International Journal of Corrosion
Volume 2019 (2019), Article ID 7023283, 12 pages
https://doi.org/10.1155/2019/7023283

Research Article

Investigation on the Relationship between the Surface Chemistry and the Corrosion Resistance of Electrochemically Nitrided AISI 304 Stainless Steel

Janaína de Lima Rocha, Rafael dos Santos Pereira, Mara Cristina Lopes de Oliveira, and Renato Altobelli Antunes

Centro de Engenharia, Modelagem e Ciências Sociais Aplicadas (CECS), Universidade Federal do ABC (UFABC), 09210-580 Santo André, SP, Brazil

Correspondence should be addressed to Renato Altobelli Antunes; renato.antunes@ufabc.edu.br

Received 28 August 2018; Revised 16 October 2018; Accepted 10 December 2018; Published 3 February 2019

Academic Editor: Ramana M. Pidaparti

Copyright © 2019 Janaína de Lima Rocha et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

The relationship between the surface chemistry and the corrosion resistance of electrochemically nitrided AISI 304 stainless steel samples has been investigated. The nitriding treatment was carried out in HNO₃ 0.1 M and HNO₃ 0.1 M + KNO₃ 0.5 M at room temperature. Samples were subjected to the nitriding procedure for 30 minutes under a cathodic potential of -0.7 VAg/AgCl. The chemical composition of the nitrided layers was assessed by X-ray photoelectron spectroscopy (XPS). Depth profiles of the main elements present in the nitrided layers were also obtained by XPS by etching them with argon ions. The corrosion behavior of the nitrided samples was evaluated by potentiodynamic polarization. The results showed that the nitrided layers consisted of a mixture of chromium nitrides, chromium oxides, iron oxides/oxyhydroxides, and nickel oxide. The best corrosion resistance was obtained by electrochemical nitriding in the HNO₃ 0.1 M + KNO₃ 0.5 M solution. This result could be correlated with the composition and thickness of the nitrided layer.

1. Introduction

Stainless steels are prone to localized corrosion in contact with chloride-containing solutions [1–3]. The stability of the naturally formed passive film accounts for its corrosion resistance in a variety of environments [4–6]. One promising way of increasing the reliability of stainless steels is to increase passive film stability [7, 8]. Nitrogen has been shown to improve the pitting and crevice corrosion resistances of stainless steels [9]. It is reported to enable the widening of passive range, decrease of passive current density, thus leading to positive effects on the resistance to stress corrosion cracking and intergranular corrosion [10, 11]. The mechanisms through which the beneficial effects of nitrogen take place are yet unclear. Several hypotheses have been proposed such as nitrogen incorporation into the passive film, suppressing anodic dissolution, the formation of nitrate ions with repulsive action against Cl⁻, or neutralization of the acidity inside corrosion pits by the formation of ions, thus resulting in repassivation [12–16].

Nitrogen incorporation into stainless steels can be achieved by different methods. Alloying is employed for high-nitrogen austenitic stainless steels but it is limited by the low nitrogen solubility in the iron matrix [17]. Nitriding plays a central role in this scenario, giving more versatility to the nitrogen content that can be added to austenitic stainless steels [18]. Plasma nitriding has gained increased technological relevance as a large-scale processing method to achieve nitrogen-rich stainless steel surfaces [19–21]. Recently, electrochemical nitriding has emerged as an alternative route to incorporate nitrogen into the surface of stainless steels [22]. Its main advantage when compared to other nitriding treatments relies on the possibility of conducting the process at room temperature. High temperature nitriding processes are typically undertaken above 500°C and low temperature ones take place at temperatures as low as 350°C [23, 24]. In this respect, electrochemical nitriding is regarded as an economic route. Pioneering works by Willenbruch et al. [25] and Kim et al. [26] investigated the nitriding mechanism of stainless steels in solutions consisting of HCl and NaNO₃. Nitrate ions would adsorb on the metallic surface, being later reduced to and metal nitride. More recently, some authors have proposed the use of electrochemical nitriding to attain high corrosion resistance and conductivity for stainless steels employed as bipolar plates for polymer electrolyte membrane fuel cells (PEMFCs) [27–29]. The composition of the nitrided layer plays a major role in the corrosion behavior of the treated surface. Wang et al. [29] observed the formation of nitrogen incorporated oxide (oxi-nitrides) in the surface of electrochemically nitrided AISI 446 stainless steels.

In spite of the existing literature, similar information is not found for the AISI 304 austenitic stainless steel in conventional chloride-containing solutions. In this work, AISI 304 stainless steel specimens were electrochemically nitrided in different nitrate-containing electrolytes. The relationship between the chemical composition of the nitrided layer and the corrosion resistance of the treated surfaces was investigated. Surface analysis was performed by X-ray photoelectron spectroscopy (XPS). The corrosion behavior was evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization.

