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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Preparation and wear properties of Ni/TiN–SiC nanocoatings obtained by

pulse current electrodeposition
Fafeng Xiaa, Qiang Lia, Chunyang Maa,∗, Wenqing Liua, Zhipeng Maa,b
a
College of Mechanical Science and Engineering, Northeast Petroleum University, Daqing, 163318, China
b
College of Mechanical and Electrical Engineering, Hohai University, Changzhou, 213022, China

A R T I C LE I N FO A B S T R A C T

Keywords: In this report, Ni/TiN–SiC nanocoatings were designed by pulse current electrodeposition (PCE) technique. The
Ni/TiN–SiC nanocoating influence of plating parameters on morphology, microstructure, microhardness, and wear behavior of the as-
Pulse current electrodeposition obtained coatings were investigated by transmission electron microscopy (TEM), scanning electron microscopy
Microstructure (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), triboindentry, and abrasion testing.
Microhardness
Results indicated incorporation of numerous TiN and SiC nanoparticles in Ni/TiN–SiC nanocoatings prepared at
Wear resistance
4 A/dm2. Average sizes of TiN and SiC nanoparticles were estimated to 45.9 nm and 37.2 nm, respectively.
Cross-sectional views of nanocoating obtained at 4 A/dm2 revealed high concentrations of Ti (19.6 at%), Si
(12.1 at%), and Ni (53.3 at%). Hence, Ni/TiN–SiC nanocoating deposited at 4 A/dm2 with average micro-
hardness of 848.5 Hv illustrated the highest microhardness when compared to other nanocoatings. On the other
hand, wear rate of Ni/TiN–SiC nanocoating prepared at 4 A/dm2 was only 13.6 mg/min, indicating excellent
wear resistance. In addition, only some small surface scratches were observed, indicating outstanding wear
performance.

1. Introduction
Nowadays, metal-based ceramic composite coatings (such as
Ni–TiN, Ni–AlN, Ni–Co/SiC, and Ni–CeO2) attracted increasing atten-
tion due to their excellent physical and chemical properties, such as
good microhardness, outstanding wear resistance, and high thermal
resistance [1–10]. These composite coatings can be prefabricated by
electrodeposition, electroless plating, and brush plating technology
[11–13]. In particular, electrodeposition processes several advantages
when compared to electroless and brush plating, including high de-
position rates, simple structures, no limitation for reinforcing particles,
and reduced electrode losses. Li et al. [14] reported on the synthesis of
Ni–B/Ni–W–BN composite coatings via co-electrodeposition. The re-
sults indicated that the crystal size of the Ni–B/Ni-W-BN coating was
smaller compared to a monolayer Ni–W–BN coating. Alizadeh et al.
[15] investigated the microstructure and properties of Ni–Mo/Al2O3
nanocoatings deposited via electrodeposition. They found that a large
number of Al2O3 nanoparticles were uniformly embedded in the na-
nocoatings. Electrodeposition process can be divided into two cate-
gories: direct current electrodeposition (DCE) and pulse current elec-
trodeposition (PCE). Li et al. [16] discussed that boron nitride
reinforced Ni–W nanocoatings were successfully prefabricated by using
PCE method. Compared to DCE, PCE has been applied in mechanical,
petroleum, chemical and military fields thanks to decreased internal
stress and porosity of coatings, refined matrix grains, and enhanced
plating rates [17–20].
TiN and SiC particles are inorganic ceramic materials with excellent
material properties. In particular, TiN nanoparticles possess high
hardness and strength with significant wear and corrosion resistance.
As such, TiN nanoparticles have been applied as a reinforced phase to
fabricate composite coatings with excellent physical and chemical
properties [21–23]. By comparison, SiC nanoparticles have excellent
thermal stability, and outstanding wear resistance, but suffer from
elevated microhardness. There has been numerous papers published
reporting on the preparation of Ni–TiN, Ni–SiC, Cu–SiC coatings de-
posited by DCE and PCE techniques. However, only a few have in-
vestigated the prefabrication of Ni/TiN–SiC nanocoatings via the PCE
technique. Therefore, this study aims to prefabricate TiN and SiC na-
noparticle reinforced metal-based ceramic composites by PCE deposi-
tion and to improve the physical and chemical properties of these
composites. Besides, the effects of plating parameters on morphology,
microstructure, microhardness and wear behavior of the as-fabricated
Ni/TiN–SiC nanocoatings by PCE technique were all examined and the
results were discussed.

