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.
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
266
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)
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.
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.
(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.
268
Fig. 4. The grain renement mechanisms in (a) NiW, (b) NiW2 g/l SiC and (c)
NiW5 g/l SiC coatings.
4tan
(2)
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).
Fig. 5. X-ray diffraction patterns of pulse electrodeposited (a) NiW, (b) NiW2 g/l
SiC and (c) NiW5 g/l SiC coatings.
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 )
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
270
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
(a)
(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.
271
Fig. 10. The corrosion mechanisms of pulse electrodeposited (a) NiW, (b) NiW
2 g/l SiC, (c) NiW 5 g/l SiC coating.
272
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