available online @ www.pccc.icrc.ac.

ir
Progress in Color Colorants Coating 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and

Electrochemical Potency

M. Rostami*1, S. Khamseh**1, M. Nemati Valandaran1, M. Ganjaee Sari1, E. Alibakhshi2, B. Ramezanzadeh2

1.
Department of Nanomaterial and Nanocoatings, Institute for Color Science and Technology (ICST), P.O. Box 16765-
654, Tehran, Iran
2.
Department of Surface Coating and Corrosion, Institute for Color Science and Technology (ICST), P.O. Box 16765-
654, Tehran, Iran

ARTICLE INFO

Article history:
PK NL steel, as a hard and process-wise stable alloy, has myriad
Received: 22 Aug 2021
Final Revised: 12 Nov 2021
Accepted: 16 Nov 2021
S applications in sheet metal forming. However, to increase the quality of
the products and decrease cost, applying a self-lubricant protective
coating on the surface seems to be an efficacious strategy. The CrN and carbon-
Available online: 11 Apr 2022
enriched CrN, i.e. (a-C: CrN), hybrid coatings are physically vapor-deposited on
Keywords: the SPK NL alloy surface. The C/N ratio on the morphology, tribological
Surface modification properties, mechanical characteristics, and anticorrosive features of the coated
SPK NL steel SPK NL substrates are studied. Results evidenced that high carbon inclusion
(a-C: CrN) increases the plastic hardness of the CrN coating up to about 35 GPa and
COF significantly improves the plasticity index to ~0.2. The COF decreases from ~0.6
Corrosion resistance. for CrN to ~0.1 for (a-C:CrN). Coatings with a high sp2 fraction impart an
excellent self-lubricant characteristic to SPK NL steel. Electrochemical
impedance spectroscopy data approve that both coatings provide high corrosion
resistance, and although CrN provides superior corrosion resistance
nonetheless. As an outcome, (a-C:CrN) hybrid coatings with high carbon
content, possessing high hardness, good tribological properties, and corrosion
resistance seems to be a prospective candidate for surface protection of SPK NL
steel. Prog. Color Colorants Coat. 15 (2022), 269-283© Institute for Color
Science and Technology.

1. Introduction Sheet metal forming as an appropriate fabricating

process has taken its place in automotive, aerospace,
Metal forming is a fundamental process of fashioning a
electronics, and building industries. The manufactured
specific shape of precise size through mechanical
objects usually have high quality and possess accurate
deformation. The metal is exposed to plastic deformation
geometry. However, it is still of great importance for the
by applying tensile, compressive, bending, shear forces,
manufacturers to increase the quality and durability of
or a mixture of them. This process is usually categorized
their products and simultaneously decrease cost by
into two main groups: i) bulk metal forming and ii) sheet
removing the present drawbacks of the process. For
metal forming. In the former, the raw materials have a
instance, in some metal forming processes such as deep
low surface-to-volume ratio, while in the latter, sheets,
drawing, wrinkle is a common fundamental problem.
plates, or strips with a larger aspect ratio are formed.

*Corresponding author: *rostami-m@icrc.ac.ir

** khamseh-sa@icrc.ac.ir
 M. Rostami et. al.

This is mainly originating from the friction between the increases the anticorrosive properties, and mechanical
blank surface and blank holder, punch, or die surfaces. strengths [16-22]. Guan et al. prepared Cr-doped GLC
The use of a liquid lubricant on the forming parts could coatings and showed anticorrosion improvements [23].
be a solution, although issues arise. Lubricants may Ming et al. reported that by the Cr incorporation into the
contain environmentally hazardous materials. It takes a-C coating, the toughness and corrosion resistance
time, energy, and sometimes it is costly to remove the enhance while internal stress decreases [24]. On the
residual lubricant from the parts. Besides, the lubricants other hand, carbon impregnation into the CrN coatings
can be corrosive and damage the forming tools and the improves the mechanical properties and lowers the
products. Therefore, considerable demands for the coefficient of friction [25-27]. Apparently, incorporating
development of lubricant-free strategies in metal a phase with a low friction coefficient, i.e. a-C, into the
forming methods are growing. Some efforts have been CrN coating reduces the friction coefficient of the final
made to omit lubricants in the deep drawing process. hybrid coating. Nevertheless, it should be noted that the
Self-lubricant coatings are recently exploited to avoid situations governing the experiment are also of great
liquid lubricant usage [1, 2]. Therefore, improving the importance. It is well accepted that there is a close
corrosion resistance of both the forming tools and the correlation between the deposition condition and
products seems to be of great significance. Hence, structure of the coatings. For instance, using various
designing an approach through which both the desired hydrocarbon gases as the carbon source in a plasma
attributions, i.e. self-lubrication and anticorrosion, are process results in coatings with different structures, and
imparted to the metallic product seems reasonable and properties [28, 29]. It has been shown that when the
well-founded. hydrocarbon gases with more C-H bonds are used, a
Amorphous carbon-based self-lubricant coatings much denser a-C coating is formed on the substrate [28].
have been used on sheet metal forming dies. The results For the case in point, the a-C coatings prepared by CH4
demonstrate that the metal forming process has been show higher density than the coatings prepared by C2H2.
significantly enhanced [1, 2]. Also, the chromium Moreover, it has been demonstrated that the a-C coatings
nitride, CrN, based protective coatings as highly hard, made by source gases of higher hydrogen to carbon
corrosion-resistant, and thermally stable coating ratios show outstanding high friction and wear
materials have been widely applied on metal forming performance and possess good performance in moist air
tools [3-6]. However, the high friction coefficient of CrN [29].
coatings is a disadvantage for processes under extreme Among the countless steel alloys, SPK NL, as a cold
conditions [7]. In consequence, finding a way to work tool steel simultaneously displays good wear
decrease the friction coefficient of the CrN coatings is of resistance and high toughness, which give it exceptional
great necessity to broaden its industrial applications. cutting edge preservation. It has found its place in sheet
Notwithstanding, the CrN and amorphous carbon- metal forming such as mold plates, inserts, wear plates,
based (a-C) protective coatings are still the most widely and cutting dies. However, its low corrosion resistance
used protective coatings in actual productions. A decreases the lifetime of the forming tools and lowers
combined hybrid coating of a-C and CrN coatings, final product quality. The dimension accuracy of the
which carries the advantages, i.e. highly anti-corrosive devices is also affected due to the forming defects such as
and low COF, and depletes the disadvantages, seems to wrinkles. Therefore, improving the alloy anti-corrosion
be a smart strategy. a-C thin protective coatings fall into properties and, in the meantime eliminating the process
two main groups considering the chemical structure: (i) defects, i.e. crease, through using an appropriate coating
diamond-like carbon (DLC) thin coatings built up of seems to be necessary and reasonable. Carbon-enriched
high content of sp3 hybridization and (ii) graphite-like CrN hybrid coatings, i.e. (a-C: CrN), whose mechanical
carbon (GLC) coatings built up of high content of sp2 and electrochemical properties are optimized, may be a
hybridization [8-11]. High hardness and good promising choice that simultaneously increases the
tribological performance are attributions of the DLC anticorrosion and decreases the friction between the
coatings, while low friction coefficient, good wear surfaces. Some studies report the microstructure and
resistance, and self-lubricating characteristics belong to properties of (a-C:CrN) hybrid coatings prepared by
GLC coatings [12-15]. It has been reported that the Cr C2H2 [30-32]. Notwithstanding, few studies investigate
and N incorporation into the a-C coating’s structure the coatings prepared using CH4 as the carbon source in