∗
Corresponding author.
E-mail address: chunyangandma1@163.com (C. Ma).

https://doi.org/10.1016/j.ceramint.2019.12.017
Received 24 September 2019; Received in revised form 22 November 2019; Accepted 2 December 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Fafeng Xia, et al., Ceramics International, https://doi.org/10.1016/j.ceramint.2019.12.017
F. Xia, et al.
Fig. 1. Experimental device for preparing Ni/TiN–SiC nanocoatings.
Fig. 2. TEM images of TiN and SiC products: (a) TiN nanoparticles, and (b) SiC
nanoparticles.
2. Experiment
Ni/TiN–SiC nanocoatings were prefabricated on Q235 steel by PCE
method from modified plating solution containing 200 g/L NiSO4
(Daqing Tongda Co., Ltd. Purity of 99.9%), 30 g/L NiCl2 (Daqing
Tongda Co., Ltd. Purity of 99.9%), 30 g/L H3BO3 (Daqing Tongda Co.,
Ltd. Purity of 99.9%), 60 mg/L cetyltrimethyl ammonium bromide
(Daqing Tongda Co., Ltd. Purity of 99.9%), 8 g/L TiN nanoparticles
(Hefei Cole Nano-technology Co., Ltd. Purity of 99.99%), and 8 g/L SiC
nanoparticles (Daqing Tongda Co., Ltd. Purity of 99.98%) [24]. The
diameters of TiN and SiC nanoparticles ranged from 20 to 40 nm. A
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pure nickel plate (diameter of 30 × 30 × 10 mm) was used as anode
and Q235 steel (diameter of 30 × 20 × 5 mm) as cathode. The distance
between the two electrodes was kept at 200 mm. The experimental
device used to produce Ni/TiN–SiC nanocoatings is presented in Fig. 1.
The device was composed of pulse current source (SMD-100, Handan
Dawei Electroplating Equipment Co., Ltd.), heating system (DRB-1000,
Boao Electric Heating Equipment Co., Ltd.), ultrasonic agitator (XL-300,
Beijing Xieli Ultrasonic Cleaning Equipment Co., Ltd.), and plating
bath. The pulse current source was utilized to generate pulse current
densities of 2, 4 and 6 A/dm2 at duty cycle kept at 40%. The heating
system was used to maintain the plating solution at 45 °C. The ultra-
sonic agitator was employed to keep dispersed TiN and SiC nano-
particles evenly suspended in the plating solution. A plating solution pH
of 4.6 was achieved by either adding hydrochloric acid (10 vol%) or
NaOH solution (10 wt%), and plating time was 40 min. After PCE, the
electrodes were cleaned by ultrasonic agitation for 10 min to dislodge
any loosely adsorbed TiN and SiC nanoparticles.
The surface morphologies, cross-sections and microstructures of the
as-obtained Ni/TiN–SiC nanocoatings were viewed by transmission
electron microscopy (TEM, Tecnai-G2-20-S-Twin) and scanning elec-
tron microscopy (SEM, S3400) equipped with IE-300X type energy
disperse spectroscopy (EDS). The surface compositions were de-
termined by Rigaku D/Max-2400 X-ray diffraction (XRD) with Cu-Ka
radiation (k=1.54 Å). The cross-section compositions of Ni/TiN–SiC
nanocoatings were investigated by X-ray photoelectron spectroscopy
(XPS, INCA X-MAX). The nanohardnesses values of Ni/TiN–SiC nano-
coatings were measured by means of TI-950 triboindenter at loading
force of 1000 μN for 10 s. To examine wear properties of Ni/TiN–SiC
nanocoatings, friction and wear tests were performed using MRH-6
abrasion tester (Jingchen Test Instrument, China). To this end, har-
dened steel barrel (GC15) was run on nanocoating surface at 5 N ap-
plied load and 0.1 m/s constant speed under dry sliding conditions at
room temperature. The wear testing time was set at 30 min and worn
surface morphologies of Ni/TiN–SiC nanocoatings were viewed by SEM
after testing. The wear rate (V) of each nanocoating was computed
according to Eq. (1):
M1 − M 2
V=
L (1)
where M1 and M2 denote the mass of each sample before and after each
wear test, respectively. The mass was measured by a lab balance (ac-
curacy: 0.1 mg). L represents the sliding length of hardened steel ball
during wear experiments.
F. Xia, et al.
