Surface & Coatings Technology 405 (2021) 126689

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Surface & Coatings Technology

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Structure and corrosion behavior of ultra-thick nitrided layer produced by

plasma nitriding of austenitic stainless steel
Zhen Huang, Zi-Xin Guo, Lei Liu, Yuan-Yuan Guo *, Jun Chen, Ze Zhang, Jin-Long Li, Yan Li,
Yan-Wen Zhou, Ying-Shuang Liang
Surface Engineering Institute, University of Science and Technology Liaoning, Anshan 114051, China

A R T I C L E I N F O A B S T R A C T

Keywords: An ultra-thick nitrided layer (>80 μm) was formed by hot wire enhanced plasma-assisted nitriding of AISI 316L
Plasma-assisted nitriding austenitic stainless steel under the higher pulsed bias to investigate the structure and the corrosion performance.
Structure The phase structure, the cross-sectional morphology, the element distribution, hardness and modulus, as well as
Hardness
the corrosion behavior of the nitrided layer were investigated by XRD, SEM, EDS, nano-indentation tester and
Corrosion resistance
electrochemical workstation, respectively. The results showed that the nitrided layer was divided into two sub-
layers: the upper thick layer composed of N-expanded austenite and CrN, and the lower thin layer mainly
composed of γN with a trace of CrN precipitate. Nitrided at − 400 V, CrN and high N-expanded austenite formed
in the upper layer, which exhibited a high hardness and an excellent corrosion resistance. As the bias increased to
− 500 V, more nitrogen atoms precipitated as CrN phase and low N-expanded austenite phase began to form, the
thickness of nitrided layer reached a maximum of 84 μm. To − 600 V, high N-expanded austenite almost
completely transformed to low N-expanded austenite, accompanied by the increase of CrN, which caused the
thickness and hardness of the nitrided layer to decrease, and the pitting corrosion occurred at − 4.1 mV.

1. Introduction precipitation-free nitrided layer (usually less than 8 μm in thickness),

Austenitic stainless steels are receiving increased attention because
of their excellent workability, corrosion resistance and biocompatibility
[1–3]. However, the low hardness and poor wear resistance severely
limit their industrial application. An increasing amount of surface
modification methods are used to improve the surface performance of
stainless steel, such as plasma nitriding, carburizing, nitrocarburizing,
boronizing, oxy-nitriding and sand blasting assisted nitriding techniques
[4–9]. Among these technologies, plasma nitriding has been widely
applied and researched, by which precipitation-free expanded austenite
phase (γN) with high hardness and good wear resistance can be formed
on the surface at low nitriding temperature (below 450 ◦ C) for short
nitriding time (less than 6 h) [10,11]. While exceeding this temperature
or prolonging nitriding time, CrN precipitates can be simultaneously
formed along with γN phase, resulting in the formation of chromium-
depleted zones and the reduction of corrosion resistance [12,13].
Therefore, the nitriding temperature and time become the decisive
factors influencing the corrosion resistance of nitrided layer. However,
low-temperature, short-time nitriding can only obtain a thinner
which is not enough to exhibit perfect bearing capacity even as a tran­
sition layer [14]. To solve this problem, a new type of hot wire enhanced
plasma-assisted nitriding (PAN) technology was proposed, which can
obtain an above 80 μm thick nitrided layer with high hardness and
excellent corrosion resistance.
In this work, austenitic stainless steel was nitrided under various
high bias voltages using a hot wire enhanced PAN technology.
Compared with conventional PAN, auxiliary W filaments act as emission
sources of electrons in order to create additional gas ionization, which
can generate more nitrogen ions (N+) and active nitrogen atoms (N*)
reaching the surface of substrate driven by a bias voltage. Increasing the
surface nitrogen potential promotes nitrogen diffusion to increase the
nitriding rate. Our previous results show that the diffusion rate of ni­
trogen increases linearly with the filament current [15]. In addition, a
pulsed bias with higher voltage is applied on the substrate, which can
not only generate an activation effect on the substrate surface to
improve the nitriding efficiency, but also avoid the excessive high
temperature of the substrate due to ion bombardment to suppress the
precipitation of CrN phase. Without the formation of precipitates, the

* Corresponding author.
E-mail address: guoyuanyuan@ustl.edu.cn (Y.-Y. Guo).