270 Prog. Color Colorants Coat. 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and…

the plasma process. Besides, there exist even fewer acetone for 15 minutes, respectively. The mirror-like
studies which provide sufficient knowledge of the cleaned substrates were consequently fixed in the
electrochemical performance of these coatings in various multi-arc ion plating chamber. The base pressure of the
environments. Carbon content is a crucial role that chamber was dropped as low as 2.2 × 10-5 Torr. The
influences the anticorrosion properties of (a-C: CrN) mixtures of argon (Ar), nitrogen (N2), and CH4 flows
hybrid coatings. Wang et al. synthesized CrCN coatings were let in the chamber as the process atmosphere. The
using graphite as a carbon source and evaluated the process was initiated by depositing a pure interlayer of
coatings’ electrochemical performance in simulated body chromium as thick as 0.3 µm on the substrates and
fluid (SBF) [33]. The results show that no carbide phase accomplished by deposition of (a-C:CrN) hybrid layers
is formed as in Raman data D and G peaks did not in the next step. The concentration of the atmosphere
emerge. Nevertheless, the CrCN coatings showed compositions was controlled by adjusting the flow rate
enhanced electrochemical performance compared to the of gas. Detailed information on the process is given in
CrN coating. In another study, the CrCN coatings with Table 1.
low carbon content (~ 12 at%) were prepared using C2H2,
and better corrosion resistance was obtained [25]. To 2.2. Coatings characterization
assess and evaluate the effect of a new carbon source, i.e. The chemical composition of the coatings was
CH4, on the microstructure and consequent mechanical analyzed by a JEOL JXA-8530 F field emission
and anti-corrosion properties alteration of the developed electron probe micro-analyzer. To investigate the
(a-C:CrN) hybrid coatings on SPK NL substrates, this crystalline structure of the deposited layers, a Phillips
study has been designed and conducted. PW-1800 X-ray diffraction (XRD) analyzer was
utilized. A CuKα rotating anode tube produces an X-
2. Experimental
ray with λmax of 0.54 nm. The chemical structure was
2.1. Deposition process characterized by Raman spectroscopy using a Takram
A multi-arc ion plating deposition technique was P50C0R10 device. A Lorentzian deconvolution method
utilized to deposit (a-C:CrN) hybrid coatings on the was employed to obtain the exact intensity and
substrates. Before the deposition process, surface amplitude of the Raman peaks. The maximum
polishing treatment to attain a mirror-like appearance deviation of two measured points multiplied by two
was applied on the substrates. Then, they were cleaned was considered as the estimated experimental error.
in an ultrasonic bath of deionized water, ethanol, and,

Table 1: Detailed information on the deposition process.

Bias voltage & Arc current N2 flow rate CH4 flow rate Ar pressure
Sample CH4/N2
amperage (A) (sccm) (sccm) (Pa)
-70 V
C-1 100 60 0 0.3 0
65 A
-70 V
C-2 100 60 15 0.3 0.25
65 A
-70 V
C-3 100 60 20 0.3 0.33
65 A
-70 V
C-4 100 60 30 0.3 0.5
65 A
-70 V
C-5 100 60 30 0.3 1
65 A

Prog. Color Colorants Coat. 15 (2022), 269-283 271

 M. Rostami et. al.

2.3. Mechanical properties area of the coatings, a barrier coating of beeswax-

colophony was applied to the samples. The EIS
A Hysitron TriboScopesNanomechanical device was
measurements were conducted in an open circuit
used to measure the hardness and Young modulus. The
potential (OCP) armature at a (±) 10 mV sinusoidal
coatings were indented by a Berkovich diamond indenter
potential perturbation across the frequency range of 10
at ambient temperature. The indentation load was kept
kHz to 10 mHz. The measurement points were
low enough that the deformation’s depth was lower than
gathered after specific immersion durations (24 h) in
10 % of the thickness of the deposited layers. In this
3.5 % NaCl solution.
manner, the substrate interference with the mechanical
properties of the coatings is sufficiently low to be
ignored. 3. Results and Discussion
A universal mechanical tester tribometer (TSN.WTC
Cr, N, and C contents of the deposited coatings are
02) was used to measure the tribological properties. A
plotted versus the CH4/N2 ratio and is given in Figure
ball−on−disk reciprocating sliding technique was
1a. As it is observed, Cr and N contents sharply
exploited. The ball was made of Si3N4, and the diameter
decrease right after introducing CH4 into the deposition
was 3 mm. The measurement was conducted at room
chamber. As CH4/N2 goes up, the N content moderately
temperature. The sliding speed was 0.05 m/s, and the
decreases while Cr does not show any significant
process was repeated at a frequency of 5 Hz. The load
change. With methane incorporation, the surface of the
was fixed at 10 N.
Cr target is covered with organic compounds, which
reduces the deposition rate of Cr. On the contrary, C
2.4. Electrochemical properties content continually increases. To correlate the
To assess the anti-corrosion attribution of the coatings, deposited coating’s elemental composition to the
electrochemical impedance spectroscopy (EIS) was composition of the plasma environment, the C/N ratio
implemented in 3.5 % sodium chloride electrolyte of the coatings is plotted versus the CH4/N2 ratio in
employing an Ivium Compactstat device. A three- Figure 1b. A nonlinear ascending correlation is seen,
electrode cell configuration, Ag/AgCl (3 M KCl) as the and C/N continuously increases as the CH4/N2 ratio
referenced and graphite (1×1 cm2) as the counter increases. It can be concluded from these results that a-
electrodes, was applied. A 1×1 cm2 area of the C impregnated CrN hybrid coatings, i.e. (a-C: CrN),
deposited coatings, as the working electrode, was with high amounts of carbon content have been
exposed to the electrolyte. To isolate the remaining successfully fabricated.