2. Experimental

2.1. Material and Electrochemical Nitriding Procedure

Cold-rolled AISI 304 stainless steel plate with a thickness of 4 mm was used as the substrate for electrochemical nitriding. Specimens for the surface treatment and subsequent characterization were square-shaped pieces with approximate dimensions of 2.5 × 2.5 cm.

Prior to electrochemical nitriding, the specimens were subjected to mechanical grinding using silicon carbide waterproof papers up to grit 600, being subsequently washed with deionized water and dried in a warm air stream provided by a conventional heat gun. Next, the specimens were electrochemically nitrided in different solutions, as described in Table 1. The treatment was performed using a conventional three-electrode cell setup with a platinum wire as the auxiliary electrode, Ag/AgCl as the reference electrode, and the AISI 304 specimen as the working electrode. Nitriding was performed by cathodic polarization at -0.7 VAg/AgCl. The treatment time was 30 minutes. Two different electrolytes were employed as shown in Table 1. All experiments were carried out at room temperature using an Ivium n-Stat potentiostat/galvanostat. After nitriding, the specimens were thoroughly washed with deionized water and dried in a warm air stream provided by a heat gun.

Table 1: Electrochemical nitriding conditions.

Sample
Electrolyte
Treatment time (minutes)

N
HNO₃ 0.1 M
30

NK
HNO₃ 0.1 M + KNO₃ 0.5 M
30

2.2. Electrochemical Characterization

The electrochemical behavior of the nitrided samples was assessed using the same three-electrode cell configuration employed for the nitriding treatment. The tests were carried out in 3.5 wt.% NaCl solution at room temperature. This electrolyte was selected as a common medium to evaluate the corrosion properties of metallic materials comparatively. Initially, the open circuit potential was monitored for 1 h. Next, the samples were subjected to potentiodynamic polarization at a sweep rate of 1 mV.s⁻¹ from -300 mV versus the OCP up to +1.0 VAg/AgCl. The tests were conducted in triplicate. After polarization, the corrosion morphology was examined by confocal laser scanning microscopy (Olympus, LEXT OLS4100).

2.3. Surface Analysis

XPS analyses of the as-nitrided layers were carried out in a ThermoVG K-alpha⁺ spectrometer operating with Al-kα X-ray source. The pressure in the analysis chamber was 10-6 Pa. Binding energy scale was calibrated using the C1s peak at 284.8 eV due to the presence of surface contamination (adventitious carbon). Data analysis was performed by Avantage software. Peak fitting was carried out by a weighted sum of Lorentzian and Gaussian curves, after background subtraction by the Smart algorithm. Depth profiles of Cr, Fe, Ni, O, and N were obtained by sputtering the nitrided surface with argon ions. Each sputtering cycle consisted of 15 s of exposure to the argon ions flux at 3 keV.

3. Results and Discussion

3.1. X-Ray Photoelectron Spectroscopy (XPS)

XPS high resolution spectra for the Cr2p3/2 core levels of the N and NK samples are shown in Figure 1. The spectrum for the untreated material is also shown for comparison (Figure 1(c)). The presence of CrN and Cr₂N was observed as indicated by the peak at approximately 574 eV for the nitrided samples (Figures 1(a) and 1(b)) whereas it was not observed for the untreated steel (Figure 1(c)). The other two peaks are related to Cr-O bonding typical of Cr₂O₃ and CrO₃ compounds [22]. The main species in the surface film are oxides, but chromium nitrides were unequivocally identified too, revealing the incorporation of nitrogen during the electrochemical nitriding procedure for both nitrided samples. Table 2 shows the atomic fraction of each species in the surface film with regard to the Cr2p3/2 core level. It is interesting to note that chromium nitrides were preferentially formed over sample NK, even considering the experimental error for XPS quantitative analysis (±10%) [30]. The peak corresponding to metallic chromium (Cr⁰) was only detected for the untreated sample.

Table 2: XPS fitting results for the Cr2p3/2 core level.

Sample
Cr⁰
CrN and Cr₂N
Cr₂O₃
CrO₃

B.E
at.%
B.E
at.%
B.E
at.%
B.E
at.%

(eV)
(eV)
(eV)
(eV)

Untreated
573.4
16.0
- - - -
- - - -
575.9
63.2
577.7
20.8

N
- - - -
- - - -
574.4
20.2
576.4
55.6
578.4
24.2

NK
- - - -
- - - -
574.1
30.9
575.8
42.6
577.7
26.5

(a)

(b)

(c)

Figure 1: XPS spectra for the Cr2p3/2 core levels: (a) N; (b) NK and (c) untreated samples.

