Applied Surface Science 364 (2016) 264272

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Microstructural, phase evolution and corrosion properties of silicon

carbide reinforced pulse electrodeposited nickeltungsten composite
coatings
Swarnima Singh a , M. Sribalaji a , Nitin P. Wasekar b , Srikant Joshi b , G. Sundararajan b ,
Raghuvir Singh c , Anup Kumar Keshri a,
a
Materials Science and Engineering, Indian Institute of Technology Patna, Navin Government Polytechnic Campus, Patliputra Colony, Patna, Bihar 800013,
India
b
International Advanced Research Centre for Powder Metallurgy & New Materials (ARCI) Hyderabad, Balapur P.O., Hyderabad, Andhra Pradesh 500005,
India
c
CSIR-National Metallurgical Laboratory, Jamshedpur, Jharkhand 831007, India

a r t i c l e

i n f o

Article history:
Received 2 October 2015
Received in revised form
13 December 2015
Accepted 21 December 2015
Available online 23 December 2015
Keywords:
Pulse electrodeposition
Nickeltungsten alloy
Silicon carbide
Surface morphology
Phase evolution
Corrosion

a b s t r a c t
Silicon carbide (SiC) reinforced nickeltungsten (NiW) coatings were successfully fabricated on steel
substrate by pulse electrodeposition method (PED) and the amount of SiC was varied as 0 g/l, 2 g/l, and
5 g/l in NiW coating. Effect of subsequent addition of SiC on microstructures, phases and on corrosion
property of the coating was investigated. Field emission scanning electron microscopy (FE-SEM) image
of the surface morphology of the coating showed the transformation from the dome like structure to
turtle shell like structure. X-ray diffraction (XRD) of NiW5 g/l SiC showed the disappearance of (220)
plane of Ni(W), peak splitting in major peak of Ni(W) and formation of distinct peak of W(Ni) solid
solution. Absence of (220) plane, peak splitting and presence of W(Ni) solid solution was explained by
the high resolution transmission electron microscopy (HR-TEM) images. Tafel polarization plot was used
to study the corrosion property of the coatings in 0.5 M NaCl solution. NiW5 g/l SiC coating was showed
higher corrosion resistance (i.e. 21% increase in corrosion potential, Ecorr ) compared to NiW coating.
Two simultaneous phenomena have been identied for the enhanced corrosion resistance of NiW5 g/l
SiC coating. (a) Presence of crystallographic texture (b) formation of continuous double barrier layer of
NiWO4 and SiO2 .
2015 Elsevier B.V. All rights reserved.

1. Introduction
Nickeltungsten (NiW) coatings have attracted signicant
attentions in various industrial components like valves, pipes,
pumps, heat exchangers in automobiles, aerospace, energy and
petroleum industries, largely due to their excellent corrosion resistant property [13]. In all these applications, NiW coatings are
more prone to harsh corrosive environments. Even, a minimal
corrosion in these coatings can lead to development of cracks or
pores resulting the breakdown of the components [4]. In order
to further improve the corrosion resistance of NiW coatings, a
number of ternary NiWX composite coatings have been developed (where X = TiO2 , SiC, BN, SiO2 , MWCNT) [510]. Most of the
NiW based composite coatings are fabricated by electrodeposition

Corresponding author.
E-mail address: anup@iitp.ac.in (A.K. Keshri).
http://dx.doi.org/10.1016/j.apsusc.2015.12.179
0169-4332/ 2015 Elsevier B.V. All rights reserved.