Figure 1: Chemical composition and C/N ratio of (a-C: CrN) hybrid coatings versus CH4/N2.

272 Prog. Color Colorants Coat. 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and…

XRD and Raman analyses give ideas about the (240) and (271) planes of the Cr3C2 phase and as it can
crystalline and chemical structures of the coatings; be seen, the intensity increases upon increasing the C/N
hence a better understanding of the microstructure can ratio. The results confirm that the CH4 incorporation
be gained. The coatings’ XRD spectra are presented in leads to a higher density of carbon species in plasma
Figure 2. There are two short diffracted peaks at around and encourages carbide phase formation in (a-C: CrN)
41 and 65 for the coatings prepared at lower C/N hybrid coatings [30]. The crystal grain size in the
ratios that are attributed to the Cr phase of the Cr coatings can be quantitatively estimated considering
droplets [26]. These peaks disappeared in the coatings the peak broadening through Scherrer's equation. The
with higher C/N ratios, i.e. C/N=1.83. Three diffracted output of this equation is, in fact, the thickness of the
peaks corresponding to (111), (200), and (220) planes crystal planes parallel to the normal direction. The CrN
of face-centered cubic, fcc, phase formed in CrN and Cr3C2 crystal grain size of the coatings as a
coating, i.e. C-1, can be seen. Nonetheless, a mixed function of C/N is given in Figure 2c. The crystal grain
structure of fcc-CrN and (220) orientation along with size of the CrN phase significantly drops from 275
orthorhombic-Cr3C2 phases, is formed in all the hybrid nm for C-1 to 10 nm for C-4. However, the crystal
coatings, i.e. C-2 to 5. It should be noted that the peak grain size of the (271) plane of Cr3C2 phase shows an
at around 43, which is attributed to the (200) plane of increment from ~70 to ~190 nm as C/N increases.
CrN phase, almost disappears in (a-C: CrN) hybrid According to Figure 1, the coatings' nitrogen content
coatings while a weak peak at about 63 exists in all decreases with increasing CH4 flow rate, which results
samples, which is correlated to the (220) plane of CrN. in lower CrN content of the coatings. It seems that with
However, this peak becomes broader at higher C/N increasing C/N ratio, solid solution hardening of the
ratios, indicating that its crystallinity and grain size are carbon phase in the CrN phase takes place and leads to
decreased [34]. Other distinctive peaks that are nucleation and growth of hard carbide, i.e. Cr 3C2, phase
correlated to the Cr3C2 phase can be seen at around in the coatings [26, 30]. It can be concluded that carbon
44.2, and 75 in (a-C: CrN) hybrid coatings. These incorporation increases the abundance and grain size of
two diffracted peaks are respectively related to the the Cr3C2 phase in (a-C: CrN) hybrid coatings.

Figure 2: X-ray diffraction patterns (a), magnified section (b), and grain size (c) of the coatings.

Prog. Color Colorants Coat. 15 (2022), 269-283 273

 M. Rostami et. al.

Raman spectra of the coatings are given in Figure It is ostensibly concluded from the microstructural
3a. Two distinctive peaks, commonly known as D- and analyses, i.e. XRD and Raman, that (a-C: CrN) hybrid
G-bands, as a typical feature of a-C coatings, are seen. coatings are composed of a two-phase amorphous
Alteration in their relative intensity, i.e. ID/IG, and carbon and CrN or Cr3C2 nanograins. Besides, the
broadening, i.e. FWHM, can be attributed to the carbon incorporation encourages chromium carbide
structure and properties of the coating. For example, in (Cr3C2 phase) formation in the coatings, and carbide
carbon-based films, FWHM of the D- and G-band content increases by increasing C/N. Moreover, the (a-C:
peaks determine crystallinity [11, 19]. It has been CrN) hybrid coatings prepared at higher C/N ratios
shown that when most of the carbon-based coating is contain greater extents of sp3 carbon, and the structural
amorphous, broad and diffuse peaks appear. Sharp order is enhanced. Therefore, to pursue the changes in
peaks emerge when the carbon coating is more structure and morphology alteration mentioned above,
crystalline [11]. ID/IG is obtained through curve area the FE-SEM technique was exploited. The images are
integration of D- and G-band peaks using a Gaussian given in Figure 4. A honeycomb-like co-continuous
curve fitting. ID/IG and FWHM are plotted as a function structure has been developed in all coatings. This was
of C/N and presented in Figure 3 b and c. Both values previously reported in Arc PVD synthesized coatings
continuously decrease as C/N increases. Hence, (a-C: [25]. The metal droplets of Cr can be seen on the
CrN) hybrid coatings prepared at higher C/N ratios surface, and the number of these droplets is maximum at
contain a more significant amount of sp3 hybridized medium C/N ratios (Figures 4c and d). This is in good
carbon and a lower degree of sp2 ones. Furthermore, agreement with the XRD analysis of the coatings. The
since FWHM reduces as C/N increases, these coatings thickness of the Cr interlayer in CrN and (a-C: CrN)
are more crystalline. hybrid coatings are about 0.3 and 2.2 μm, respectively.

Figure 3: Raman spectra (a), ID/IG (b) and FWHM (c) versus C/N ratio.

274 Prog. Color Colorants Coat. 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and…

Figure 4: Plane view FE-SEM images of (a-C: CrN) hybrid coatings, i.e. C-1 to C-5 (a-f).

