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APSUSC-27637; No. of Pages 9 ARTICLE IN PRESS


Applied Surface Science xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Applied Surface Science


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

Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite


coatings electrodeposited by sediment codeposition technique
Babak Bakhit a,∗ , Alireza Akbari a , Farzad Nasirpouri a , Mir Ghasem Hosseini b
a
Surface Engineering Group, Advanced Materials Research Center, Faculty of Materials Engineering, Sahand University of Technology, PO Box 51335-1996,
Tabriz, Iran
b
Electrochemistry Research Laboratory, Department of Physical Chemistry, Chemistry Faculty, University of Tabriz, Tabriz, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrodeposited in a modified
Received 24 December 2013 Watts bath using sediment codeposition (SCD) technique was evaluated by potentiodynamic polariza-
Received in revised form 5 April 2014 tion measurements in the 3.5% NaCl solution and studied as a function of deposition conditions In order
Accepted 6 April 2014
to characterize the morphology, chemical and phase compositions of the coatings, scanning electron
Available online xxx
microscopy (SEM), energy dispersive X-ray spectrometry (EDS) and X-ray diffraction (XRD) were uti-
lized, respectively. It was observed that the cobalt content in the Ni–Co alloy coatings was increased
Keywords:
through an anomalous behavior by increasing the cobalt concentration in the electrolyte. The highest
Nanocomposite coatings
Sediment codeposition
percentage of SiC nano-particles (8.1 vol.%) in the Ni–Co/SiC nanocomposite coatings was achieved at
Microstructure 3 A/dm2 deposition current density and 5 g/l particle concentration. SEM and EDS analysis illustrated
Corrosion resistance that SiC nano-particles were distributed uniformly throughout the nanocomposite coatings. The poten-
tiodynamic polarization tests indicated that the corrosion resistance of the Ni–Co alloy coatings was
varied as a function of the cobalt content, and the corrosion resistance of the Ni–Co/SiC nanocompos-
ite coatings was markedly higher than the corrosion resistance of the Ni–Co alloy coatings. Among the
studied coatings, Ni–Co/SiC nanocomposite coatings containing 8.1 vol.% SiC nano-particles exhibited the
best corrosion resistance.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction On the other hand, considerable interest in investigating com-


posite coatings has been increased due to their unique mechanical
Previous studies indicated that Ni–Co alloy coatings have better properties, self-lubricity, thermal stability, oxidation, corrosion and
properties compared to Ni coatings. Srivastava et al. [1] reported wear resistance [4–9]. Composite electrodeposition refers to a
that Ni–20Co alloy coatings electrodeposited in Sulphamate bath process in which particles are suspended in the electrolyte and
showed better corrosion resistance than other Ni–Co alloy and Ni subsequently embedded into an electro-formed solid phase [10].
coatings. Yang et al. [2] also stated that Ni–Co alloy coatings had In metal–matrix composite coatings, the metallic matrix provides
better corrosion properties and could provide suitable protections an adhesion to the substrate and keeps particles together [11].
in the 3.5% NaCl solution in comparison with Ni coatings. Wang Electrodeposition of composite coatings containing particles like
et al. [3] investigated the influence of the cobalt content on the carbides [12], oxides [13,14], nitrides [15], graphite [16], diamond
microstructure and mechanical properties of Ni–Co alloy coatings. [17], metallic [18] and polymeric particles [6] was widely studied
It was pointed out that the microhardness of Ni–49Co alloy coatings to achieve distinctive properties. Employed particles in composite
was approximately as twice as the microhardness of Ni coatings. coatings can be categorized into two major groups: hard and soft
Besides, Ni–49Co alloy coatings showed a lower wear rate com- particles. Unlike hard particles, soft particles such as PTFE [6], PE
pared to Ni coatings. [19], MoS2 [20] and graphite [16] act as self-lubricant materials to
reduce friction coefficient and wear between sliding surfaces.
Particle content and particle distribution in composite coatings
depend on several interrelated parameters. These factors can
∗ Corresponding author. Tel.: +982144152762/+989166167328; be divided into three main categories: (i) particle properties
fax: +982144152762.
(type, shape and size), (ii) electrolyte composition (constituents,
E-mail addresses: b bakhit@sut.ac.ir, bakhit.babak@gmail.com (B. Bakhit). pH and additives), and (iii) deposition variables (particle

http://dx.doi.org/10.1016/j.apsusc.2014.04.037
0169-4332/© 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: B. Bakhit, et al., Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrode-
posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037
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2 B. Bakhit et al. / Applied Surface Science xxx (2014) xxx–xxx

Table 1
Ni–Co alloy and Ni–Co/SiC nanocomposite electrolyte compositions.