method because of its dense microstructure, higher deposition rate,

reproducibility, easy operation, no post-deposition treatment and
lower cost [8,11]. Electrodeposition technique could be performed
with direct and pulse current, where the pulse electrodeposition
(PED) method has superior benets on direct current electrodeposition. PED technique could provide the deposits with desired
compositions, optimized structure and porosity by modifying pulse
parameters, reduced bath additives, uniform/ne surface nish
with higher deposition rate [6,12,13]. In addition, PED technique
absorbs less hydrogen, which leads to dense coating and ultimately
results in increased corrosion resistant of the coating [6,12,13].
Several researchers have utilized PED technique and reinforced various reinforcement in NiW based composite coating and reported
signicant improvement in corrosion resistance of the coatings
[5,6,8,10,14].
Goldasteh et al. reinforced TiO2 in pulse electrodeposited NiW
coating and evaluated the corrosion resistance in 0.5 M NaCl solution [5]. Substantial improvement of 62% in corrosion resistance

S. Singh et al. / Applied Surface Science 364 (2016) 264272

was observed in NiWTiO2 coating compared to NiW coating,

which was attributed to two simultaneous phenomena. Firstly, TiO2
particles acted as an inert physical barrier for initiation and development of corrosion in NiW matrix. Secondly, uniform dispersion
of TiO2 resulted the formation of microcells throughout the matrix
and hence, inhibits localized corrosion [5]. Similarly, Kumar et al.
reported relative improvement of 79% in corrosion resistance of
pulse electrodeposited NiWTiO2 coating in 3.5 wt.% NaCl solution [6]. Enhancement in corrosion resistance was attributed to
the uniform dispersion of TiO2 that prevents the dissolution of
NiW by absorbing corrosive anodic sites [6]. Sassi et al. found
similar reason for the 99% improvement in corrosion resistance
of pulse electrodeposited NiWSiO2 coating compare to NiW
coating [10].
In another study, Sangeetha et al. reported the 42% improvement in corrosion resistance on reinforcement of boron nitride
(BN) in pulse electrodeposited NiW coating in 3.5 wt.% NaCl solution [8]. Further, increased charge transfer resistance of 40%
was observed for NiWBN than NiW after electrochemical
impedance spectroscopy (EIS) experiment. Increase in corrosion
resistance and charge transfer resistance was attributed to the uniform distribution of BN and formation of passive lm over NiW
matrix.
Recently, Li et al. fabricated NiW(05 g/l) MWCNT (multiwalled carbon nanotube) composite coating using PED technique
and showed relative improvement of 78% in corrosion resistance
[14]. Further, charge transfer resistance of NiW coating increased
by 22% on reinforcement of MWCNT. Signicant enhancement in
corrosion resistance of NiWMWCNT coating was attributed to
two parallel phenomena. Firstly, MWCNT could ll the gaps, cracks
and micro holes of NiW coating and could act as physical barrier
to the growth of corrosion defect. Secondly, uniform distribution of
MWCNT could lead to uniform corrosion and inhibits the localized
corrosion [14].
In all of the above mentioned studies, effect of several reinforcement on corrosion property of pulse electrodeposited NiW
coating has been seen. Recently, silicon carbide (SiC) has attracted
considerable attentions as a potential reinforcing agent due to its
excellent properties such as resistance to thermal shock, oxidation,
and corrosion at high temperature and pressure [15], high hardness,
high thermal stability, and high chemical resistance [16]. Yao et al.
reinforced 10 g/l SiC in NiW coating and fabricated the NiWSiC
composite coating using direct current electrodeposition. Enhancement of 60% in corrosion resistance was found on adding 10 g/l SiC
in NiW coating, which acts as an physical barrier to initiation and
development of corrosion [7]. In addition, SiC played an important
role in grain rening as well as in restricting the growth of nickel
grain [17,18].
However, there is scarcity of the work reporting the fabrication of NiWSiC composite coating using pulse electrodeposition
method. Further, effect of SiC on microstructure, phases and
corrosion resistance is completely unknown for the pulse electrodeposited NiWSiC composite coating.
Motivated by this scenario, the focus of the present communication deals with the fabrication of the NiW composite coatings
with varying amount of SiC content using pulse electrodeposition
method. Microstructural and surface morphology of the coatings
are characterized by eld emission scanning electron microscopy
(FE-SEM) and energy dispersive X-ray spectroscopy (EDAX). Phase
evolution of the coatings with different amount of SiC content
are investigated by X-ray diffraction (XRD) and high resolution
transmission electron microscopy (HR-TEM). Corrosion behaviour
of the NiWSiC composite coating in 0.5 M NaCl solution is
evaluated by performing Tafel polarization. Post-polarization barrier layer is identied using X-ray photoelectron spectroscopy
(XPS).