As mentioned previously, the mechanical hybrid coatings prepared using C2H2 gas as the carbon
characterization was carried out by analyzing the source, the coatings showed lower carbon content and
hardness, and Young modulus of the obtained coatings. lower hardness values compared to the results of the
The variation of hardness, Young modulus, and H3/E2 current study [25, 26, 30, 31]. The results of the present
of the (a-C: CrN) hybrid coatings as a function of C/N study show that (a-C: CrN) hybrid coatings with higher
are presented in Figure 5. It can be seen that the carbon content and higher hardness can be obtained
hardness value of SPK NL substrate increased via its using CH4 gas as the carbon source in the plasma
surface modification and all coated substrates showed environment and this coating is a good candidate for
higher hardness values. Seemingly, hardness has an surface protection of SPK NL.
ascending trend as C/N increases and reaches a The plasticity index, i.e. H3/E2, of the coatings, has
maximum value of ~35 GPa for CrCN-5 and all the (a- been presented in Figure 5c as a function of C/N. This
C: CrN) hybrid coatings are harder than CrN. index represents the coating resistance against plastic
However, the Young modulus demonstrates a second- deformation. This applied parameter is an indicator of
degree parabolic trend with a minimum at C/N=1.8 and evaluating the coatings' tribological properties [36–38].
a maximum at C/N=2.09. These behaviors might be As the diagram depicts, the plasticity index continuously
explained through the microstructure of the coatings. increases as C/N rises. Higher plasticity index and at the
According to the XRD results, all (a-C: CrN) hybrid same time, higher hardness indicate a hard
coatings contained a mixed structure of amorphous C, nanocomposite coating. As an accepted knowledge, the
CrN, and Cr3C2 phases yet at various concentrations. existence of two phases, one continuous amorphous
One reason causes the higher hardness for (a-C: CrN) phase, and one nano-grains dispersed phase, together
hybrid coatings compared to CrN might be the solid improves the mechanical properties of the
solution hardening effects of the carbon phase on the nanocomposite coatings [39, 40]. According to the
CrN phase that leads to nucleation and growth of hard microstructural analysis of the coatings, i.e. XRD and
carbide, i.e. Cr3C2, phase in the coatings [26, 30]. This Raman, (a-C: CrN) hybrid coatings are composed of a
effect is even enhanced as C/N increases. Moreover, mixed structure of Cr3C2 and CrN nano-grain phases
Raman outcomes showed that (a-C: CrN) hybrid dispersed in a continuous a-C phase which in turn is
coatings prepared at higher C/N contain a-C structure, comprised of different contents of sp2 and sp3
which is composed of a higher share of sp3 hybridizations. Hence, the structure is quite resembling a
hybridization or the so-called diamond-like carbon. nanocomposite material [36-38]. This structure is
This phase can increase the hardness of the whole responsible for the increases in the plasticity index of the
structure, hence (a-C: CrN) the hybrid coatings coatings and enhanced mechanical properties [36-40].
prepared at a higher C/N ratio are harder (Figure 3). From the above mentioned results it can be concluded
Although it is an accepted term that a-C based coatings that surface treatment of SPK NL substrate has a great
which contain a higher amount of sp3 hybridization are impact on mechanical and tribological properties.
harder [35], in some related studies that (a-C: CrN)

Prog. Color Colorants Coat. 15 (2022), 269-283 275

 M. Rostami et. al.

3 2
Figure 5: Variation of hardness (a), Young modulus (b), and H /E (c) of CrN and (a-C: CrN) hybrid coatings as a
function of C/N.

Figure 6: Variation of COF value (a) and friction behaviors (b) of CrN and (a-C: CrN) hybrid coatings.

Figure 6a gives the average coefficients of friction sections: An abrupt increase across the first 300 s and
versus C/N, and Figure 6b shows the friction behaviors then a relatively steady-state region. Notwithstanding,
as a function of time while the normal load is applied the C-5 shows friction coefficients as significant as
on the CrN and (a-C: CrN) hybrid coatings. The CrN yet smaller fluctuations. For other (a-C: CrN)
coatings slide against Si3N4 balls in ambient air. The hybrid coatings with lower C/N ratios, the first stage is
CrN friction curve shows a rapid increase within the less abrupt than is accomplished within the early 200 s
first 400 s and then becomes steady-state with a and the steady-state region, which is distinctively
relatively small amplitude of fluctuations. However, shorter compared to C-1 and C-5. It can be concluded
the (a-C: CrN) hybrid coatings offer different behavior. from the COF diagram that the average COF of the
Their trend can be divided into two distinguished coatings prepared at lower C/N ratios is less than CrN.

276 Prog. Color Colorants Coat. 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and…

Obviously, (a-C: CrN) hybrid coatings possess adhesion between contacted surfaces. This results in
improved wear resistance. To explain this behavior, a low surface energy either [41]. The same explanation
flashback to the structural results is required. The justifies elevated COF for C-5. The lower fraction of
Raman outcomes showed that (a-C: CrN) hybrid sp2 carbon in (a-C: CrN) hybrid coatings prepared at
coatings prepared at lower C/N composed of a higher higher C/N weakens the anti-wear capacity.
fraction of sp2 hybridization or graphite-like carbon. EIS analyses have been carried out at various time
This smooth structure shows a self-lubricant effect intervals, i.e. 1, 4, and 24 h, of immersion in 3.5%
during the friction measurement and significantly NaCl electrolyte to evaluate the corrosion protection of
reduces friction. The planar 2D structure of sp 2 carbon the coatings on the SPK NL substrates. The Bode-
at the interface minimizes swinging effects of σ bonds phase and Nyquist diagrams for these as-prepared
at the contacted surfaces and attenuates the strong coatings are illustrated in Figures 7 and 8.

Figure 7: Impedance modulus and phase angle as functions of frequency at various intervals (Bode-Phase angle)
diagrams: (a) blank, (b) C-1, (c) C-2, (d) C-3, (e) C-4 and (f) C-5.

Prog. Color Colorants Coat. 15 (2022), 269-283 277

 M. Rostami et. al.

Figure 8: Nyquist diagrams for: (a) blank, (b) C-1, (c) C-2, (d) C-3, (e) C-4 and (f) C-5.