https://doi.org/10.1016/j.surfcoat.2020.126689
Received 10 September 2020; Received in revised form 3 November 2020; Accepted 27 November 2020
Available online 30 November 2020
0257-8972/© 2020 Elsevier B.V. All rights reserved.
Z. Huang et al. Surface & Coatings Technology 405 (2021) 126689

Fig. 1. Schematic diagram of the hot wire enhanced plasma-assisted

nitriding system.

thickness of nitrided layer can exceed 10 μm. Austenitic stainless steel

Fig. 2. XRD patterns of the substrate and nitrided samples.
after nitriding has a broad range of potential applications, such as pump
components, chemical equipment, biomedical tools [16,17] and fuel cell
bipolar plates [18]. phase structure of the nitrided layer with a scanning angle from 30◦ to
Therefore, in order to obtain an ultra-thick nitrided layer in the short 80◦ , which was operated using Cu Kα1 at a wavelength of 0.15406 nm in
time and study the evolution of mechanical and corrosion properties of Bragg-Brentano configuration. Zeiss-SIGMA HD field emission scanning
the nitrided layer with CrN precipitates, the nitriding need to be carried electron microscope (SEM) equipped with energy-dispersive X-ray
out at higher temperature. In the case of CrN precipitation, how and why spectrometer (EDS) was used to observe the cross-sectional morphology
to not damage the corrosion resistance of the nitrided layer is an and to measure the thickness of the nitrided layer, as well as to analyze
important objective of this study. The other aim of this study is to the elements distribution in the nitrided layer. The nano-hardness and
investigate the effect of high bias voltage on phase structure, mechanical Young’s modulus measurements were carried out on the cross section
properties and corrosion behavior of nitrided layer. using G200 nano-indentation tester with a standard Berkovich indenter
under a load of 50 μN according to the continuous stiffness measurement
(CSM). The load displacement was set to 2000 nm, and an average value
2. Experimental
of nano-hardness and Young’s modulus was taken of 10 different posi­
tions at the same depth. The corrosion resistance of nitrided samples and
2.1. Sample preparation
the substrate was examined by the Dutch IVIUM electrochemical
workstation (Vertex.C). The measurements were carried out in a three-
The substrate materials used in this work were 316 L austenitic
electrode system, in which a saturated calomel electrode (SCE) acted
stainless steel (17.2 wt% Cr, 10.0 wt% Ni, 2.0 wt% Mo, 1.3 wt% Mn, 0.6
as the reference electrode, a platinum sheet as an auxiliary electrode and
wt% Si, 0.08 wt% C, and Fe as balance) sheets cut from a cylindrical rod
the sample as the working electrode. The edges of the samples were
(30 mm of diameter) and with a thickness of 3 mm. The substrates were
sealed by insulating epoxy resin, only leaving a 0.7 cm2 surface exposed
mechanically polished to a mirror-like finish, and then were ultrasoni­
to the electrolyte. The open circuit potential was measured with the
cally cleaned in alcohol for 30 min, dried and placed in a vacuum
scanning time of 1800 s in 3.5% NaCl solution at 25 ◦ C. Then the both of
chamber.
electrochemical impedance spectroscopy (EIS) and potential dynamic
The nitriding experiments were carried out in a hot wire enhanced
polarization were carried out. EIS were obtained in the frequency range
PAN system, as shown in Fig. 1. Four tungsten filaments were installed
of 105 to 10− 2 Hz. Potential dynamic polarization was performed at a
around the chamber wall, acting as cathodes. They were connected to a
scan rate of 1.6 mV/s. After washing with deionized water and drying,
50 Hz AC power to heat the electrons and biased at − 120 V by a DC
the surface morphology of corroded samples was observed by SEM.
power supply which is isolated with the AC power. The sample holder
was negatively biased using a square waveform pulsed power supply at a
3. Result and discussion
frequency of 60 kHz and duty cycle of 80%. The chamber temperature
was controlled at 460 ◦ C by six heaters and filament power. After the
3.1. Microstructure and morphology
pressure of the vacuum chamber decreased to 3.0 × 10− 3 Pa, the gas
mixture of 55 vol% argon and 45 vol% hydrogen was introduced into the
Fig. 2 shows the XRD patterns of the substrate and the nitrided
chamber, the current of each filament was adjusted to 5 A to produce the
samples treated under the different bias voltages. It can be seen from
plasma, and the substrate bias was set to − 300 V to perform an in-situ
Fig. 2 that the substrate had a face-centered cubic structure with (111),
cleaning pre-treatment for 30 min, in order to better remove the oxide
(200) and (220) diffraction peaks. After nitriding, no sign of substrate
layer on the substrate surface. Maintaining the discharge, the samples
could be detected due to the very high thickness of nitrided layer.
were nitrided at 0.5 Pa in pure nitrogen for 4 h under the pulsed bias
Instead, the diffraction peaks of high N-expanded austenite and CrN
voltage of − 400 V, − 500 V and − 600 V, at which the corresponding
phases appeared after nitriding at − 400 V. Previous literatures have
substrate temperatures measured with a thermocouple embedded in the
revealed that nitrogen atoms diffuse into the austenite interstitial site to
sample were 510 ◦ C, 550 ◦ C and 580 ◦ C, respectively.
form γN phase [19]. As the nitriding temperature or time increased, the
nitrogen atoms preferentially bond with Cr to form CrN phase, owing to
2.2. Structure characterization the higher heat of formation of CrN than FeNx [20]. When the bias was
− 500 V, high N-expanded austenite began to transform to low N-
X’ Pert Powder X-ray diffraction (XRD) was used to determine the expanded austenite with the peaks (111), (200) and (220) occurred at

