steel. be different in the case of plasma nitrided specimens whereas
It is well established that the pitting corrosion resistance of such a difference was not found in the plasma nitrocarburized
the untreated 2205 duplex stainless steel depends mainly upon specimens.
their chromium, molybdenum, and nitrogen contents as revealed 5. Both the surface roughness and hardness were found to increase
by their high Epit/trans value of ∼962 mV (vs. SCE) and PREN of 32.4. with increase in treatment temperatures. However, between the
132 J. Alphonsa et al. / Corrosion Science 100 (2015) 121–132

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