The low-frequency impedance modulus can be modulus of the CrN (C-1) coating is higher than that for
considered as a precise ruler, which evaluates the the (a-C: CrN) (C-2 to 5) hybrid coatings at the end of
corrosion protection of the coatings [42, 43]. Moreover, the immersion time. This is confirmed by the lowest
the high-frequency phase angle values provide accurate capacitive-loop size of this sample in the Nyquist
information on the barrier performance of the coatings diagrams (Figure 8). The (a-C: CrN) hybrid coatings
[44, 45]. As it is obtainable from the Bode-Phase show similar impedance modulus values at around 104
diagrams, the uncoated (bare) sample has the lowest Ω.cm2 at the early stage of the immersion; however, the
low-frequency impedance modulus. The most positive resistance abruptly decreases as time passes. Seemingly,
high-frequency phase angle also belongs to the bare these coatings are initially protecting the surface, yet the
substrate at different immersion intervals. In other breaks due to the continuous exposure to the harsh and
words, the capacitive-loop size is enlarged as the aggressive environment. The best performance among
coatings are applied on the surface. The capacitive-loop these hybrid coatings belongs to the C-5. Using the
size in the Nyquist diagrams is associated with the total Bode-Phase diagrams, it is also possible to describe the
resistance of the coated samples [46]. These results type of electrochemical reactions occurring at the
confirm that the SPK NL surface has become immune coating and metal-solution interface. These reactions are
by a protecting layer. The low-frequency impedance directly correlated to the corrosion resistance [47, 48].

278 Prog. Color Colorants Coat. 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and…

These diagrams also depict two-time constants for the decrease as the immersion prolongs. This decrease in
coated substrates at each immersion interval. These Rc of the (a-C: CrN) hybrid coatings may be correlated
high-frequency and low-frequency time constants are to the accumulation of conducting species of the
correlated to the deposition of the coating, and the corrosion products into the coating porosity. Also, Cc
formation of corrosion products at the exposed surface, for CrN is lower than that for the (a-C: CrN) hybrid
respectively [49]. coatings meaning that a relative deterioration in
An equivalent circuit (two-time constant corrosion resistance has occurred by impregnating
equivalence) was modeled using the impedance results carbon into the structure. Nevertheless, the absolute
(Figure 9) for CrN and )a-C: CrN( hybrid coatings. As it measure of the corrosion moduli for these coatings is
still significant. This reduction could be attributed to
is depicted in Figure 9a, the modeled circuit for the bare
the higher concentration of Cr in CrN than the (a-C:
metal reveals three moduli; (i) a resistance (Rs)
CrN) ones. Among the hybrid coatings, CrCN-5
associated with the solution or electrolyte, (ii) a
demonstrates the best corrosion protection. They can
resistance (Rct) assigned to the charge transfer resistance
be ordered as CrCN-5< CrCN-4 < CrCN-3 < CrCN-2.
of the reactions, which happen at the metal/solution
This is mainly attributed to the chromium carbide
interface, and (iii) a double layer constant phase element
(Cr3C2) phase formed in (a-C:CrN) hybrid coatings.
created at the mentioned interface (CPEdl). In Figure 9b,
The corrosion resistance enhances as the concentration
two other moduli, namely Rc (coating resistance) and
of this phase increases and the highest concentration of
CPEc (coating constant phase element), are given. The
Cr3C2 phase belongs to C-5.
quantitative outcomes are presented in Table 2. In this
It is evident from the EIS results that, CrN and (a-C:
table, Y0 and n are the admittance and index of the
CrN) hybrid coatings can provide the SPK NL substrate
surface irregularity, respectively. It is clear from the data
with relatively significant corrosion resistance. Besides,
that as the immersion time increases, the Rct decreases
the anti-corrosion performance of CrN itself is superior
while Y0,dl increases. These are solid proofs that the SPK
to the (a-C:CrN) hybrid coatings. According to Figure 4,
NL corrosion has initiated in the corrosive electrolyte,
all the coatings show the same honey-comb-like
and low corrosion resistance is observed. However, the
morphology. It seems that the surface morphology does
deposition of CrN and (a-C: CrN) hybrid coatings on the
not affect the corrosion resistance. However, the Cr
surface causes Rct to improve, and a new resistance
content of the CrN coating is the highest. It is well
emerges for all of the immersion periods. The increment
known that Cr forms a passive chromium oxide or
of Rct is mainly due to the protecting layer of the coatings
chromium hydroxide layer at the interface that hinders
that hinders electrolyte access to the surface [50].
the substrate contact with corrosive species [52, 53]. The
Moreover, Rp (collection of Rct and Rc) for CrN is higher
efficient formation of such a layer is most probable for
than that for the (a-C: CrN) hybrid coatings across the
CrN compared to (a-C: CrN) the hybrid coatings. An
whole immersion durations. Also, this modulus
interesting correlation can be found between the carbon
increases as the immersion time goes by. The latter is
content and anticorrosion properties of the hybrid
vice versa for the (a-C: CrN) hybrid coatings meaning
coatings. The resistance improves as the carbon content
that the Rp decreases as the immersion time increases.
increases.
Accordingly, Y0,dl for CrN is lower than that for the (a-C:
CrN) hybrid coatings and decreases as the immersion
prolongs. This behavior can be attributed to the
alteration of the chemical composition of CrN. It is well
accepted that the changes in the chemical composition of
the layer lead to changes in the double-layer properties
of the coated substrate. Altogether, the electrochemical
behavior of CrN concludes that an active/protecting
performance mechanism governs the coatings. Figure 9: Electrical equivalent circuits used for
modeling of impedance data; (a) one-time constant and
Changes in Rc give information on the barrier (b) two-times constants.
performance of the coating [51]. Rc for CrN is higher
than that for (a-C: CrN) hybrid coatings across the
whole immersion durations, although they all relatively

Prog. Color Colorants Coat. 15 (2022), 269-283 279

 M. Rostami et. al.

According to XRD analyses outcomes (Figure 2), the better corrosion resistance. However, the current study
chromium carbide (Cr3C2) phase formed in (a-C: CrN) results somehow contradict some of the others; for
hybrid coatings structure increases by increasing the instance, the studies of Ye et al. [25] and Wang et al.
C/N ratio. The crystalline chromium carbide can [33]. There are two probable reasons for these
effectively isolate the structural defects of (a-C: CrN) differences; (i) carbon content of the coatings prepared
hybrid coatings resulting in an improvement in by Ye et al. was ~12 at%, which is much lower than in
corrosion resistance [54]. Also, the chromium carbide this paper, i.e. 47%. As mentioned above, there is a
with higher carbon content offers superior corrosion strong correlation between the carbon content and
resistance [55]. Accordingly, the higher availability of corrosion resistance of the hybrid coatings [55], and (ii)
the chromium carbide (Cr3C2) phase in the structure in Wang et al. study; they used SBF as the electrolyte,
might be the main reason for the improvement of the which is a much weaker corrosive medium compared
corrosion resistance. Wang et al. evaluated bio- to the solution of 3.5 wt% NaCl. The current study
corrosion resistance of CrCN coatings in SBF solution. results show that the carbon does not positively impact
They showed that when the coating’s carbon content is the corrosion resistance of CrN notwithstanding, (a-C:
less than ~52 at%, the coatings contain a stable N-C CrN) hybrid coatings with higher carbon contents
bond, which is challenging to be broken in the demonstrate sufficiently enough anticorrosion
corrosive media (SBF for that research) [33], leading to performance in 3.5 wt% NaCl.