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Z. Huang et al.
Fig. 3. Cross-sectional morphologies and EDS results of the nitrided layer: (a-c) − 400 V; (d) − 500 V; (e, f) − 600 V.
42.70◦ , 49.85◦ and 72.90◦ , respectively. As the bias increased to − 600 V,
the diffraction peaks of low N-expanded austenite and CrN heightened,
accompanied by the weakening of diffraction peaks of high N-expanded
austenite, and the nitrided layer was mainly composed of low N-
expanded austenite and CrN phases. Therefore, it can be concluded that
as the bias voltage increases, on the one hand, the bombardment of high-
energy ions onto the surface creates a large number of defects, which
provides an effective channel for the diffusion of nitrogen and promotes
more N atoms to involve into austenite lattice; on the other hand, the
bombardment of high-energy ions increases the substrate temperature,
and more Cr obtaining enough energy by thermal vibration get rid of the
lattice, which contributes to the combination between the enriched N
and Cr. As CrN precipitates continuously, the nitrogen involved in
expanded austenite decreased, causing high N-expanded austenite to
transform to low N-expanded austenite [21].
The cross-sectional morphologies and element depth profiles of the
nitrided layers obtained under different pulsed bias are shown in Figs. 3
and 4, respectively. To improve the contrast difference, an etching re­
agent of Curran (10 g FeCl3 + 30 mL HCl + 120 mL H2O) was used after
the samples were grinded and polished. From Fig. 3 (a), it can be seen
that the nitrided layer had a double-layer microstructure with an outer
thick layer (denoted as compound layer, C-layer) composed mainly of
CrN and high N-expanded austenite that were detected by XRD, and an
inner thin layer (denoted as solution layer, S-layer) compound of γN
phase and a trace of CrN precipitates appeared at the grain boundary
(indicated by dashes) [22]. The total thickness of the nitrided layer was
about 82 μm, of which the C-layer was 52 μm and the S-layer was 30 μm.
There were some small white particles (indicated by arrows) distributed
in C-layer, shown in Fig. 3 (b). The corresponding EDS analysis results of
point 1 and 2 were shown in Fig. 3 (c). Due to the uncertainty on the
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Surface & Coatings Technology 405 (2021) 126689
measurement of light elements by EDS [23], the present element content
was only a relative value for comparison. Comparing the difference in
composition between the two points, it can be found that the Fe contents
of point 1 was higher than that of point 2, so it is speculated that these
white particles were high N-expanded austenite phases. Interestingly, Cr
content in C-layer was significantly higher than that of untreated sam­
ple, which was attributed to Cr out-diffusion from the interior to the
nitrided surface. Thermodynamically, the formation energy of Cr–N is
greater than that of Cr–Fe in the austenite lattice, so the energy dif­
ference between the two phases becomes the driving force for Cr
diffusion. The solubility of Cr in the austenite decrease with the pre­
cipitation of CrN, forming a concentration gradient from the interior to
the surface, which leads to the outward diffusion of Cr. Kinetically, the
ion bombardment and introduction of nitrogen atoms cause lattice
distortion and defects, which provides an effective channel for the
outward diffusion of Cr atoms. At the same time, it cannot be ignored
that the higher temperature also provides a necessary condition for the
diffusion of Cr atoms, enhancing the diffusion kinetics. Therefore, a Cr-
rich layer was formed on the surface, which contributed to the
improvement of the corrosion resistance. Kong J H et.al [24,25] also
found the chromium moved from the interior to the nitrided surface
during the high-temperature gas nitriding, due to the strong affinity
between nitrogen and chromium. As shown in Fig. 4(a), the Cr content in
C-layer increased to 24.6 at.%, which was higher than that of untreated
sample (15.7 at.%). Meanwhile, the Cr content at the displacement into
surface of 80 to 120 μm was about 12 at.%, lower than that of untreated
sample, which further confirmed the diffusion of Cr from the interior to
the surface. Similarly, the Fe content in C-layer was significantly lower
than that of untreated sample (54.4 at.%), while the one (~58 at.%) at
the depth of 80–120 μm was higher than that of untreated sample,
Z. Huang et al. Surface & Coatings Technology 405 (2021) 126689