265

Table 1
Pulse electrodeposition parameters for depositing NiWSiC coating on plain carbon
steel.
Current density (A/dm2 )
Temperature ( C)
Stirring speed (rpm)
Time (h)
Duty cycle
pH

10
75 1
300
1
87%
8.75

2. Experimental procedure
2.1. Pulse electrodeposited NiWSiC coating
Pulse electrodeposited NiW coating with varying amount of
SiC was obtained from the International Advanced Research Centre for Powder Metallurgy & New Materials (ARCI) laboratory,
Hyderabad, India. Two different compositions i.e. NiW2 g/l SiC
and NiW5 g/l SiC coating were deposited on plain carbon steel
(60 mm 60 mm 5 mm). Pulse electrodeposited NiW coating
was used as a control sample. During the pulse electrodeposition
process, solution was magnetically stirred at the speed of around
300 rpm in order to keep the SiC particles suspended in solution. Low carbon steel was chosen as cathode and Nickel as anode,
distance between them was maintained at 3 cm. Pulse electrodeposition parameters for depositing the coating have been shown in
Table 1.
2.2. Microstructural and phase characterizations
Cross-sectional and surface morphology of the pulse electrodeposited coatings were examined using a eld emission scanning
electron microscope of make S-4800, HITACHI, Japan and X-Max 50,
Oxford Instruments, UK respectively. Energy Dispersive X-ray Spectroscopy (EDAX) attached with FE-SEM (S-4800) was used for X-ray
mapping of NiW2 g/l SiC and NiW5 g/l SiC coatings. In addition,
surface morphology of NiW, NiW2 g/l SiC and NiW5 g/l SiC
coatings after polarization in 0.5 M NaCl solution were examined by
using optical microscope (BX51, OLYMPUS, Japan). Phase analysis
was performed on NiW, NiW2 g/l SiC and NiW5 g/l SiC composite coatings using X-ray diffraction (TTRAX III, Rigaku, Japan) of
CuK radiation of 1.54 A wavelength. The scanning range and the
scanning rate were maintained as 2080 and 2 /min respectively.
Further, high resolution transmission electron microscope (HRTEM) (JEM 2100, JEOL, Japan) operating at an accelerating voltage
of 300 kV was used to validate the phases in NiWSiC composite
coatings.
2.3. Corrosion test
The electrochemical investigation of the coating was performed
in 0.5 M NaCl solution by using Potentiostat/Galvanostat (Reference
600, Gamry, UK). The electrochemical measurements were done
using conventional three electrode system at room temperature.
The pulse electrodeposited coatings acts as working electrode with
the exposure area of 1 cm2 , whereas saturated calomel electrode
(SCE) and graphite electrode was used as reference and counter
electrodes respectively. All the three coatings were cleaned using
acetone and then cleaned by distilled water before conducting
electrochemical measurements. The open circuit potential (OCP)
measurement was performed on all the coatings in 0.5 M NaCl
solution for 1 hour to attain a stabilized potential. The anodic polarization test was carried out by scanning the samples from cathodic
region 0.25 V to anodic region 2 V at scan rate of 100 mV/min,
with respect to OCP condition. Echem AnalystTM software (Gamry
instruments, USA) is being used for the estimation of corrosion rate

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S. Singh et al. / Applied Surface Science 364 (2016) 264272

of all three coatings, which uses the standard Tafel method (ASTM
standard G102-89) for calibrating it. This standard method uses an
Eq. (1), derived from the Faradays law, as shown below.
Corrosion rate =