The spectra for the N1s core levels of samples N and NK are shown in Figures 2(a) and 2(b), respectively. The spectra unequivocally confirm the formation of chromium nitride species as observed at 397.6 eV which is in good agreement with the literature [31, 32]. In addition, the peak at higher binding energies is ascribed to NH₃ groups that are present in smaller fractions when compared to chromium nitrides. The quantitative analysis of the fitted spectra is presented in Table 3. The presence of NH₃ is reported by other authors, being associated with the reaction of nitrides with adsorbed water in the electrolyte [22]. The data shown in Table 3 reveal a predominance of chromium nitride species over NH₃ groups for the either N or NK samples. The electrochemical nitriding procedure conducted at both solutions yielded a similar composition for the nitrided layer with respect to Cr and N species.

Table 3: XPS fitting results for the N1s core level.

Sample
CrN and Cr₂N
NH₃

B.E (eV)
at.%
B.E (eV)
at.%

N
397.6
71.9
400.4
28.1

NK
397.6
68.6
398.1
31.4

(a)

(b)

Figure 2: XPS spectra for the N1s core levels: (a) N and (b) NK samples.

The composition of the surface layer was further characterized by evaluating the Fe2p3/2 core levels. The spectra are shown in Figure 3. The fitting results are presented in Table 4.

Table 4: XPS fitting results for the Fe2p3/2 core level.

Sample
Fe⁰
FeO
Fe₂O₃
FeOOH

B.E (eV)
at.%
B.E (eV)
at.%
B.E (eV)
at.%
B.E (eV)
at.%

Untreated
706.0
28.6
706.9
14.4
708.9
36.0
711.9
21.0

N
707.0
33.9
708.0
18.2
709.8
30.3
712.7
17.6

NK
706.8
36.8
707.7
17.6
709.5
29.4
712.8
16.2

(a)

(b)

(c)

Figure 3: XPS spectra for the Fe2p3/2 core levels: (a) N; (b) NK; and (c) untreated samples.

Fitting results for the Fe2p3/2 spectra indicated the presence of metallic iron (Fe⁰) and a mixture of iron oxides and oxyhydroxides either for the untreated or nitrided samples. The binding energies are in good agreement with the literature [33–35]. Metallic iron signal arises from the steel substrate [6]. The results point that the surface of the untreated sample contains both iron and chromium oxides and hydroxides but nitrides are not present. The surface of the nitrided samples, in turn, contains chromium nitrides in addition to chromium and iron oxides/hydroxides. It is interesting to note that the metallic chromium signal was absent for the nitrided layers but the metallic iron signal was clearly detected. Moreover, it was even more intense for the nitrided layers than on the untreated surface. Our results point to an enrichment of chromium nitrides and oxide species with the electrochemical nitriding procedure whereas the iron oxides and hydroxides were proportionally lowered with respect to the metallic iron signal.

The spectra for the Ni2p3/2 core levels are shown in Figure 4. The main signal is referred to metallic nickel. Small fractions of NiO species are also detected at higher binding energies.

(a)

(b)

(c)

Figure 4: XPS spectra for the Ni2p3/2 core levels: (a) N; (b) NK; and (c) untreated samples.

The strong Ni⁰ signal is frequently reported for passive films formed on stainless steel surfaces, being associated with the lower oxidation susceptibility of nickel when compared to chromium and iron [36]. The fitting results for the Ni2p3/2 core levels are displayed in Table 5. The peak energies of Ni⁰ and NiO species are in good agreement with the literature [37]. It is interesting to note that the N sample presents a higher content of Ni0 when compared with the NK sample which, in turn, shows Ni⁰ content compatible with that of the untreated steel. According to Dadfar et al. [6] the signal of the metallic substrate is an indication that the surface film is not homogeneous. Likewise, the stronger Ni⁰ signal for the N sample suggests that its nitrided layer can be less homogeneous when compared to that of the NK sample.

Table 5: XPS fitting results for the Ni2p3/2 core level.

Sample
Ni⁰
NiO

B.E (eV)
at.%
B.E (eV)
at.%

Untreated
852.3
57.0
853.7
43.0

N
853.1
70.1
854.2
29.9

NK
852.9
57.3
853.4
42.7

The O1s spectra are shown in Figure 5. Fitting of these spectra showed two components for all samples, O²⁻ and OH⁻. These species are typical of stainless steel passive films and also for nitrided layers [6, 38, 39]. The fitted data are displayed in Table 6. It is seen that the NK sample is more oxidized than the N sample, since the OH⁻ species is present in higher contents.