Fig. 5. Current density-potential curves of the substrate and nitrided samples.

indicating that Fe atoms inward diffused from the surface. Such a small
amount of Fe in C-layer justified the good corrosion behavior of the
nitrided layer.
As the bias voltage increased to − 500 V, the morphology of the
nitrided layer changed significantly, as shown in Fig. 3 (d). First, the
boundary between C-layer and S-layer was no longer obvious. However,
according to the element depth profiles, shown in Fig. 4 (b), this double-
layer structure can still be distinguished. Second, in C-layer, the white
particles disappeared and the tissue became loose; while in S-layer, there
was no obvious grain boundary and the tissue was relatively denser.
Finally, the total thickness (84 μm) of the nitrided layer increased
slightly with bias voltage, but the thickness of C-layer (63 μm) increased
significantly and that of S-layer (21 μm) decreased. In addition, the ni­
trogen content in the whole nitrided layer increased by about 6 at.% as
compared to that treated at − 400 V, shown in Fig. 4 (a) and (b). This
indicates that with increasing the bias, more nitrogen atoms diffused
into the austenite lattice, which led to continuous precipitation of CrN
phase from γN phase across a moving boundary until the austenite grains
completely decomposed. Therefore, the double-layer structural
morphology disappeared.
Nitrided at − 600 V, as a large amount of CrN phase precipitated and
high N-expanded austenite decomposed, the total thickness of the
nitrided layer reduced to 60 μm, and the thickness of each sub-layer also
reduced accordingly, shown in Fig. 3 (e). This is because the diffusivity
of nitrogen in CrN is four orders of magnitude lower than in high N-
expanded austenite [21]. The double-layer structure was still observed
in the partial enlargement of Fig. 3 (f), although the boundary between
the nitrided layer and the substrate became less obvious. Combining the
morphology and element profiles of Fig. 4 (c), it can be seen that the
obvious interface was attributed to the jump-like change of Fe content,
whether between C-layer and S-layer or between S-layer and the sub­
strate. Meanwhile, the element depth profiles in S-layer changed from a
platform to a gradient region as the bias increased from − 500 V to − 600
V.
Several studies [26,27] reported that the expanded austenite
decomposed into CrN + α ferrite + lower nitrogen austenite, whereas
others [28,29] found that no ferrite was formed. Our observations were
consistent with the latter. It can be inferred that the out-diffusion of Cr
plays a positive role on the incorporation of high levels of nitrogen in the
matrix, due to strong Cr–N bond, which stabilizes the austenite phase.