K1 icorr EW
d

(1)

where, icorr is the corrosion current density in A/cm2 which was

calculated by drawing a tangential line on the anodic as well as
on the cathodic branches of tafel plot. EW is the equivalent weight
of working electrode in grams/equivalent, d denotes the density in
g/cm3 and K1 is the unit for corrosion rate which is 1.288 105 mpy.
2.4. X-ray photoelectron spectroscopy (XPS) analysis of polarized
NiWSiC coating
X-ray photoelectron spectroscopy (XPS) (SPECS, Germany)
using Al monochromator (binding energy: 1486.6 eV) and Mg-K
(binding energy: 1253.6 eV) source, operating at a vacuum more
than 1 109 Torr was used to investigate the probable formation of barrier layer in polarized NiWSiC coating. The survey
spectra was carried out from 0 to 1000 eV to know the elements
present in polarized NiWSiC composite coating with pass energies of 50 eV. The slow scan were carried out for Ni2p (900830 eV),
W4f (4524 eV), Si2p (11585 eV), C1s (300270 eV) with pass
energy of 25 eV. The deconvolution of XPS spectra was done using
Computer Aided Surface Analysis (CASA) XPS software and Ni2p,
W4f, Si2p peak were calibrated by C1s peak at binding energy
of 284.6 eV.
3. Results and discussion
3.1. Microstructural characterization
Fig. 1(ac) represents the cross-sectional FE-SEM images of
NiW, NiW2 g/l SiC and NiW5 g/l SiC coatings respectively. The
cross-sectional images revealed that coating was dense and crack
free. Coating thickness of NiW was found to be 23 m which

did not change on addition of 2 g/l SiC particles. However, addition

of 5 g/l SiC particles in the NiW coating signicantly reduced the
coating thickness from 23 m to 5 m. This drastic reduction of
78% in coating thickness could be attributed to the incorporation
of relatively higher amount of SiC particles that might acts as physical barrier and hinder the rate of the grain growth. Borkar et al.
found the similar trend (i.e. 42% reduction) in coating thickness on
addition of Al2 O3 (40 g/l) in electrodeposited Ni. They attributed
the reduction in coating thickness to grain growth hindrance by
Al2 O3 particle [19].
Fig. 2(ac) illustrates the FE-SEM images of the surface morphology of NiW, NiW2 g/l SiC and NiW5 g/l SiC coatings
respectively. The surface morphology of all three coatings shows
the distinct features. As-deposited NW coating exhibits the
equiaxed dome like structure which changed to coarse turtle shell
like structure on adding 2 g/l SiC and further changes to ner turtle shell like structure upon subsequent addition of 5 g/l SiC. Few
researchers have reported the microstructural transformation, due
to reinforcement of ternary element in Ni based matrix [5,17,20].
However, the reason for this kind of transformation has not been
reported.
This change in surface morphology could be attributed to the
uniform distribution of SiC over the NiW matrix which accelerates
the grain renement process. Fig. 3(a and b) shows the X-ray mapping of the surface of NiW2 g/l SiC and NiW5 g/l SiC showing
the uniform distribution of Si particles over NiW matrix. The effect
of these uniformly distributed SiC particles on the grain renement
process could be understood using the schematic.
Fig. 4 is the schematic showing the step-by-step grain renement process on adding SiC. Fig. 4(a) explains the formation of
equiaxial dome like structure in NiW coating due to the homogeneous nucleation of NiW grains. On adding 2 g/l SiC particles
to the solution, equiaxial dome like structure transformed into
coarse turtle shell like structure which might be the resultant of
two opposing phenomena. Firstly, SiC acts as nucleation sites which
favours the nucleation of more NiW grain. However, the growth
of these nucleated NiW grain could be restricted by the SiC itself,

Fig. 1. represents the cross-sectional FE-SEM images of pulse electrodeposited (a) NiW, (b) NiW2 g/l SiC and (c) NiW5 g/l SiC coatings.