Fig. 3. SEM images of Ni/TiN–SiC nanocoatings prepared with different pulse current densities: (a) 2 A/dm2, (b) 4 A/dm2, and (c) 6 A/dm2.
3. Results and discussion
3.1. TiN and SiC nanoparticles
Fig. 2 exhibits the morphologies of as-received TiN and SiC nano-
particles. The average diameters of TiN and SiC nanoparticles were
determined as 40 and 35 nm, respectively. TiN and SiC nanoparticles
were prone to aggregation due to their small sizes [25,26]. In addition,
TiN and SiC nanoparticles displayed regular crystal structures in the
micro-regions.
3.2. SEM analysis
Fig. 3a~c illustrate the SEM surface morphologies of Ni/TiN–SiC
nanocoatings prepared at pulse current densities of 2, 4 and 6 A/dm2,
respectively. The corresponding cross-section morphologies Ni/TiN–SiC
nanocoatings are displayed in Fig. 3a’~c’. The pulse current density
revealed great influence on surface morphologies of Ni/TiN–SiC na-
nocoatings (Fig. 3a~c). At pulse current density of 2 A/dm2, numerous
large-sized grains were formed on Ni/TiN–SiC coating with uneven and
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coarse structure. As pulse current density increased to 4 A/dm2, Ni/
TiN–SiC nanocoatings with smooth, uniform and fine surface
morphologies were observed by SEM. However, the grains sizes of Ni/
TiN–SiC nanocoatings became larger than those produced at 4 A/dm2 at
pulse current density further of 6 A/dm2. Sajjadnejad et al. [27] re-
ported that the microstructure of nickel-based coatings was controlled
by electroplating parameters such as pulse current density, pulse fre-
quency, and duty cycle, etc. They found that pulse current density could
effectively refine the grain size.
In addition, the thicknesses of Ni/TiN–SiC nanocoatings increased
from 46.8 μm to 58.7 μm as pulse current density rose from 2 A/dm2 to
6 A/dm2 (Fig. 3a’~c’), demonstrating the effect of pulse current density
on the deposition rate of nickel grains. The results are in agreement
with those reported by Sajjadnejad [28].
3.3. TEM
Fig. 4 shows TEM micrographs of Ni/TiN–SiC nanocoatings pre-
pared at different pulse current densities. The black sections in
Fig. 4a~c showed TiN and SiC nanoparticles whereas the white sections
F. Xia, et al.
Fig. 4. TEM micrographs of Ni/TiN–SiC nanocoatings prepared with different pulse current densities: (a) 2 A/dm2, (b) 4 A/dm2, and (c) 6 A/dm2.
were nickel grains. Some TiN and SiC nanoparticles appeared on Ni/
TiN–SiC nanocoating deposited at 2 A/dm2, whereas numerous TiN and
SiC nanoparticles became incorporated at 4 A/dm2. The average sizes of
TiN and SiC nanoparticles were recorded as 45.9 nm and 37.2 nm,
respectively. The reason for this had possibly to do with the moderate
pulse current density, which effectively inhibited TiN and SiC nano-
particles in Ni/TiN–SiC nanocoating. However, Ni/TiN–SiC
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nanocoating deposited at 6 A/dm2 possessed larger nickel grains
structures with serious agglomeration of TiN and SiC nanoparticles.
Fig. 5 displays TEM bright-field images of Ni, Ti, Si, N and C ele-
ments distributed in spectral area II of Ni/TiN–SiC nanocoating de-
posited at 4 A/dm2. Ni, Ti, Si, N, and C elements looked well-dispersed
in the nanocoating, testifying of the successful embedding of both TiN
and SiC nanoparticles in nickel matrix.
F. Xia, et al.
Fig. 5. TEM bright field image of Ni/TiN–SiC nanocoating deposited at pulse current density of 4 A/dm2.
3.4. Codeposition mechanism
Fig. 6 displays the co-deposition mechanism of nickel ions, TiN
nanoparticles and SiC nanoparticles during PCE process, which can be
explained by Guglielmi's theory. The nickel ions present in plating so-
lution were first adsorbed on TiN and SiC nanoparticles surfaces. Nu-
merous ion clouds then formed and became suspended in the bath. The