Electrolyte ingredients Ni–Co Ni–Co/SiC


Concentration (g/l) Concentration (g/l)

Nickel sulphate 250 250


Nickel chloride 40 40
Cobalt sulphate 0–50 50
Boric acid 40 40
Sodium Dodecyl Sulphate 0.35 0.35
SiC (Plasmachem GmbH) – 0–20

concentration, current density, electrolyte agitation and temper-


ature) [11]. In comparison with common metallic coatings and
composite coatings containing micro sized particles, nanocom-
posite coatings usually exhibit much better behavior in different
service conditions [21]. But, electrodeposition of composite
coatings containing nano sized particles is more difficult than
electrodeposition of composite coatings containing micro sized Fig. 1. Schematic image of the electrodeposition setup; (a) power supply, (b) epoxy
cover, (c) particles, (d) anode, (e) cathode, (f) external pH-temperature probe and
particles owing to the agglomeration of suspended particles in the (g) magnetic bar.
electrolyte [22,23]. Therefore, in order to increase the particle con-
tent and provide a uniform-particle distribution, several techniques
have been studied [21,24–28]. Adding Co2+ cations to the elec- generated by a Hielscher-UP100H ultrasonic disperser, and vigor-
trolyte is a suitable technique for increasing the particle content ous magnetic agitation (∼700 rpm) alternatively for 24 h.
in composite coatings because adsorption of Co2+ cations on the Deposition time was varied to obtain a constant coating thick-
particle surface is easier and higher than adsorption of Ni2+ cations ness, (approximately 30 ␮m). The pH of the electrolyte was
[23,29]. Another technique to increase the particle content is using measured before, during and after each electrodeposition process
the sediment codeposition (SCD) technique. Despite the conven- and adjusted at 4.3 ± 0.01 by H2 SO4 and NaOH solutions. During
tional electro-codeposition (CECD) technique, the electrodes are the electrodeposition process, the electrolyte pH near the cathode
positioned horizontally inside the bath in the SCD technique, and was 0.5 units higher than before the process due to the hydrogen
the gravity force helps and facilitates particle incorporation [21]. evolution. The electrolyte temperature was maintained at 45 ± 2 ◦ C.
Although a substantial number of publications have been The distance between anode and cathode was 3 cm. The electrolyte
devoted to composite and nanocomposite coatings, there are few was stirred periodically during the electrodeposition process by an
works that have been assigned to investigate the corrosion behavior agitation rate of 350 rpm (ton /toff time ratio: 300 s/10 s). After the
of the Ni–Co/SiC nanocomposite coatings electrodeposited by the electrodeposition process, the coatings were ultrasonically cleaned
SCD technique. This study is aimed to investigate the influences in distilled water about 5 min to remove the loosely adsorbed SiC
of electrodeposition parameters on microstructure and corro- nano-particles from the coating surface.
sion properties of the Ni–Co alloy and Ni–Co/SiC nanocomposite Surface morphology of the coatings was investigated by Scan-
coatings deposited in the modified Watts bath by the SCD tech- ning Electron Microscope (SEM, CamScan MV2300). The Oxford
nique. The corrosion properties of Ni–Co alloy coatings were also Energy Dispersive X-ray Spectrometer (EDS) coupled to the SEM
studied in order to represent a clear comparison between the cor- was used to determine the particle content and chemical analy-
rosion properties and corrosion mechanisms of Ni–Co alloy and sis of the coatings. Five randomly chosen areas were analyzed at
Ni–Co/SiC nanocomposite coatings. a magnification of 500×, and an average value was calculated. The
phase structure, average grain size, and preferred orientation of the
studied coatings were determined by D8 Advance-Bruker AXS X-
2. Experimental ray diffractometer. The relative texture coefficient (RTC(hkl) ) of the
deposited coatings was evaluated using the following equation.
Ni–Co alloy and Ni–Co/SiC nanocomposite coatings were elec-
o
Ihkl /Ihkl
trodeposited in a modified Watts bath by using a DC power supply
at various current densities. The electrolyte composition for elec-
RTC(hkl) = 3 × 100% (1)
I /I o
1 hkl hkl
trodeposition of the Ni–Co alloy and Ni–Co/SiC nanocomposite
coatings are given in Table 1. The utilized ␤-SiC nano-particles for o are the diffraction intensities of (hkl) planes mea-
Ihkl and Ihkl
electrodeposition of the nanocomposite coatings had an average sured from the XRD patterns of the Ni–Co solid solution and a
particle size of 20 nm. standard reference sample, respectively.
Electrodeposition was carried out in a 200 ml glass beaker with Potentiodynamic polarization measurements were used to
parallel electrodes positioned horizontally inside the electrolyte study the corrosion resistance of the deposited coatings. All electro-
(the cathode was positioned under the anode) as it is illustrated in chemical measurements were carried out in the 3.5% NaCl corrosive
Fig. 1. A pure nickel was used as the anode, and the coatings were medium without agitation, at the room temperature (25 ◦ C) and
electrodeposited on copper plates as cathodes. Substrates were by using an EG&G-Parstat 2263 potentiostat/galvanostat system. A
mechanically polished with silicon carbide abrasive papers (80 to saturated calomel electrode (SCE) was used as the reference elec-
4000 European FEPA or P-Grading) and ultrasonically cleaned in the trode and a platinum electrode with exposed area about 10 times
ethanol and acetone consecutively for 10 min. Thereafter, the sub- larger than working electrode was used as the counter electrode.
strates were washed in distilled water and activated in 10% H2 SO4 The specimens were immersed in the corrosive medium to attain
for 60 s at room temperature before the electrodeposition process. open circuit potential (Eocp ) about 60 min and 30 min for the Ni–Co
In order to insure that the SiC nano-particles were dispersed uni- alloy coatings and the Ni–Co/SiC nanocomposite coatings, respec-
formly in the electrolyte and to minimize particle agglomeration, tively. Immediately afterwards, the potentiodynamic sweeping
the electrolyte was subjected to ultrasound waves, which were was performed in the potential range of ±600 mV for the alloy