S. Singh et al. / Applied Surface Science 364 (2016) 264272

267

Fig. 2. The FE-SEM images of the surface morphology of pulse electrodeposited (a) NiW, (b) NiW2 g/l SiC and (c) NiW5 g/l SiC coatings.

which acts as a physical barrier between these grains (as shown in

Fig. 4b). On increasing the SiC content from 2 g/l to 5 g/l in solution,
nucleation rate of NiW grains increases due to the increased number of nucleation sites. However, the grain growth of the nucleated
NiW grains are also restricted severely compared to NiW2 g/l
SiC coating, resulting ner turtle shell like structure as shown in
Fig. 4(c).
3.2. Phase evolution
X-ray diffraction (XRD) patterns of pulse electrodeposited NiW
coating as well as NiW2 g/l SiC and NiW5 g/l SiC coatings are
shown in Fig. 5(ac) respectively. The diffraction pattern of NiW
coating shown in Fig. 5(a) displays one high intensity broad peak
at 43.78 and another low intensity peak at 50 and 75.08 which
corresponds to the (111), (200) and (220) planes of face-centred
cubic (FCC) Ni respectively. However, JCPDS standard of FCC-Ni

(04-0850) indicates that the (111), (200) and (220) planes have
been shifted towards lower 2 angle. This shift could be attributed
lattice by the 10%
to the expansion of Ni (atomic radius: 1.24 A)
Due to the addition of W in Ni, the peaks
larger W atoms (1.39 A).
at 43.78 , 50 and 75.08 could better be indexed as diffraction pattern of Ni (W) solid solution instead of the pure nickel phase. There
are few literatures which shows the shifting of Ni planes to lower
2 angle in NiW coating and indexed the planes as solid solution
of Ni(W) instead of pure Ni [5,21]. Broadness in the major peak of
all the three spectra indicates the presence of amorphous phases in
the NiW, NiW2 g/l SiC and NiW5 g/l SiC composite coating.
On adding 2 g/l SiC in NiW matrix, a low intensity peak has
emerged at 35.68 (Fig. 5b), that corresponds to (102) plane of SiC.
Apart from this, the diffraction pattern of NiW2 g/l SiC coating did
not show any signicant changes with respect to NiW coating.
Further addition of SiC (i.e. 5 g/l) showed the remarkable
changes in the diffraction pattern of NiW5 g/l SiC coating (Fig. 5c).

Fig. 3. The X-ray mapping of Si particles from the surfaces of pulse electrodeposited (a) NiW2 g/l SiC and (b) NiW5 g/l SiC coatings.

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S. Singh et al. / Applied Surface Science 364 (2016) 264272

Fig. 4. The grain renement mechanisms in (a) NiW, (b) NiW2 g/l SiC and (c)
NiW5 g/l SiC coatings.

Firstly, low intensity peak of Ni(W) at 50 and 75.08 disappeared

in NiW5 g/l SiC composite coating, which might be due to the
reduction of Ni content in the coating as a result of relatively higher
amount of SiC addition.
Secondly, peak splitting between 43 to 45 in NiW5 g/l SiC
coating. Goldasteh et al. also found the similar dominant (200)
W(Ni) solid solution peak emerged from the (111) Ni peak resulting the peak splitting in pulse electrodeposited NiWTiO2 coating
[6]. However, mechanism of peak splitting is not mentioned in their
study.
Peak splitting might be due to the strain in the lattices of Ni and
W due to the addition of relatively higher amount of SiC. In order
to conrm this, micro-strain has been calculated for NiW2 g/l SiC
and NiW5 g/l SiC coating with using Eq. (2).
=

4tan 

(2)

where, is the micro-strain, is broadening due to deformation and

 is the Bragg angle, which has been taken from the X-ray diffraction
pattern of both the coating. Micro-strain was found just double
i.e. 2.255 for NiW5 g/l SiC compared to NiW2 g/l SiC which is
1.205. Excessive amount of strain in the NiW5 g/l SiC might be
the reason for the peak splitting in Ni(W) phase.