Table 6: XPS fitting results for the O1s core level.

Sample
O²⁻
OH⁻

B.E (eV)
at.%
B.E (eV)
at.%

Untreated
530.5
53.8
532.0
46.2

N
530.6
54.8
532.0
45.2

NK
530.3
35.9
531.8
64.1

(a)

(b)

(c)

Figure 5: XPS spectra for the O1s core levels: (a) N; (b) NK; and (c) untreated samples.

By evaluating the XPS high resolution spectra, it was found that the nitrided layers consisted of a mixture of chromium nitrides, iron oxides/hydroxides, and nickel oxide. The main differences between N and NK samples are the lower NiO content of the N sample and higher OH⁻ content of the NK sample.

Additional analysis of the nitrided surfaces was based on XPS depth profiling. Depth profiles for Cr, Fe, O, N, and Ni are shown in Figure 6 for the N and NK samples. The nitrogen content was higher for the NK sample (Figure 6(b)) than for the N sample (Figure 6(a)). Nitrogen incorporation was favored for this sample as indicated by its higher atomic fraction, suggesting the mixed electrolyte was more effective as a nitrogen source for the stainless steel surface.

(a)

(b)

Figure 6: Depth profiles for the nitrided layers of (a) N and (b) NK samples.

Yet, it is noteworthy that the oxygen atomic concentration was less affected by the sputtering cycles for the NK sample as shown in Figure 6(b). For the N sample, the passive film is more easily removed (Figure 6(a)). Furthermore, the nitrogen atomic fraction is lower for the N sample. As a consequence of the removal of the nitrided layer, the iron concentration shows an opposite trend with respect to the oxygen and nitrogen concentration, increasing sharply with the sputtering time.

The chromium content was higher for the NK sample, suggesting its passive film is enriched in chromium, thus favoring the corrosion resistance. The nickel concentration in the surface layer is much lower than that of chromium either for N or NK samples.

3.2. Corrosion Behavior

3.2.1. Electrochemical Nitriding

The variation of the current density with the treatment time for the N and NK samples is shown in Figure 7. The current densities are negative and achieved a steady state after approximately one minute of the nitriding treatment. The negative current densities are typical of the cathodic polarization employed during nitriding. The samples nitrided in the HNO₃ 0.1 M + KNO₃ 0.5 M solution (NK samples) presented higher current densities (less cathodic), indicating the electrochemical reactions are more intense when the samples are treated in this electrolyte. The sequence of events during electrochemical nitriding is the reaction between metal and nitrate ions, leading to an adsorbed nitrate, followed by the reaction of this adsorbed species with H⁺ ions, giving rise to metal nitrides. One additional reaction occurs between nitrate ions and H⁺, forming ammonium ion [40, 41]. The formation of chromium nitrides was unequivocally observed by the XPS results presented in Figure 1 as well NH₃ species (Figure 2).

Figure 7: Variation of the current density with the treatment time for the electrochemically nitrided samples.

3.2.2. Open Circuit Potential

The variation of the open circuit potential with the immersion time in 3.5 wt.% NaCl solution at room temperature is shown in Figure 8 for the untreated and nitrided samples. The untreated sample presented the most negative potential values over the whole monitoring time, indicating a higher electrochemical activity when compared to the nitrided ones. There was an ascending trend of the open circuit potential in the beginning of the monitoring period for all samples, indicating that the passive film is likely to become thicker with time. The N sample presented the more anodic potential up to 2800 s when it presented a decreasing trend up to the end of the monitoring period, indicating that the passive film was no longer stable as at the first part of the test. The NK sample, in turn, presented a stable potential up to the end of the test, suggesting it is less prone to corrosion when compared to the N sample and the untreated substrate [42, 43]. The results suggest that the electrochemical nitriding treatment decreased the susceptibility of the 304 stainless steel substrate to corrosion and that the nitrided layer of the NK samples present the best stability in the electrolyte.

Figure 8: Variation of the open circuit potential with the immersion time for the untreated and nitrided samples. Electrolyte: 3.5 wt.% NaCl solution at room temperature.

3.2.3. Potentiodynamic Polarization Curves

Potentiodynamic polarization curves for the untreated and nitrided samples immersed in 3.5 wt.% NaCl solution at room temperature are shown in Figure 9.

Figure 9: Potentiodynamic polarization curves for the untreated and nitrided samples. Electrolyte: 3.5 wt.% NaCl solution at room temperature.