Please cite this article in press as: B. Bakhit, et al., Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrode-
posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037
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B. Bakhit et al. / Applied Surface Science xxx (2014) xxx–xxx 3
Cobalt content in the alloy coatings (Wt.%)
600
50 0 Wt.% Co
400 17 Wt.% Co
45 42 Wt.% Co
200
40

Potential (mV)
0
35
-200
30
-400
25
-600
20
-800
15
-1000
10
-1200
5 -1400
-2 -1 0 1 2 3 4 5 6
0
logi (i in µA.cm-2)
0 5 10 15 20 25 30 35 40 45 50 55
Cobalt concentration in the electrolyte (g/l) Fig. 3. The potentiodynamic polarization curves of the Ni–Co alloy coatings as a
function of the cobalt content.
Fig. 2. The cobalt content in the Ni–Co alloy coatings as a function of the cobalt
concentration in the electrolyte. Co. Therefore, Ni–17Co alloy coatings exhibit the lowest corrosion
rate.
The corrosion resistance of alloy coatings may be correlated to
coatings and ±250 mV for the nanocomposite coatings with respect simultaneous effects of several important factors such as chemi-
to the Eocp by 1 mV/s sweeping rate. The corrosion current den- cal composition, phase structure, preferred orientation, and grain
sity was calculated according to the Stern–Geary equation from size. In order to explain the chemical composition influence of
the polarization measurement [30]: alloy coatings, it was shown that alloying can affect the corrosion
ˇa × ˇc resistance by changing the nobility of materials [35]. Since cobalt
icorr =   (2) is more active than nickel, it is expected that the electrochemi-
2303 × Rp ˇa + ˇc
cal activity of the Ni–Co alloy coatings to be greater than pure
where icorr is the corrosion current density, Rp is the polarization Ni coatings, particularly by increasing the cobalt content [36]. The
resistance, ˇa and ˇc are the anodic and cathodic Tafel slopes, other factor which has a major impact on the corrosion behavior of
respectively. In addition, the polarization resistance was calculated alloy coatings is microstructure. In general, two-phase structures
according to the following equation: are less corrosion resistant than single-phase structures because
 galvanic cells can be formed between phases (along grain bound-
dE  E aries) and facilitate corrosion attacks, especially when phases have
Rp = 
di E=Eocp