Table 2: Electrochemical parameters extracted from EIS data for the prepared samples at various exposure times.
CPEdl CPEc
Time Rcta RCa
Sample Y0b
Y0b
(h) (ohm.cm2) nc (ohm.cm2) nc
(μs .ohm . cm )
n -1 -2
(μs .ohm-1. cm-2)
n

1 1531 197.7 0.74 - - -

Blank (without
4 1358 263 0.81 - - -
coating)
24 1178 299.4 0.81 - - -
1 263800 3.7 0.66 9698 0.5 0.49
C-1 4 174800 9.6 0.48 6467 5.5 0.68
24 158900 10.6 0.63 6319 4.5 0.34
1 16830 133.1 0.56 1731 14.9 0.78
C-2 4 13580 161.8 0.56 1391 20.1 0.75
24 8331 169.2 0.52 379.9 33.6 0.69
1 37630 14.5 0.78 2900 9.0 0.79
C-3 4 10600 128.9 0.74 37.9 99.1 0.53
24 10200 141.9 0.69 484.6 78 0.70
1 75620 7.8 0.67 304.5 4.2 0.69
C-4 4 71260 8.5 0.68 431.4 0.5 0.89
24 61200 13.5 0.78 5979 0.8 0.78
1 151300 3.7 0.63 4995 0.60 0.66
C-5 4 101600 4.8 0.96 4050 18.9 0.63
24 70570 8.1 0.69 6577 10.3 0.49
a
The standard deviation range for resistance values is between 2.1% and 9.4%.
b
The standard deviation range for admittance values is between 1.3% and 5.6%.
c
The standard deviation range for n values is between 0.8% and 1.2%.

280 Prog. Color Colorants Coat. 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and…

4. Conclusions self-lubricant characteristic of the (a-C:CrN) hybrid

coatings, and the vital role of the sp2 fraction on the COF
In the current study, the SPK NL substrates were surface
was approved. In conclusion, it is possible to protect the
treated via deposition of CrN and carbon enriched CrN,
surface of SPK NL alloy against wear, and corrosion
i.e. (a-C: CrN) hybrid coatings, by the aid of a multi-arc
using (a-C:CrN) hybrid coatings prepared by CH4 as the
ion plating device. The improvement in the mechanical
carbon source. These coatings contain higher carbon
properties and enhancement of the wear and corrosion
content and show higher hardness than the reports in
resistance were considered. The influence of the C/N
which C2H2 had been used as the carbon source. From
ratio on the microstructure, mechanical properties, COF,
the viewpoint of the coatings applications on metal
and electrochemical characteristics of the coatings was
forming parts, (a-C:CrN) hybrid coatings having an
investigated. The results showed that the carbon
average C/N ratio are promising candidates that have
incorporation improves the mechanical properties of
enhanced mechanical and tribological properties, low
CrN coatings however; it relatively deteriorates the
COF, and good corrosion resistance. The results of the
corrosion resistance. Notwithstanding, (a-C:CrN) hybrid
current study clarified the vital role of protective
coatings still possess significant corrosion resistance and
coatings on mechanical, tribological and electrochemical
protect the surface of SPK NL substrates against
performance of SPK NL substrates.
corrosive species. Moreover, the results confirmed the

5. References
1. M. Murakawa, N. Koga, T. Kumagai, Deep-drawing deposited (a-C: Nb) thin-film coating on GTD-450
of aluminum sheets without lubricant by use of stainless steel: enhancing mechanical and corrosion
diamond-like carbon coated dies, Surf. Coatings protection characteristics, Chem. Eng. J., 404(2020),
Technol. 76–77(1995), 553-558. 126490.
2. A. Mousavi, T. Kunze, T. Roch, A. Lasagni, A. 10. S. Khamseh, E. Alibakhshi, M. Mahdavian, M.R.
Brosius, Deep drawing process without lubrication - Saeb, H. Vahabi, J.-S. Lecomte, P. Laheurte, High-
An adapted tool for a stable, economic and performance hybrid coatings based on diamond-like
environmentally friendly process, Procedia Eng., carbon and copper for carbon steel protection, Diam.
207(2017), 48-53. Relat. Mater., 80(2017), 84-92.
3. Q. Wang, F. Zhou, X. Wang, K. Chen, M. Wang, T. 11. S. Khamseh, E. Alibakhshi, M. Mahdavian, M.R.
Qian, Y. Li, Comparison of tribological properties of Saeb, H. Vahabi, N. Kokanyan, P. Laheurte,
CrN, TiCN and TiAlN coatings sliding against SiC Magnetron-sputtered copper/diamond-like composite
balls in water, Appl. Surf. Sci., 257(2011), 7813-7820. thin films with super anti-corrosion properties, Surf.
4. D. M. Sanders, A. Anders, Review of cathodic arc Coatings Technol., 333(2018), 148-157.
deposition technology at the start of the new 12. L. Qiang, K. Gao, L. Zhang, J. Wang, B. Zhang, J.
millennium, Surf. Coatings Technol., 133-134(2000), Zhang, Further improving the mechanical and
78-90. tribological properties of low content Ti-doped DLC
5. C. Liu, Q. Bi, A. Matthews, EIS comparison on film by W incorporating, Appl. Surf. Sci., 353(2015),
corrosion performance of PVD TiN and CrN coated 522-529.
mild steel in 0.5 N NaCl aqueous solution, Corros. 13. M. Masuko, T. Ono, S. Aoki, A. Suzuki, H. Ito,
Sci., 43(2001), 1953-1961. Friction and wear characteristics of DLC coatings with
6. G. Bertrand, H. Mahdjoub, C. Meunier, A study of the different hydrogen content lubricated with several
corrosion behaviour and protective quality of Mo-containing compounds and their related
sputtered chromium nitride coatings, Surf. Coatings compounds, Tribol. Int., 82(2015), 350-357.
Technol., 126(2000), 199-209. 14. L. Wang, X. Guan, G. Zhang, Friction and wear
7. J. Wang, A. Zhang, L. Wang, The influence of metal behaviors of carbon-based multilayer coatings sliding
alloyed on the structure and wear properties of CrN against different rubbers in water environment, Tribol.
coatings, Lubr. Eng., 33(2008), 30-32. Int., 64(2013), 69-77.
8. S. Khamseh, E. Alibakhshi, B. Ramezanzadeh, M.G. 15. Y. Wang, L. Wang, Q. Xue, Improvement in the
Sari, A.K. Nezhad, Developing a graphite like tribological performances of Si3N4, SiC and WC by
carbon:niobium thin film on GTD-450 stainless steel graphite-like carbon films under dry and water-
substrate, Appl. Surf. Sci., 511(2020), 145613. lubricated sliding conditions, Surf. Coatings Technol.,
9. S. Khamseh, E. Alibakhshi, B. Ramezanzadeh, M. 205(2011), 2770-2777.
Ganjaee, A tailored pulsed substrate bias voltage