The electrochemical parameters determined from the potentiodynamic polarization curves are displayed in Table 7. The corrosion potential (Ecorr) of the NK sample is the noblest, being slightly more anodic than the value for the N sample. The untreated material, in turn, in spite of presenting the lowest value of Ecorr presented the highest pitting potential (Epit), suggesting that it is more resistant to the onset of pitting corrosion. Notwithstanding, its passive current density (ipass) was the highest, indicating that the corrosion kinetics is higher for the untreated surface. When the metallic surface is in the passive state, the passive current density is a measure of the corrosion resistance of the material [44]. The values of ipass were determined at the middle of the passive region, according to Ningshen et al. [45]. Additionally, the protection efficiency (P%) of the electrochemical nitriding procedure was calculated based on equation (1), where ipass-t is the passive current density for the treated samples and ipass is the passive current density for the untreated sample. The values of protection efficiency were 33% for the N sample and 62% for the NK sample based on the mean values of ipass presented in Table 7.

Table 7: Electrochemical parameters determined from the potentiodynamic polarization curves.

Sample

(mVAg/AgCl)
(mVAg/AgCl)
(μA.cm⁻²)

N
-74 ± 9
205 ± 26
0.14 ± 0.04

NK
-65 ± 4
261 ± 18
0.08 ± 0.02

Untreated
-119 ± 26
388 ± 18
0.21 ± 0.02

The NK sample presented an intermediate pitting potential and the lowest value of ipass. Additionally, it is important to observe that the current spikes observed in the passive region of the untreated material are not found for the nitrided samples. These features are associated with metastable pitting, being related to the instability of the passive film and imminence of its breakdown [46, 47]. Although the susceptibility to pitting corrosion is related to the Epit, current spikes indicating metastable pitting are undesirable, since the passive film does not sustain its stability through the whole potential range.

The nitrided layer of the NK sample can be considered stable, since it does not show the formation of metastable pits and presents the lowest value of ipass. However, it is not immune to the onset of localized corrosion. Furthermore, even though the results displayed in Table 7 point to an improvement of the corrosion resistance after the electrochemical nitriding procedure, the standard deviations must be taken into account. In this respect, the differences of ipass do not point to a marked improvement, especially for the N condition.

In order to give further understanding about the protective efficiency of the nitrided surfaces, confocal laser scanning microscopy (CLSM) was employed to examine the corrosion morphology of the specimens subjected to potentiodynamic polarization. Representative pits and their corresponding transverse profiles are shown in Figures 10, 11, and 12 for the N, NK, and untreated samples, respectively.

(a)

(b)

Figure 10: CLSM micrograph of a pit (a) and its corresponding transverse profile (b) for a representative N sample.

(a)

(b)

Figure 11: CLSM micrograph of a pit (a) and its corresponding transverse profile (b) for a representative NK sample.

(a)

(b)

(c)

Figure 12: CLSM micrographs for a representative untreated sample ((a) and (b)); (c) the transverse profile for the pit shown in (b).

It is interesting to note that pit growth was characterized by the formation of small pits surrounding bigger ones for the untreated sample, as observed in Figures 12(a) and 12(b). This feature was not observed for the nitrided samples. Pit dimensions were determined from the CLSM micrographs. The maximum diameter and maximum depth were measured. The results are displayed in Table 8. Pit diameter was lower for the nitrided samples whereas pit depth was similar the NK and the untreated material. Notwithstanding, the lowest diameter of the NK condition suggests its pit growth was slow, in accordance with its low ipass values shown in Table 7.

Table 8: Pit dimensions determined by CLSM.

Sample
Maximum width
Maximum depth

(μm)
(μm)

N
668 ± 16
56 ± 25

NK
585 ± 24
101 ± 13

Untreated
880 ± 9
104 ± 15

These results can be correlated with those obtained by XPS. The relative poor corrosion resistance of the N sample when compared to NK would derive from its less thick nitrided layer. Depth profiles shown in Figure 6 clearly indicate that the nitrided layer formed on the NK sample is not as easily removed as that produced on the N samples, suggesting it is thinner and, therefore, less protective. This effect would be dominant over any difference of chemical composition. Indeed, the main composition differences were not observed for the chromium nitride compounds, but for the metallic nickel signal and for the oxygen species present on the sample surface. The higher metallic nickel signal of the N sample would indicate its less oxidized nature as well as its lower OH⁻ content when compared to NK. These features would arise from the higher current densities experienced by the samples subjected to electrochemical nitriding in the HNO₃ 0.1 M + KNO₃ 0.5 M solution (NK samples), giving rise to a more protective nitrided layer. In this respect, the nitrided layer formed on NK samples, although it is more heterogeneous than the layer produced on the N samples (as shown by the XPS depth profiles presented in Figure 6), provided the best corrosion resistance due to a combination of its more oxidized state and higher thickness.