nickel ions, TiN and SiC nanoparticles then moved towards the cathode
surface under the action of electric field force (F). Meanwhile, hydrogen
evolution occurred on the cathode surface. TiN and SiC nanoparticles
passed both the electric double and hydrogen evolution layers to be-
come tightly embedded in Ni matrix metal.
The pulse current density also showed notable influence on dis-
tribution and amount of embedded TiN and SiC nanoparticles in Ni/
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TiN–SiC nanocoatings [29]. The relationship between electric field
force and pulse current density can be expressed by Eq. (2):
I×q
F=
σ (2)
where I denotes the pulse current density, q is the ironic charge, and σ
represents the conductivity of plating solution.
During PCE deposition of Ni/TiN–SiC nanocoatings, the effect of
electric field force on TiN and SiC nanoparticles looked not obvious
under low pulse current densities (such as 2 A/dm2), leading to low
amounts of incorporated TiN and SiC nanoparticles in the coating.
Thus, TiN and SiC nanoparticles did not significantly inhibit the growth
of nickel grains, resulting in free nickel grain growth and formation of
numerous large-sized grains. By comparison, suitable pulse current
F. Xia, et al.
Fig. 6. The co-deposition mechanism of the nickel irons, TiN nanoparticles and SiC nanoparticles during PCE process.
Fig. 7. XRD patterns of Ni/TiN–SiC nanocoatings produced with different pulse
current densities: (a) 2 A/dm2, (b) 4 A/dm2, and (c) 6 A/dm2.
densities (such as 4 A/dm2) could effectively increase the electric field
force and significantly reduce the thickness of hydrogen evolution
layer, leading to incorporation of significant amounts of TiN and SiC
nanoparticles in Ni/TiN–SiC nanocoating. Hence, TiN and SiC nano-
particles supplied large numbers of nuclei for formation of Ni grains
and restricted sustained growth of Ni grains, leading to formation of Ni/
TiN–SiC nanocoatings with smooth, uniform, and fine morphologies.
However, substantial amounts of hydrogen bubbles formed at the
cathode surface at pulse current density of 6 A/dm2, leading to in-
creased the thickness of hydrogen evolution layer. This, in turn, hin-
dered deposition of TiN and SiC nanoparticles on the cathode surface,
reducing the amounts of embedded TiN and SiC nanoparticles in Ni/
TiN–SiC nanocoatings. This also declined the inhibitory effect of nickel
grains, increasing their grain sizes. Overall, these results were con-
sistent with those from SEM and TEM.
3.5. Microstructure
3.5.1. XRD
Fig. 7 presents the XRD patterns of Ni/TiN–SiC nanocoatings pro-
duced at different pulse current densities. Ni, SiC and TiN phases were
all present in Ni/TiN–SiC nanocoatings obtained at 2 A/dm2, 4 A/dm2,
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and 6 A/dm2. For Ni grains, three strong diffractions peaked were ob-
served at 44.8°, 52.2° and 76.7°, corresponding to (1 1 1), (2 0 0) and (2
2 0) planes, respectively. For TiN nanoparticles, three strong diffrac-
tions emerged at 36.6°, 42.6° and 61.8°, attributed to (1 1 1), (2 0 0) and
(2 2 0) planes, respectively. For SiC nanoparticles, three strong dif-
fractions located at 34.2°, 41.5° and 59.8° were noticed and assigned to
(1 1 1), (2 0 0) and (2 2 0) planes, respectively.
In Fig. 7, the diffraction peaks of Ni grains first decreased and then
increased as pulse current density rose from 2 A/dm2 to 6 A/dm2. Pulse
current densities on the order of 4 A/dm2 could potentially increase the
amounts of TiN and SiC nanoparticles in Ni/TiN–SiC nanocoating. Thus,
TiN and SiC nanoparticles supplied large numbers of nuclei for for-
mation of Ni grains and restricted sustained growth of Ni grains, leading
to formation of Ni/TiN–SiC nanocoatings with smooth, uniform, and