Fig. 6. (a) The HR-TEM images of pulse electrodeposited NiW5 g/l SiC composite
coating (b) magnied image of (a) showing the presence of SiC crystallites, Ni(W)
and W(Ni). IFFT (Inverse Fast Fourier Transformation) image conrmed the lattice
spacing of SiC crystallites, Ni(W) and W(Ni).

Thirdly, an additional peak observed for W(Ni) in NiW5 g/l

SiC composite coating. This could be due to the addition of higher
amount of SiC which leads to segregation of Ni rich i.e. Ni(W) and
W rich i.e. W(Ni) phase. Signature of W(Ni) has been seen in diffraction pattern of NiW5 g/l SiC, which might have signicant impact
on corrosion behaviour of coating. Further, the formation of W(Ni)
phase on addition of SiC can be reconrmed by the HR-TEM images.
Fig. 6(a) displays the HR-TEM image of NiW5 g/l SiC coating,
where black patches are observed throughout the coating. A higher
magnication image on the region shown in Fig. 6(a) clearly shows
the presence of lattice fringes in black patches. The Inverse Fast
Fourier Transformed (IFFT) image of black patches showed a lattice
spacing of 0.25 nm that corresponds to (102) plane of SiC (JCPDS
card no.: 00-049-1428) crystallites. The IFFT images of the other
marked regions indicated in Fig. 6(b), conrms the presence of (111)
plane of Ni(W) solid solution as well as (200) and (220) planes
of W(Ni) solid solution, which matches well with the diffraction
pattern of NiW5 g/l SiC coating (Fig. 5c). This indicates the segregation of Ni(W) and W(Ni) phase on incorporation of SiC. However,
the lattices of these W(Ni) and Ni(W) planes was found distorted,
which might be due to the lattice disturbance caused by the incorporation of relatively higher amount of hexagonally close packed
(HCP) SiC particles in FCC Ni(W) lattices. Around the SiC crystallites,
existence of amorphous region was observed (Fig. 6b), which is in
accordance with the broadness of spectra in diffraction pattern as
observed in Fig. 5(c).
3.3. Corrosion behaviour

Fig. 5. X-ray diffraction patterns of pulse electrodeposited (a) NiW, (b) NiW2 g/l
SiC and (c) NiW5 g/l SiC coatings.

Corrosion behaviour of all pulse electrodeposited coatings was

evaluated by the corrosion potential (Ecorr ) and corrosion current
density (icorr ) values after polarization of each coating. Further, corrosion behaviour was analyzed by estimating the corrosion rate of
all three coatings.
The anodic polarization curves of NiW, NiW2 g/l SiC and
NiW5 g/l SiC coatings were obtained in 0.5 M NaCl solution as
shown in Fig. 7(ac) respectively. The Ecorr and icorr values were
obtained by extrapolating the anodic and cathodic branches using
Tafel method and tabulated in Table 2. It is evident from Table 2,
with increasing the SiC content in NiW composite coating, icorr
value decreased. Further, Ecorr showed an increasing trend with

S. Singh et al. / Applied Surface Science 364 (2016) 264272

269

Fig. 7. The anodic polarization curves of pulse electrodeposited NiW, NiW2 g/l SiC, NiW5 g/l SiC coatings.