Prog. Color Colorants Coat. 15 (2022), 269-283 281

 M. Rostami et. al.

16. C. Zou, W. Xie, X. Tang, Further improvement of various source gas plasmas, Surf. Coatings Technol.,
mechanical and tribological properties of Cr-doped 120-121(1999), 589-593.
diamond-like carbon nanocomposite coatings by N 30. Y. Yuwei, W. Yongxin, W. Chunting, L. Jinlong, Y.
codoping, Jpn. J. Appl. Phys., 55(2016), 115501. Yirong, An analysis on tribological performance of
17. W. Dai, G. Wu, A. Wang, Preparation, CrCN coatings with different carbon contents in
characterization and properties of Cr-incorporated seawater, Tribiology Int., 91(2015), 131-139.
DLC films on magnesium alloy, Diam. Relat. Mater., 31. T. Polcar, T. Vitu, L. Cvrcek, J. Vyskocil, A.
19(2010), 1307-1315. Cavaleiro, Effects of carbon content on the high
18. W. Dai, H. Zheng, G. Wu, A. Wang, Effect of bias temperature friction and wear of chromium
voltage on growth property of Cr-DLC film prepared carbonitride coatings, Tribiology Int., 43(2010), 1228-
by linear ion beam deposition technique, Vacuum, 1233.
85(2010), 231-235. 32. J. Hu, X. Tian, M. Yang, C. Gong, J. Lin,
19. J. Sun, Z.Q. Fu, W. Zhang, C.B. Wang, W. Yue, S.S. Improvement of discharge and microstructure of Cr-
Lin, M.J. Dai, Friction and wear of Cr-doped DLC C-N coatings by electromagnetically enhanced
films under different lubrication conditions, Vacuum, magnetron sputtering, Vaccum, 148(2018), 98-105.
94(2013), 1-5. 33. Q. Wang, F. Zhou, Z. Zhou, L.K. Li, J. Yan,
20. D. Bootkul, B. Supsermpol, N. Saenphinit, C. Influence of carbon concentration on the
Aramwit, S. Intarasiri, Nitrogen doping for adhesion electrochemical behavior of CrCN coatings in
improvement of DLC film deposited on Si substrate simulated body fluid, Surf. Coat. Technol., 265(2015),
by Filtered Cathodic Vacuum Arc (FCVA) technique, 16-23.
Appl. Surf. Sci., 310(2014), 284-292. 34. S. Khamseh, M. Nose, T. Kawabata, A. Saiki, K.
21. M. H. Ahmed, J. A. Byrne, Effect of surface structure Matsuda, K. Terayama, S. Ikeno, Effect of deposition
and wettability of DLC and N-DLC thin films on conditions on the structure and properties of CrAlN
adsorption of glycine, Appl. Surf. Sci., 258(2012), films prepared by pulsed DC reactive sputtering in
5166-5174. FTS mode at high Al content, Mater. Trans.,
22. Y. Mabuchi, T. Higuchi, V. Weihnacht, Effect of 49(2008), 2082–2090.
sp2/sp3 bonding ratio and nitrogen content on friction 35. Q. Wang, F. Zhou, X. Ding, Z. Zhou, C. Wang, W.
properties of hydrogen-free DLC coatings, Tribol. Int., Zhang, L.K. Li, S. Lee, Microstructure and water-
62(2013), 130-140. lubricated friction and wear properties of CrN (C)
23. X. Guan, Y. Wang, J. Wang, Q. Xue, Adaptive coatings with different carbon contents, Appl. Surf.
capacities of chromium doped graphite-like carbon Sci., 268(2013), 579-587.
films in aggressive solutions with variable pH, Tribol. 36. R. Bayon, A. Igartua, J.J. Gonzalez, U. Ruiz De
Int., 96(2016), 307-316. Gopegui, Influence of the carbon content on the
24. M. Y. Ming, X. Jiang, D. G. Piliptsou, Y. Zhuang, A. corrosion and tribocorrosion performance of Ti-DLC
V. Rogachev, A.S. Rudenkov, A. Balmakou, coatings for biomedical alloys, Tribol. Int., 88(2015),
Chromium-modified a-C films with advanced 115-125.
structural, mechanical and corrosive-resistant 37. A.C. Ferrari, Raman spectroscopy of graphene and
characteristics, Appl. Surf. Sci., 379(2016), 424-432. graphite : Disorder, electron-phonon coupling, doping
25. Y. Ye, Y. Wang, H. Chen, J. Li, Y. Yao, C. Wang, and nonadiabatic effects, Solid State Commun.,
Doping carbon to improve the tribological 143(2007), 47-57.
performance of CrN coatings in seawater, Tribol. Int., 38. A. Das, B. Chakraborty, A.K. Sood, Raman
90(2015), 362-371. spectroscopy of graphene on different substrates and
26. C. Y. Tong, J. W. Lee, C. C. Kuo, S.H. Huang, Y. C. influence, Bull. Mater. Sci., 31(2008), 579-584.
Chan, H. W. Chen, J. G. Duh, Effects of carbon 39. J. Musil, H. Poláková, Hard nanocomposite Zr-Y-N
content on the microstructure and mechanical property coatings, correlation between hardness and structure,
of cathodic arc evaporation deposited CrCN thin Surf. Coatings Technol., 127(2000), 99-106.
films, Surf. Coatings Technol., 231(2013), 482-486. 40. F. Regent, J. Musil, Magnetron sputtered Cr-Ni-N
27. T. Bakalova, N. Petkov, H. Bahchedzhiev, P. Kejzlar, and Ti-Mo-N films: Comparison of mechanical
L. Voleský, Monitoring Changes in the tribological properties, Surf. Coatings Technol., 142-144(2001),
behaviour of CrCN thin layers with different CH4/N2 146-151.
gas ratios at room and elevated temperatures, Manuf. 41. Y. Wang, L. Wang, G. Zhang, S.C. Wang, R.J.K.
Technol., 18(2018), 533-537. Wood, Q. Xue, Effect of bias voltage on
28. K. P. Furlan, A. N. Klein, D. Hotza, Diamond-like microstructure and properties of Ti-doped graphite-
carbon films deposited by hydrocarbon plasma like carbon fi lms synthesized by magnetron
sources, Rev. Adv. Mater. Sci., 34(2013), 165-172. sputtering, Surf. Coat. Technol., 205(2010), 793-800.
29. A. Erdemir, I. B. Nilufer, O. L. Eryilmaz, M. 42. A. Salmasifar, M. Edraki, E. Alibakhshi, B.
Beschliesser, G.R. Fenske, Friction and wear Ramezanzadeh, G. Bahlakeh, Combined
performance of diamond-like carbon films grown in electrochemical/surface investigations and computer
modeling of the aquatic Artichoke extract molecules