Our results point to a marginal improvement of the corrosion resistance for the N samples and a better protective ability for the NK condition. It is important to emphasize that the electrochemical nitriding treatment undertaken in the present work can be optimized to reach more significant performance against corrosion, exploring other concentrations of the chemical species or treatment times. The main contribution of this work is to firstly investigate the correlation between the surface chemistry and the corrosion resistance of electrochemically nitrided AISI 304 stainless steel samples. In this respect, it is the first step into a deeper understanding of the marked influence of surface chemistry and the possibility of controlling the corrosion resistance by modifying the electrolyte composition.

4. Conclusions

Electrochemical nitriding of AISI 304 stainless steel samples was successfully performed in HNO₃ 0.1 M and HNO₃ 0.1 M + KNO₃ 0.5 M at room temperature by applying a cathodic potential to the steel samples. The nitrided layers consisted of a mixture of chromium nitrides with chromium oxides, iron oxides/oxyhydroxidesa, and nickel oxide. The samples nitrided in the HNO₃ 0.1 M + KNO₃ 0.5 M solution (NK) presented higher atomic concentrations of nitrogen species across the thickness of the nitrided layer, as shown by XPS depth profiles. The lowest values of passive current densities for the NK samples and its higher pitting potential indicated that the corrosion resistance of the nitrided samples was affected by the solution employed for electrochemical nitriding. NK samples presented an apparently thicker nitrided layer, although it grew more heterogeneously than the layer formed on the N samples, as indicated by the XPS depth profiles. The results show that it is possible to control the corrosion resistance of the nitrided layer, depending on the electrolyte employed for the nitriding treatment.

Data Availability

The data used to support the findings of this study are available from the corresponding author upon request.

Conflicts of Interest

The authors declare that there are no conflicts of interest regarding the publication of this paper.

References

G. S. Frankel, “Pitting corrosion of metals: a review of the critical factors,” Journal of The Electrochemical Society, vol. 145, no. 6, pp. 2186–2198, 1998.

S. Deng, S. Wang, L. Wang, J. Liu, and Y. Wang, “Influence of chloride on passive film chemistry of 304 stainless steel in sulphuric acid solution by glow discharge optical emission spectrometry analysis,” International Journal of Electrochemical Science, vol. 12, no. 2, pp. 1106–1117, 2017.

P. Sharma and H. Roy, “Pitting corrosion failure of an AISI stainless steel pointer rod,” Engineering Failure Analysis, vol. 44, pp. 400–407, 2014.

Z. B. Zheng and Y. G. Zheng, “Effects of surface treatments on the corrosion and erosion-corrosion of 304 stainless steel in 3.5% NaCl solution,” Corrosion Science, vol. 112, pp. 657–668, 2016.

J. Lv and H. Luo, “Electrochemical investigation of passive film in pre-deformation AISI 304 stainless steels,” Applied Surface Science, vol. 263, pp. 29–37, 2012.

M. Dadfar, M. Salehi, M. A. Golozar, S. Trasatti, and M. P. Casaletto, “Surface and corrosion properties of modified passive layer on 304 stainless steel as bipolar plates for PEMFCs,” International Journal of Hydrogen Energy, vol. 42, no. 41, pp. 25869–25876, 2017.

Y. Fu, X. Wu, E.-H. Han, W. Ke, K. Yang, and Z. Jiang, “Effects of nitrogen on the passivation of nickel-free high nitrogen and manganese stainless steels in acidic chloride solutions,” Electrochimica Acta, vol. 54, no. 16, pp. 4005–4014, 2009.

C. Loable, I. N. Viçosa, T. J. Mesquita et al., “Synergy between molybdenum and nitrogen on the pitting corrosion and passive film resistance of austenitic stainless steels as a pH-dependent effect,” Materials Chemistry and Physics, vol. 186, pp. 237–245, 2017.

H. Baba, T. Kodama, and Y. Katada, “Role of nitrogen on the corrosion behavior of austenitic stainlesss steels,” Corrosion Science, vol. 44, no. 10, pp. 2393–2407, 2002.

R. F. A. Jargelius-Pettersson, “Electrochemical investigation of the influence of nitrogen alloying on pitting corrosion of austenitic stainless steels,” Corrosion Science, vol. 41, no. 8, pp. 1639–1664, 1999.

F. Borgioli, E. Galvanetto, and T. Bacci, “Corrosion behaviour of low temperature nitrided nickel-free, AISI 200 and AISI 300 series austenitic stainless steels in NaCl solution,” Corrosion Science, vol. 136, pp. 352–365, 2018.