increasing SiC content and this was found higher (0.479 V) for
the NiW5 g/l SiC composite coating. Total increase of 21% in
Ecorr was observed on reinforcement of 5 g/l SiC in NiW coating.
Relatively higher Ecorr and lowest icorr indicates the enhanced corrosion resistance of NiW5 g/l SiC coating compared to NiW and
NiW2 g/l SiC coatings.
Corrosion rate of all three coating was estimated and tabulated in Table 2. NiW coating shows the highest corrosion rate of
5.639 mpy, which reduced to 5.427 mpy for NiW2 g/l SiC and further reduced to 4.698 mpy for NiW5 g/l SiC coating. This clearly
indicates the effect of reinforcement of 5 g/l SiC in NiW coating
which lowered the corrosion rate by 17%.
Enhanced corrosion resistance of NiW5 g/l SiC was majorly
been attributed to the two simultaneous phenomena (a) presence
of crystallographic texture i.e. (200) of W(Ni) and (b) formation of
barrier layer after polarization. Several researchers have reported
that a grain with preferred orientation shows higher corrosion
resistance [22,23]. The pronounced orientation in NiW5 g/l SiC
coating was found to be (200) texture of W(Ni) as seen previously in X-ray diffraction pattern (Fig. 5c) and HRTEM (Fig. 6). This
was reconrmed by carrying out the texture content calculation
on (200) and (111) textures of NiW5 g/l SiC coating using the
following Eq. (3) [22].
C(200) =

(3)

1 + 1.25 I(111)
(200)

Table 2
summarizes the icorr and Ecorr after polarization, corrosion rate and inhibition efciency of pulse electrodeposited NiW(05 g/l) SiC coating.
Sample nomenclatures

Ecorr (V)

icorr (A/cm2 )

Corrosion rate (mpy)

NiW
NiW2 g/l SiC
NiW5 g/l SiC

0.582
0.574
0.479

12.6 106
12.2 106
10.9 106

5.639
5.427
4.698

where, I(111) and I(200) are the intensities of (111) and (200) diffraction peaks respectively. It is evident from this calculation that the
extent of preferred orientation of (200) texture present NiW5 g/l
SiC was 18% higher than the (111) texture. The higher preferred
orientation of (200) plane could strongly attribute to the enhanced
corrosion resistance of NiW5 g/l SiC coating. Wang et al. did
the laser surface treatment of 321 austenitic steel and found the
higher preferred orientation of (200) textures, which contributed
towards improved pitting corrosion resistance [22]. Venegas
et al. also reported the similar results in agreement of Wang
et al. [23].
In order to further investigate, the pitting corrosion resistance
was evaluated after polarization of all three coatings using an
optical microscope. Fig. 8(ac) shows the pits formed in NiW,
NiW2 g/l SiC and NiW5 g/l SiC coatings after polarization in
0.5 M NaCl solution. The average pit size of NiW coating was
observed to be 326 m (Fig. 8a), which reduced to 265 m (i.e.
18% reduction) on adding 2 g/l SiC in NiW matrix (Fig. 8b). Further, addition of 5 g/l SiC to NiW matrix has signicantly reduced
the pit size to an average value of 50 m (i.e. 84% reduction)
compared to NiW coating. The large reduction in the pit size of
5 g/l SiC coating might be due to the presence of pronounced (200)
texture because of the SiC particles. Shi et al. also reported the
restrictions in the growth of corrosive pits due to the presence of
SiC particles [20].
Another reason responsible for higher corrosion resistance of
NiW5 g/l SiC coating could be the formation of barrier layer
over the coating. Many researchers claimed the presence of oxide
based barrier layer as signicant factor for enhancing the corrosion
resistance of electrodeposited coatings [1,10,24]. In order to understand the barrier layer formation, XPS analysis was performed
on the polarized coating having least amount of SiC (NiW2 g/l
SiC).
The formation of NiWO4 and SiO2 layer was experimentally conrmed by performing XPS analyses on polarized NiW2 g/l SiC

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S. Singh et al. / Applied Surface Science 364 (2016) 264272

Fig. 8. Optical micrograph of pit formation on (a) NiW, (b) NiW2 g/l SiC, (c) NiW5 g/l SiC alloy after polarization in 0.5 M NaCl solution.

sample. XPS technique allowed the measurement of oxide formation upto 10 nm. The XPS analysis of NiW2 g/l SiC composite
coating reveals the presence of NiWO4 and SiO2 as shown in slow
scan (Fig. 9ac). The presence of NiWO4 was observed at binding energy of 856.17 eV, 862 eV, 35.36 eV, and 37.52 eV and SiO2 at
37.52 eV, which is in good agreement with the literature reported