Fig. 4. Element depth profiles of the nitrided layer: (a) − 400 V; (b) − 500 V; (c)
− 600 V. 3.2. Corrosion behavior

The corrosion properties of present nitrided samples were estimated

using two electrochemical procedures: potentiodynamic polarization

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Z. Huang et al. Surface & Coatings Technology 405 (2021) 126689

Table 1 C-layer detected by EDS. Besides, according to the pitting resistance

Electrochemical parameters estimated from the polarization tests of substrate number (PREN = [%Cr] + 3.3[%Mo] + (16–30)[%N]) [32], the high
and nitrided samples. content of nitrogen in solution not only can delay the pitting corrosion
Samples Ecorr (mV) icorr (A⋅cm− 2) Corrosion rate (mm/y) [33], but also can stabilize the passive film and prevent the attack from
316 L − 106.1 1.1 × 10− 7
1.31 × 10− 3 Cl− [34], so no obvious pitting corrosion was observed in Fig. 5.
− 400 V − 15.0 3.2 × 10− 8
3.77 × 10− 4 Moreover, when the corrosion potential was lower than 137 mV, the
− 500 V − 82.8 4.1 × 10− 8
4.87 × 10− 4
passive current density (Ipass) of the sample nitrided at − 400 V was
7 3
− 600 V − 345.0 9.6 × 10− 9.70 × 10− lower than that of the one at − 500 V, whereas for the case of above 137
mV, the former was higher than the latter. However, in the case of − 400
V bias, a stable passivation occurred at the corrosion potential of 220
and electrochemical impedance spectroscopy. Fig. 5 shows that the
mV, exhibiting a more excellent pitting resistance. This could be
polarization curves for the untreated and nitrided samples in 3.5% NaCl
attributed to the enrichment of nitrogen on the surface of passive films,
solution. Based on the curves, the self-corrosion potential (Ecorr),
which forms ammonium ions increasing the local pH value and facili­
corrosion current density (icorr) and corrosion rate were determined
tating repassivation [32,35]. Instead, in the case of − 500 V bias, the
using Tafel method and listed in Table 1. Compared with the substrate,
stable passivation did not occur, because the high N-expanded austenite
the corrosion resistance of the nitrided samples with − 400 V and − 500
changed to the low N-expanded austenite, causing the decrease of ni­
V bias was improved as seen from a rise in self-corrosion potential and a
trogen content. Finally, hardly any more iron was detected in the su­
decrease in corrosion current density, especially for − 400 V. Because
perficial layer, which also gave a good protection. Therefore, the
the C-layer was mainly composed of CrN with better corrosion resistance
corrosion resistance of the samples nitrided at − 400 V and − 500 V has
and expanded austenite, its corrosion resistance was determined by that
not been damaged, instead has been significantly improved compared
of the later. Following the substantial literatures [12,13,30,31], it is
with the substrate.
known that the precipitation of CrN after high temperature nitriding
As the bias increased to − 600 V, the continuous precipitation of CrN
leads to the depletion of Cr in the expanded austenite, playing a negative
phase led to decomposition of high N-expanded austenite to form low N-
role in corrosion resistance. However, the present nitriding results show
expanded austenite, resulting in a decrease in the solid-solution N and Cr
that the corrosion resistance does not deteriorate due to the precipita­
content. Reducing the N and Cr content accelerated pitting corrosion
tion of CrN, which is attributed to the out-diffusion of Cr from the
and destroyed passive film, thereby decreasing the corrosion resistance
interior to the nitrided surface, thereby compensating the depletion of
of the nitrided layer. It can be seen from the blue line in Fig. 5, the anodic
Cr due to precipitation. This is consistent with the high Cr content in the
branch of the curve presented the passivation-pitting transition and the

Fig. 6. Corroded surface morphologies of the untreated and the nitrided samples: (a) 316 L; (b) − 400 V; (c) − 500 V; (d) − 600 V.