fine morphologies. Therefore, proper current densities can effectively
refine Ni grains of Ni/TiN–SiC nanocoatings.
3.5.2. XPS
Fig. 8 depicts cross-sectional composition distributions of Ni/
TiN–SiC nanocoatings deposited at different pulse current densities. TiN
and SiC nanoparticles became completely incorporated in Ni/TiN–SiC
nanocoatings. Ni/TiN–SiC nanocoating prepared at 2 A/dm2 showed
fewer TiN and SiC nanoparticles than those prepared at 4 A/dm2 and 6
A/dm2 (Fig. 8a). By contrast, high concentrations of Ti (19.6 at%), Si
(12.1 at%) and Ni (53.3 at%) were measured throughout the cross-
section of nanocoating obtained at 4 A/dm2. At 6 A/dm2, the con-
centrations of Ti, Si and Ni elements slightly reduced since the elevated
pulse current densities promoted co-deposition of Ni irons, TiN, and SiC
nanoparticles.
3.6. Microhardness test
The effects of pulse current density on microhardness values of Ni/
TiN–SiC nanocoatings deposited at different pulse current densities are
displayed in Fig. 9. Ni/TiN–SiC nanocoating deposited at 4 A/dm2 with
average microhardness of 848.5 Hv clearly depicted the highest mi-
crohardness than other nanocoatings. By comparison, Ni/TiN–SiC na-
nocoating obtained at 2 A/dm2 depicted an average microhardness of
only 699.2 Hv. According to previous studies [30–32], microhardness
of nanocoatings should not only depend on content of TiN and SiC
nanoparticles but also on distribution of nanoparticles throughout the
coating. High contents and uniform distributions of TiN and SiC na-
noparticles existed in Ni/TiN–SiC nanocoatings obtained at 4 A/dm2,
leading to dispersion–hardening effect and high microhardness. Be-
sides, TiN and SiC nanoparticles independently possessed microhard-
ness values, further improving the microhardness of the coatings.
F. Xia, et al.
Fig. 8. XPS cross-sectional profiles of Ni/TiN–SiC nanocoatings produced with
different pulse current densities: (a) 2 A/dm2, (b) 4 A/dm2, and (c) 6 A/dm2.
3.7. Wear test
3.7.1. Wear rate
Fig. 10 illustrates the wear rates of Ni/TiN–SiC nanocoatings de-
posited at different pulse current densities. The wear rates of all three
nanocoatings slightly enhanced during wear testing. Ni/TiN–SiC
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Fig. 9. Effect of pulse current density on microhardnesses of Ni/TiN–SiC na-
nocoatings.
Fig. 10. Wear rates of Ni/TiN–SiC nanocoatings produced with different pulse
current densities: (a) 2 A/dm2, (b) 4 A/dm2, and (c) 6 A/dm2.
nanocoating prepared at 2 A/dm2 showed maximum wear rate of
27.1 mg/min. Nevertheless, wear rate of Ni/TiN–SiC nanocoating pre-
pared at 4 A/dm2 was only 13.6 mg/min, indicating Ni/TiN–SiC na-
nocoatings with excellent wear resistance.
3.7.2. Worn surface morphology
Fig. 11 displays the worn surface morphologies of Ni/TiN–SiC na-
nocoatings deposited at different pulse current densities. Numerous
deep grooves and pits appeared on worn surfaces of Ni/TiN–SiC na-
nocoating deposited at 2 A/dm2, demonstrating nanocoating surface
with serious wear state. By contrast, only small scratches were dis-
played on nanocoating surface deposited at 4 A/dm2, testifying of
outstanding wear performance. However, pulse current densities
around 6 A/dm2 induced some large-sized grooves on nanocoating
surface.
3.7.3. Friction coefficient
Friction coefficient curves of Ni/TiN–SiC nanocoatings deposited at
various pulse current densities are displayed in Fig. 12. Among all three
nanocoatings, Ni/TiN–SiC nanocoating prepared at 4 A/dm2 had the
smallest average friction coefficient of 0.49. The nanocoating deposited
at 2 A/dm2 had the highest average friction coefficient with a value of
F. Xia, et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 12. Friction coefficients of Ni/TiN–SiC nanocoatings produced with dif-