F. Bottoli, M. S. Jellesen, T. L. Christiansen, G. Winther, and M. A. J. Somers, “High temperature solution-nitriding and low-temperature nitriding of AISI 316: Effect on pitting potential and crevice corrosion performance,” Applied Surface Science, vol. 431, pp. 24–31, 2018.

I. Olefjord and L. Wegrelius, “The influence of nitrogen on the passivation of stainless steels,” Corrosion Science, vol. 38, no. 7, pp. 1203–1220, 1996.

S. Ningshen, U. K. Mudali, V. K. Mittal, and H. S. Khatak, “Semiconducting and passive film properties of nitrogen-containing type 316LN stainless steels,” Corrosion Science, vol. 49, no. 2, pp. 481–496, 2007.

L. Vehovar, A. Vehovar, M. Metikoš-Huković, and M. Tandler, “Investigations into the stress corrosion cracking of stainless steel alloyed with nitrogen,” Materials and Corrosion, vol. 53, no. 5, pp. 316–327, 2002.

F. M. Bayoumi and W. A. Ghanem, “Effect of nitrogen on the corrosion behavior of austenitic stainless steel in chloride solutions,” Materials Letters, vol. 59, no. 26, pp. 3311–3314, 2005.

W.-L. Park, S.-M. Jung, and Y. Sasaki, “Fabrication of ultra high nitrogen austenitic stainless steel by NH 3 solution nitriding,” ISIJ International, vol. 50, no. 11, pp. 1546–1551, 2010.

M. Basiaga and J. Przondziono, “Influence of the ion nitriding process on the electrochemical properties of X39Cr13 steel used for surgical instruments,” Solid State Phenomena, vol. 212, pp. 111–114, 2014.

H. Riazi, F. Ashrafizadeh, and A. Eslami, “Effect of plasma nitriding parameters on corrosion performance of 17-4 PH stainless steel,” Canadian Metallurgical Quarterly, vol. 56, no. 3, pp. 322–331, 2017.

F. Cajner, S. Kovacic, H. Rafael, A. Vugrincic, V. Simunovic, and B. Grzeta, “Influence of nitriding on corrosion resistance of martensitic X17CrNi16-2 stainless steel,” Materials Science Engineering Technology, vol. 46, pp. 69–77, 2015.

M. Łępicka and M. Grądzka-Dahlke, “Effect of plasma nitriding process conditions on corrosion resistance of 440B martensitic stainless steel,” Acta Mechanica et Automatica, vol. 8, no. 3, pp. 156–159, 2014.

S. P. Mani and N. Rajendran, “Corrosion and interfacial contact resistance behavior of electrochemically nitrided 316L SS bipolar plates for proton exchange membrane fuel cells,” Energy, vol. 133, pp. 1050–1062, 2017.

D. Mareci, S. I. Strugaru, C. Munteanu, G. Bolat, and R. M. Souto, “Evaluation of the corrosion resistance of plasma nitrided austenitic stainless steel,” International Journal of Materials Research, vol. 106, no. 3, pp. 267–274, 2015.

W. J. Yang, M. Zhang, Y. H. Zhao et al., “Enhancement of mechanical property and corrosion resistance of 316 L stainless steels by low temperature arc plasma nitriding,” Surface and Coatings Technology, vol. 298, pp. 64–72, 2016.

R. D. Willenbruch, C. R. Clayton, M. Oversluizen, D. Kim, and Y. Lu, “An XPS and electrochemical study of the influence of molybdenum and nitrogen on the passivity of austenitic stainless steel,” Corrosion Science, vol. 31, no. C, pp. 179–190, 1990.

D. Kim, C. R. Clayton, and M. Oversluizen, “On the question of nitrate formation by N-containing austenitic stainless steels,” Materials Science and Engineering: A Structural Materials: Properties, Microstructure and Processing, vol. 186, no. 1-2, pp. 163–169, 1994.

H. Wang, G. Teeter, and J. A. Turner, “Modifying a stainless steel via electrochemical nitridation,” Journal of Materials Chemistry, vol. 21, no. 7, pp. 2064–2066, 2011.

H. L. Wang and J. A. Turner, “Electrochemical nitridation of a stainless steel for PEMFC bipolar plates,” International Journal of Hydrogen Energy, vol. 36, no. 20, pp. 13008–13013, 2011.

H. Wang and J. A. Turner, “Modifying a stainless steel for PEMFC bipolar plates via electrochemical nitridation,” Fuel Cells, vol. 13, no. 5, pp. 917–921, 2013.