[1,25]. The formation of these barrier layers after polarization might

happen due to the following reactions [24,26,27].
Ni2+ + WO4 2 NiWO4

(a)

SiC + 4H2 O SiO2 + 8H+ + CO2 + 8e

(b)

Fig. 9. The XPS deconvoluted proles of Ni 2p, W 4f, SiC 2p peaks for NiW2 g/l SiC (ac) samples fabricated by pulse electrodeposition method.

S. Singh et al. / Applied Surface Science 364 (2016) 264272

271

SiO2 which acted as barrier to the initiation and development of

corrosion.
Acknowledgements
Authors at Indian Institute of Technology Patna (IIT-P) acknowledge the Department of Physics, IIT-P for providing XRD
characterization facility. Authors also thank Mr. Y.N. Singh Babu,
PhD scholar, CSIR-NML for carrying out XPS analysis and Mr.
Biswajyoti Mukherjee, PhD scholar, IIT Patna for their constructive
suggestions.
References

Fig. 10. The corrosion mechanisms of pulse electrodeposited (a) NiW, (b) NiW
2 g/l SiC, (c) NiW 5 g/l SiC coating.

XPS spectra conrmed the formation of NiWO4 and SiO2 barrier

layer which can enhance the corrosion resistance. Formation of barrier layer on all these three coatings could be understood using a
schematic as shown in Fig. 10.
Fig. 10(a) is the schematic showing the formation of discontinuous NiWO4 layer in the NiW coating. Discontinuous layer of
NiWO4 might be attributed to presence of the coarser grain in NiW
coating as discussed earlier. Few literatures have reported the formation of uniform barrier layer to ne grained microstructures
and vice versa [28,29]. This discontinuous NiWO4 barrier layer
contributes towards enhanced corrosion resistance of the NiW
coating.
Fig. 10(b) is the schematic showing the formation of NiWO4 and
SiO2 layer in the NiW2 g/l SiC coating. Since, grain is relatively
ner compare to NiW, the lm formation could start transforming
from discontinuous to the continuous layer resulting enhanced corrosion resistance of NiW2 g/l SiC compared to NiW coating.
Fig. 10(c) is the schematic showing the formation of double barrier layer i.e. NiWO4 and SiO2 layer in the NiW5 g/l SiC coating.
Since, grain is much ner compare to NiW and NiW2 g/l SiC, the
lm formation could be almost continuous stopping the penetration of Cl ion inside the coating, resulting the drastic enhancement
in corrosion resistance of NiW5 g/l SiC compared to NiW and
NiW2 g/l SiC coatings.
Apart from the presence of crystallographic texture and formation of barrier layer, micro-cell also forms on addition of SiC. Since,
standard potential of SiC was more positive than NiW, SiC act as
a cathode and NiW act as an anode. So, SiC particles might help in
inhibiting the localized corrosion. Also, addition of relatively excess
amount of SiC particle might help in lowering the metallic area
required for corrosion, leading to enhanced corrosion resistances
of the SiC reinforced NiW coating.
4. Conclusion
Pulse electrodeposited SiC reinforced NiW coating was fabricated and effect of SiC on microstructure, phases and corrosion
property was investigated. The inclusion of SiC in NiW coating
transformed the surface morphology from dome shaped structure
to turtle shell like structure. Ni rich phase i.e. Ni(W) and W rich
phase i.e. W(Ni) was segregated by the reinforcement of 5 g/l SiC.
Signature peak of W(Ni) solid solution was seen in the XRD spectra.
Increase of 21% in Ecorr indicates the higher corrosion resistance
of NiW coating with 5 g/l SiC. Enhanced corrosion resistance was
majorly been attributed to the presence of crystallographic textures and the formation of continuous double layer of NiWO4 and

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