i
(3)
different nobilities. Moreover, the corrosion resistance of face cen-
tered cubic (fcc) phases is higher than the corrosion resistance
3. Results of base centered cubic (bcc) phases due to their higher packing
factor. According to obtained results, the phase structure of the
3.1. Ni–Co alloy coatings studied Ni–Co alloy coatings, which was fcc single-phase solid solu-
tion, was not changed by the variation of the cobalt content in the
3.1.1. Electrodeposition coatings. Therefore, the phase structure had an approximately con-
Fig. 2 shows the variation of the cobalt content in the Ni–Co alloy stant influence on the corrosion properties of the studied Ni–Co
coatings as a function of the cobalt concentration in the electrolyte. alloy coatings.
There is a substantial upward trend in the cobalt content from 0 to The preferred orientation is another factor playing a signifi-
45 wt.% Co. The cobalt content in the alloy coatings is significantly cant role in corrosion resistance of coatings. Ramanauskas et al.
higher than the cobalt concentration in the electrolyte. According [37] suggested that the higher corrosion resistance of Zn–Ni alloys
to Brenner [31], this behavior is classified as an anomalous codepo- is owing to the predominant presence of crystallographic planes
sition. The anomalous codeposition of the Ni–Co alloy coatings was with a higher packing density. Fig. 4 shows the influence of the
explained by different mechanisms such as depletion of the diffu- cobalt content on the relative texture coefficient (RTC) of (1 1 1),
sion layer due to the preferential deposition of cobalt cations [32], (2 0 0), and (2 2 0) planes in the studied Ni–Co alloy coatings. Since
two-step codeposition of cobalt cations and decreasing the nickel a preferred orientation of a (hkl) plane is shown by the values of
deposition in the second step [33], and formation and adsorption of RTC(hkl) ≥ 33.33%, it can be seen that the preferred orientation in all
metal hydroxides because of a local increase in the pH, and higher studied Ni–Co alloy coatings is (1 1 1). However, the RTC(hkl) per-
adsorption of cobalt hydroxides [34]. centage of the studied alloy coatings is changed as a function of
the cobalt content. Although the RTC of (2 2 0) planes, which have a
3.1.2. Corrosion properties low packing density in fcc phase structures, is increased noticeably
Fig. 3 illustrates the potentiodynamic polarization curves of the from 0.54% to 28%, the RTC of (2 0 0) planes is approximately halved
Ni–Co alloy coatings. There is no passivation tendency over the from 38% to 16% by increasing the cobalt content in the deposits.
swept range of potentials. The electrochemical data extracted from Moreover, the RTC of (1 1 1) planes, which have the highest packing
the polarization curves are also summarized in Table 2. The low- density in fcc phase structures, is increased by 15% between 0 and
est corrosion current density (icorr ) and the highest polarization 38 wt.% Co. Yet, there is a collapse of 20% in the RTC of (1 1 1) planes
resistance (Rp ) are related to an alloy coating containing 17 wt.% after reaching a peak of 76%. This figure illustrates that the amount

Please cite this article in press as: B. Bakhit, et al., Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrode-
posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037
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Table 2
Electrochemical data extracted from the potentiodynamic polarization curves of the Ni–Co alloy coatings.

Coating Eocp (mV) ˇa (mV/dec) ˇc (mV/dec) Ecorr (mV) icorr (␮A/cm2 ) Rp (k.cm2 )