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Z. Huang et al.
Fig. 7. Nyquist (a) and Bode plots (b) of the substrate and nitrided samples.
pitting corrosion occurred at − 4.1 mV, which could not be clearly
identified in the other nitrided samples. In addition, the out-diffusing Cr
was not enough to compensate the depletion due to CrN precipitation,
resulting in a significant decrease in Ecorr and an increase in corrosion
current by about an order of magnitude.
Fig. 6 shows the surface morphologies of the untreated and the
nitrided samples after polarization test. Large and deep pits can be
clearly seen in the corroded surface for the untreated sample in Fig. 6
(a), which indicates that the surface of the substrate was severely
attacked by pitting corrosion. Compared with the substrate, some small
sized holes occurred on all the nitrided surfaces, as denoted by the
yellow arrow; meanwhile the passivation film occurred on the surface of
nitrided sample with − 400 V and − 500 V bias, as denoted by black ring,
as shown in Fig. 6 (b) and (c). This passivation film effectively prevented
the attack from Cl− , improving the pitting corrosion resistance of the
samples, and thus the pitting corrosion did not occur in these two
nitrided samples, which was consistent with the polarization curve. For
the sample nitrided at − 600 V, the size of holes increased and the
passivation film disappeared on the corroded surface. Moreover, some
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Surface & Coatings Technology 405 (2021) 126689
Table 2
EIS fitting parameters of the substrate and nitrided samples in 3.5% NaCl.
Sample Rs (Ω⋅cm2) CPE (Ω− 1⋅cm− 2⋅ sn) n Rct (Ω⋅cm2)
− 5
316 L 29.0 2.17 × 10 0.88 4.2 × 105
5
− 400 V 30.0 1.36 × 10− 0.80 1.2 × 106
5
− 500 V 32.0 1.89 × 10− 0.76 2.9 × 106
5
− 600 V 31.0 2.26 × 10− 0.84 1.9 × 105
larger and shallower pits than those of the substrate appeared on the
surface with low magnification, as shown in the inset of Fig. 6 (d). Using
energy spectrum analysis (Mapping), it was found that the pits were
enriched with C, O and Cr elements, as well as less Fe and Ni elements
compared with the substrate. A small amount of Cl element from 3.5%
NaCl electrolyte solution (2.23 wt%) was also detected by EDS.
In order to further investigate the electrochemical mechanism taking
place during corrosion, EIS measurements for the substrate and nitrided
samples were conducted in 3.5% NaCl solution. The typical Nyquist and
Bode plots are presented Fig. 7. From the Fig. 7 (a), it can be seen that
the Nyquist plots of all the samples exhibited a depressed capacitive
loop, which was related to the electrochemical reaction of the samples
that charge transfer was dominated during the corrosion process. The
impedance of the nitrided samples with − 400 V and − 500 V bias was
greater than that of the substrate, whereas the nitrided sample with
− 600 V bias in contrast. This indicates that the passive film formed on
the surface of the former provided a better protection from the attack of
Cl− ions. However, the depletion of Cr and N in surficial layer of the
latter led to the disappearance of passive film and the appearance of
porous and loose surface, as shown in Fig. 6 (d), which cannot effectively
hinder charge transfer, and thus the impedance decreased.
According to Bode plots in Fig. 7 (b), all the samples exhibit one time
constant. The time constant with the maximum at around 10 Hz in the
Bode-phase plot may be attributed to the charge transfer resistance and
double layer/space charge capacitance of corrosion process [35].
Different from the present observations, Mareci et al. [36] reported that
two time constants were observed in the Bode-phase plot determined for
nitrided austenite at 500 ◦ C, whereas only one appeared for the non-
nitrided sample, consistent with our observation. This may be due to
the fact that the nitrided layer was mainly composed of CrN phase.
However, according to the research by J. Alphonsa et al. [37], the
duplex stainless steel nitrided at 350 to 450 ◦ C also exhibited a single
time constant. When the nitriding temperature was 500 ◦ C, two ones
were observed in the Bode-phase plot, accompanied by a large amount
of CrN precipitates in the nitrided layer. Therefore, it can be inferred
that the precipitation of CrN causing the depletion of Cr is the reason
why the phase angle curve characterized by one time constant changes
to by two ones. However, only one time constant appeared in our ob­
servations for all the nitrided samples, which was mainly attributed to
the out-diffusion of Cr.
The equivalent electrical circuits used to fit the obtained EIS spectra
are shown in the insert of Fig. 7 (a), where Rs is the solution resistance,
Rct is the charge transfer resistance, the value of the exponent n indicates
the deviation from ideal capacitive behavior (when n = 1) in case of non-
ideal capacitance (when n < 1), and the CPE is used instead of the