282 Prog. Color Colorants Coat. 15 (2022), 269-283

Surface Modification of SPK NL Steel: Relevance to Tribological and…

corrosion inhibition properties on the mild steel 49. M. Mahdavian, A. R. Tehrani-Bagha, E. Alibakhshi,
surface immersed in the acidic medium, J. Mol. Liq. In S. Ashhari, M.J. Palimi, S. Farashi, S. Javadian, F.
Press, (2020), 114856. Ektefa, Corrosion of mild steel in hydrochloric acid
43. S. Khamseh, E. Alibakhshi, B. Ramezanzadeh, J.-S. solution in the presence of two cationic gemini
Lecomte, P. Laheurte, X. Noirefalize, F. Laoutid, H. surfactants with and without hydroxyl substituted
Vahabi, Tailoring hardness and electrochemical spacers, Corros. Sci., 137(2018), 62-75.
performance of TC4 coated Cu/a-C thin coating with 50. A. Nemati, M. Saghafi, S. Khamseh, E. Alibakhshi,
introducing second metal Zr, Corros. Sci., 172(2020), P. Zarrintaj, M.R. Saeb, Magnetron-sputtered
108713. TixNythin films applied on titanium-based alloys for
44. R. Samiee, B. Ramezanzadeh, M. Mahdavian, E. biomedical applications: Composition-microstructure-
Alibakhshi, Designing a non-hazardous nano-carrier property relationships, Surf. Coat. Technol.,
based on graphene oxide @ Polyaniline- 349(2018), 251-259.
Praseodymium (III) for fabrication of the Active 51. E. Alibakhshi, E. Ghasemi, M. Mahdavian, B.
/Passive anti- corrosion coating, J. Hazard., Ramezanzadeh, A comparative study on corrosion
398(2020), 123136. inhibitive effect of nitrate and phosphate intercalated
45. R. Samiee, B. Ramezanzadeh, M. Mahdavian, E. Zn-Al- layered double hydroxides (LDHs)
Alibakhshi, Assessment of the smart self-healing nanocontainers incorporated into a hybrid silane layer
corrosion protection properties of a water-base hybrid and their effect on cathodic delamination of epoxy
organo-silane film combined with non-toxic topcoat, Corros. Sci., 115(2017), 159-174.
organic/inorganic environmentally friendly corrosion 52. M. Darja Kek, P. Peter, C. Miha, M. Marijan, The
inhibitors on mild steel, J. Clean. Prod., 220(2019), corrosion behavior of Cr-(C, N) PVD hard coatings
17-27. deposited on various substrates, Electrochem. Acta.,
46. R. Samiee, B. Ramezanzadeh, M. Mahdavian, E. 49(2004), 1527-1533.
Alibakhshi, G. Bahlakeh, Graphene oxide nano-sheets 53. J. B. Bajat, I. Milosev, Z. Jovanocic, V.B. Miskovic-
loading with praseodymium cations: Adsorption- Stankovic, Studies on adhesion characteristics and
desorption study, quantum mechanics calculations and corrosion behaviour of vinyltriethoxysilane/epoxy
dual active-barrier effect for smart coatings coating protective system on aluminium, Appl. Surf.
fabrication, J. Ind. Eng. Chem., 78(2019), 36-48. Sci., 256(2010), 3508-3517.
47. E. Alibakhshi, E. Ghasemi, M. Mahdavian, The effect 54. X. Guan, Y. Wang, G. Zhang, X. Jiang, L. Wang, Q.
of interlayer spacing on the inhibitor release capability Xue, Microstructures and properties of Zr/CrN
of layered double hydroxide based nanocontainers, J. multilayer coatings fabricated by multi-arc ion plating,
Clean. Prod., 251(2020), 119676. Tribiology Int., (2016), 0-1.
48. M.J. Palimi, E. Alibakhshi, B. Ramezanzadeh, G. 55. C. Lu, N. Pu, K. Hou, C. Tseng, M. Ger, The effect of
Bahlakeh, M. Mahdavian, Screening the anti- formic acid concentration on the conductivity and
corrosion effect of a hybrid pigment based on zinc corrosion resistance of chromium carbide coatings
acetyl acetonate on the corrosion protection electroplated with trivalent chromium, Appl. Surf. Sci.,
performance of an epoxy-ester polymeric coating, J. 282(2013), 544-551.
Taiwan Inst. Chem. Eng., 82(2018), 261-272.

How to cite this article:

M. Rostami, S. Khamseh, M. Nemati Valandaran, M. Ganjaee Sari, E. Alibakhshi, B.
Ramezanzadeh, Surface Modification of SPK NL Steel: Relevance to Tribological and
Electrochemical Potency. Prog. Color Colorants Coat., 15 (2022), 269-283.

Prog. Color Colorants Coat. 15 (2022), 269-283 283