S. Tougaard, “Surface nanostructure determination by X-ray phoemission spectroscopy peak shape analysis,” Journal of Vacuum Science & Technology A, vol. 14, pp. 1415–1423, 1996.

J. Lv and T. Liang, “Improved corrosion resistance of 316L stainless steel by nanocrystalline and electrochemical nitridation in artificial saliva solution,” Applied Surface Science, vol. 359, pp. 158–165, 2015.

L. Jinlong, L. Tongxiang, and L. Hongyun, “Effect of grain refinement and electrochemical nitridation on corrosion resistance of the 316L stainless steel for bipolar plates in PEMFCs environment,” Journal of Power Sources, vol. 293, pp. 692–697, 2015.

T. Sönmez, M. Fazeli Jadidi, K. Kazmanli, Ö. Birer, and M. Ürgen, “Role of different plasma gases on the surface chemistry and wettability of RF plasma treated stainless steel,” Vacuum, vol. 129, pp. 63–73, 2016.

C. Zhang, Z.-W. Zhang, and L. Liu, “Degradation in pitting resistance of 316L stainless steel under hydrostatic pressure,” Electrochimica Acta, vol. 210, pp. 401–406, 2016.

A. N. Mansour and R. A. Brizzolara, “Characterization of the Surface of FeO Powder by XPS,” Surface Science Spectra, vol. 4, no. 4, pp. 345–350, 1996.

H. Luo, X. G. Li, C. F. Dong, K. Xiao, and X. Q. Cheng, “Influence of uv light on passive behavior of the 304 stainless steel in acid solution,” Journal of Physics and Chemistry of Solids, vol. 74, no. 5, pp. 691–697, 2013.

Z. B. Wang, H. X. Hu, and Y. G. Zheng, “Synergistic effects of fluoride and chloride on general corrosion behavior of AISI 316 stainless steel and pure titanium in H2SO4 solutions,” Corrosion Science, vol. 130, pp. 203–217, 2018.

H. Luo, X. Wang, C. Dong, K. Xiao, and X. Li, “Effect of cold deformation on the corrosion behaviour of UNS S31803 duplex stainless steel in simulated concrete pore solution,” Corrosion Science, vol. 124, pp. 178–192, 2017.

Y. Hedberg, M. Karlsson, Z. Wei, M. Žnidaršič, I. Odnevall Wallinder, and J. Hedberg, “Interaction of Albumin and Fibrinogen with Stainless Steel: Influence of Sequential Exposure and Protein Aggregation on Metal Release and Corrosion Resistance,” Corrosion, vol. 73, no. 12, pp. 1423–1436, 2017.

G. T. Burstein, I. M. Hutchings, and K. Sasaki, “Electrochemically induced annealing of stainless-steel surfaces,” Nature, vol. 407, no. 6806, pp. 885–887, 2000.

C. R. Clayton, G. P. Halada, and J. R. Kearns, “Passivity of high-nitrogen stainless alloys: the role of metal oxyanions and salt films,” Materials Science and Engineering: A Structural Materials: Properties, Microstructure and Processing, vol. 198, no. 1-2, pp. 135–144, 1995.

G. Bolat, D. Mareci, R. Chelariu, J. Izquierdo, S. González, and R. M. Souto, “Investigation of the electrochemical behaviour of TiMo alloys in simulated physiological solutions,” Electrochimica Acta, vol. 113, pp. 470–480, 2013.

D. J. Dos Santos, L. B. Tavares, R. A. Antunes, R. Droppa, T. F. Da Silva, and M. C. Salvadori, “Properties of aluminum oxide thin film obtained by metal plasma immersion ion implantation and deposition after zirconium-based pretreatment,” Vacuum, vol. 121, pp. 32–41, 2015.

V. A. Alves and C. M. A. Brett, “Influence of alloying on the passive behaviour of steels in bicarbonate medium,” Corrosion Science, vol. 44, no. 9, pp. 1949–1965, 2002.

S. Ningshen, M. Sakairi, K. Suzuki, and S. Ukai, “The corrosion resistance and passive film compositions of 12% Cr and 15% Cr oxide dispersion strengthened steels in nitric acid media,” Corrosion Science, vol. 78, pp. 322–334, 2014.

W. Tian, N. Du, S. Li, S. Chen, and Q. Wu, “Metastable pitting corrosion of 304 stainless steel in 3.5% NaCl solution,” Corrosion Science, vol. 85, pp. 372–379, 2014.

N. Hara, K. Hirabayashi, Y. Sugawara, and I. Muto, “Improvement of pitting corrosion resistance of type 316L stainless steel by potentiostatic removal of surface MnS inclusions,” International Journal of Corrosion, vol. 2012, Article ID 482730, 6 pages, 2012.