ferent pulse current densities: (a) 2 A/dm2, (b) 4 A/dm2, and (c) 6 A/dm2.

Fig. 11. SEM images of the worn surface of Ni/TiN–SiC nanocoatings produced
with different pulse current densities: (a) 2 A/dm2, (b) 4 A/dm2, and (c) 6 A/
dm2.

0.76. TiN and SiC nanoparticles contents and microhardnesses of the

nanocoating are the main factors that ensure the friction coefficient of
Ni/TiN–SiC nanocoatings [33]. When the coatings TiN and SiC nano-
particle content was increased, numerous TiN and SiC nanoparticles
were separated from the nickel matrix under the action of friction
during wear tests. This reduced the friction coefficient by changing the
friction mode between the Ni/TiN–SiC nanocoating and the steel barrel
from sliding to rolling.
3.7.4. Wear mechanism
Fig. 13 illustrates the wear mechanisms of Ni/TiN–SiC nanocoatings
deposited at different pulse current densities. The wear resistances of
Ni/TiN–SiC nanocoatings were mainly affected by microhardness and
microstructure of each coating. Inappropriate pulse current densities
(such as 2 A/dm2 and 6 A/dm2) during PCE induced few TiN and SiC
nanoparticles in Ni/TiN–SiC nanocoatings (Fig. 13a). The microhard-
ness values of both nanocoatings were small. Hence, hardened steel
barrel could easily tear down large pieces of coating, leading to Ni/
Fig. 13. Abrasion diagrams of Ni/TiN–SiC nanocoatings produced with dif-
ferent pulse current densities: (a) 2 A/dm2, and (b) 4 A/dm2.
TiN–SiC nanocoating with poor wear resistance.
However, Ni/TiN–SiC nanocoating deposited at 4 A/dm2 showed
uniform and fine microstructure with large amounts of TiN and SiC
nanoparticles (Fig. 13b), effectively prohibiting any deep damage of
hardened steel barrel on nanocoating surface. Therefore, only some
small scratches were observed on Ni/TiN–SiC nanocoating surface de-
posited at 4 A/dm2, revealing superior wear resistance.
4. Conclusion
(1) At pulse current density of 4 A/dm2, Ni/TiN–SiC nanocoatings with
smooth, uniform and fine surface morphologies were observed by

8
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SEM. Some TiN and SiC nanoparticles appeared on Ni/TiN–SiC
nanocoating deposited at 2 A/dm2, whereas numerous TiN and SiC
nanoparticles became incorporated at 4 A/dm2. The average sizes
of TiN and SiC nanoparticles were recorded as 45.9 nm and
37.2 nm, respectively.
(2) Ni, SiC and TiN phases were all present in Ni/TiN–SiC nanocoatings
obtained at 2 A/dm2, 4 A/dm2, and 6 A/dm2. Ni/TiN–SiC nano-
coating prepared at 2 A/dm2 showed fewer TiN and SiC nano-
particles than those prepared at 4 A/dm2 and 6 A/dm2 (Fig. 9a). By
contrast, high concentrations of Ti (19.6 at%), Si (12.1 at%) and Ni
(53.3 at%) were measured throughout the crosssection of nano-
coating obtained at 4 A/dm2.
(3) Ni/TiN–SiC nanocoating deposited at 4 A/dm2 with average mi-
crohardness of 848.5 Hv clearly depicted the highest microhardness
than other nanocoatings. By comparison, Ni/TiN–SiC nanocoating
obtained at 2 A/dm2 depicted an average microhardness of only
699.2 Hv.
(4) The wear rate of Ni/TiN–SiC nanocoating prepared at 4 A/dm2 was
only 13.6 mg/min, indicating Ni/TiN–SiC nanocoatings with ex-
cellent wear resistance. In addition, Ni/TiN–SiC nanocoating pre-
pared at 4 A/dm2 had the smallest average friction coefficient of
0.49. However, the nanocoating deposited at 2 A/dm2 had the
highest average friction coefficient with a value of 0.76.
Declaration of competing InterestCOI
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This work has been supported by the National Natural Science
Foundation of China (Grant Nos. 51974089, 51674090), Natural
Science Foundation of Heilongjiang Province of China (Grant No.
LC2018020), Innovative and Entrepreneurship Training Program for
College Students in Heilongjiang Province (Grant No. 201910220060).
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