double-layer capacitance(Cdl) to account for surface heterogeneity. All
these parameters are listed in Table 2. The samples nitrided at − 400 V
and − 500 V exhibited an excellent corrosion resistance. The nitrided
sample with − 400 V bias possessed the minimum CPE values of 1.36 ×
10− 5 Ω− 1⋅cm− 2⋅ sn, which indicates that the passive film formed on the
surface of nitrided layer was thick and dense enough to act as an
effective barrier against the diffusion of reactive ions, and thus improved
the corrosion resistance. As the bias increased to − 500 V, the excessive
precipitation of CrN led to Cr and N depletion, and thus the passive film
became thin and looser, shown in Fig. 6 (c). As a result, this barrier was
weakened, showing a slight increase in CPE value of 1.89 × 10− 5
Ω− 1⋅cm− 2⋅ sn. However, the Rct values were 2.9 × 106 Ω⋅cm2, greater
Z. Huang et al.
Fig. 8. Nano-hardness (a) and modulus (b) profile of nitrided layer with
different biases.
than that of the nitrided sample with − 400 V bias (1.2 × 106 Ω⋅cm2),
which was attributed to its thicker compound layer. Nitrided at − 600 V,
a large amount of CrN precipitation led to sever depletion of Cr, due to
lack of sufficient supplementary from out-diffusion of Cr, so that the
effective film cannot be formed. Therefore, the nitrided sample with
− 600 V bias possessed lower Rct and higher CPE values as compared to
the substrate, showing the worst corrosion resistance.
3.3. Mechanical properties
The nano-hardness (H) and elastic modulus (E) of the nitrided layer
were also evaluated since the mechanical properties are important
criteria for their use in practical application. Fig. 8 shows the H and E
profiles of nitrided layers with different biases. Obviously, the H and E of
all the nitrided samples can be significantly improved as compared to
the substrate. The value of H and E in the compound layer remained
substantially unchanged for the sample nitrided at − 400 V and − 500 V,
were about 15 GPa and 267 GPa, respectively; whereas a gradual
decrease of H and E occurred in the compound layer of the nitrided
sample with − 600 V bias, from 13.9 GPa and 256.4 GPa to 10.9 GPa and
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Surface & Coatings Technology 405 (2021) 126689
234.0 GPa. Meanwhile, the average value of H and E in the whole
compound layer decreased with increasing the bias, which was attrib­
uted to the phase transformation from a harder phase of high N-
expanded austenite (870–1140 HV) [38] to low N-expanded austenite
(approaching to the substrate of ~200 HV) in the compound layer, as
shown in Fig. 2.
4. Conclusions
In summary, an ultra-thick nitrided layer with excellent corrosion
resistance and high hardness was formed by hot wire enhanced PAN
under the bias voltage of − 400 V. The nitrided layer exhibited a double-
layer structure with an outer composed layer and an inner solid-solution
layer, the total thickness of which exceeded 80 μm. The outer layer was
composed of high N-expanded austenite and CrN phases, in which Cr
content reached 24.6 at.% (higher than 15.7 at.% of the substrate) due to
out-diffusion of Cr, while the inner layer was mainly composed of γN
with a trace of CrN precipitates. The precipitation of CrN resulted in the
improvement of the corrosion resistance, instead of deterioration, which
is attributed to the fact that the out-diffusion of Cr compensated the
depletion of Cr due to the precipitation of CrN, as seen from significant
rise of Cr content in the surficial layer. As the bias voltage increased, the
CrN phase precipitated continuously, companied by the transition from
high N-expanded austenite to low N-expanded austenite, causing a
depletion of Cr and N dissolved in the austenitic matrix. The depletion of
Cr that could not be compensated by the out-diffusing Cr, leading to a
decrease in the corrosion resistance, and the dissolution of N resulted in
the loss of passivity and occurrence of the pitting. Moreover, the hard­
ness and modulus also decreased with the increase of bias voltage.
CRediT authorship contribution statement
Yuan-Yuan Guo: Conceptualization, Supervision, Writing-review and
editing. Zhen Huang: Conceptualization and Writing-original draft and
editing. Zi-Xin Guo: Data curation, Software. Lei Liu: Methodology,
Writing-review. Jun Chen & Ze Zhang: Investigation. Jin-Long Li:
Methodology. Yan Li: Validation. Yan-Wen Zhou &Ying-Shuang Liang:
Supervision, Investigation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research work was supported by National Natural Science
Foundation of China (No. 51502126, 51972155 and 11805089),
Excellent Talents Project from Educational Department of Liaoning
Province (2020LNQN09), Provincial Key Laboratory Open Project of
USTL (USTLKFSY201705), Science Foundation for Youth Scholars of
USTL (2018QN12), and Training Program of Innovation and Entrepre­
neurship for College Students of Liaoning Province (S202010146016).
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