Pure Ni −305 174.8 140.7 −303 6.22 5.44


Ni–17Co −307 171.4 128.6 −305 3.16 10.08
Ni–42Co −368 180.2 98.6 −372 8.33 3.32

of close-packed (1 1 1) planes in the Ni–Co coatings is decreased by properties, which were attained in the previous work at 50 g/l
a further increase in the cobalt content while the amount of (2 2 0) cobalt [23], as well as the highest corrosion properties simulta-
planes, which are not dense, is increased. Hence, it can be deduced neously.
that a part of the higher corrosion resistance of the Ni–17Co alloy The effect of both particle concentration and deposition cur-
coatings is resulted from the presence of an fcc phase with predom- rent density on incorporation of SiC nano-particles is shown in
inant close-packed (1 1 1) planes and the low percentage of (2 2 0) Fig. 5. The SiC nano-particle content in the deposits is decreased by
planes. increasing the particle concentration in the bath. Although there
On the other hand, the grain size of coatings has a considerable is a gradual decrease in the particle content of nanocomposite
effect on the corrosion rate because the grain boundaries are prone coatings deposited at 1 and 4 A/dm2 , the percentage of incorporated
to corrosion attacks, and the corrosion resistance is decreased by particles in nanocomposite coatings deposited at 2 and 3 A/dm2
increasing the density of grain boundaries [38,39]. The grain size of shows a drop between 10 g/l and 15 g/l particle concentration. This
the studied alloy coatings was obtained from XRD peak broaden- decreasing trend can be correlated with nanoparticle agglomera-
ing analysis and calculated from integral width of the (2 0 0) peaks tion [23].
using the Scherrer equation [40] after excluding the instrumen- The transfer rate of suspended particles in the electrolyte is
tal broadening. Results show that the grain size of the coatings related to the hydrodynamic forces resulted from the electrolyte
is reduced strikingly from 48 nm in Ni–17Co coatings to 26 nm in agitation rate and the electrophoretic forces resulted from the
Ni–27Co coatings and then, 15 nm in Ni–42Co coatings. The grain deposition current density. At a constant agitation rate of the elec-
size reduction in the Ni–Co alloy coatings was linked to the forma- trolyte (350 rpm), the SiC nano-particle content shows an upward
tion of metal hydroxides in the electrolyte which are able to absorb trend with a peak at 3 A/dm2 and then a decrease by increasing
on active growth centers, block them and act as grain refiners [41]. the deposition current density. This might be described through a
As a consequence, besides the negative effect of the presence of competitive process between the reduction rate of metallic cations
the low density (2 2 0) planes, another reason for decreasing the and the incorporation rate of suspended particles. At low deposi-
corrosion resistance of the Ni–Co alloy coatings containing more tion current densities, the rate of cation reduction is higher than
than 17 wt.% Co could be related to their grain sizes. Therefore, the rate of particle incorporation. Then, the particle incorporation
higher corrosion resistance of the Ni–17Co alloy coatings is linked rate is increased moderately by raising the deposition current den-
to a moderate grain size, a single-phase fcc structure, and a relative sity until reaching a peak. After that, the reduction rate of metallic
predominance of (1 1 1) preferred orientation. cations is increased again at higher deposition current densities.

3.2. Ni–Co/SiC nanocomposite coatings 3.2.2. Surface morphology


In order to clarify the influence of deposition current density on
3.2.1. Electrodeposition the surface morphology and particle distribution, SEM images and
Although the best corrosion resistance was achieved for the dot-map patterns are presented in Figs. 6 and 7. Fig. 6 illustrates a
Ni–17Co alloy coatings electrodeposited in a modified Watts bath uniform distribution of the agglomerated particles throughout the
containing 10 g/l cobalt, the electrodeposition of the Ni–Co/SiC surface of the coatings in two different magnifications. Despite the
nanocomposite coatings was performed in a modified Watts bath
containing 50 g/l cobalt because the aim of studying the Ni–Co/SiC
nanocomposite coatings was obtaining the best mechanical 9
nanocomposite coatings (Vol.%)

2
SiC nano-particle content in the

1 A/dm
2
2 A/dm
2
100 8 3 A/dm
(111) 2
Relative texture coefficient (RTC)

4 A/dm
90 (200)
(220)
80
7
70
60
6
50
40
30 5
20
10 4
0 5 10 15 20
0 8 17 27 38 42 SiC nano-particle concentration
Cobalt content (Wt.%) in the electrolyte (g/l)
Fig. 4. The relative texture coefficient (RTC) percentage of (1 1 1), (2 0 0) and (2 2 0) Fig. 5. The particle content in the Ni–Co/SiC nanocomposite coatings as a function
planes in the Ni–Co alloy coatings as a function of the cobalt content in the deposits. of the particle concentration and deposition current density.

Please cite this article in press as: B. Bakhit, et al., Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrode-
posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037
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Fig. 6. The surface morphology of the Ni–Co/SiC nanocomposite coatings deposited at different deposition current densities of (a and e) 1 A/dm2 , (b and f) 2 A/dm2 , (c and
g) 3 A/dm2 , and (d and h) 4 A/dm2 at two different magnifications: 15k× and 30k×.

uniform distribution, the number of agglomerated particles in the Additionally, EDS spectra in Fig. 7 reveal that the intensity of Ni
surface of nanocomposite coatings deposited at 2 and 3 A/dm2 is and Co peaks is lengthened by increasing the deposition current
higher than nanocomposite coatings deposited at 1 and 4 A/dm2 . density. This can be an appropriate proof for the fact that the reduc-
The pyramidal morphology in Fig. 6d and h proves a rapid fall in tion rate of metallic cations is increased as a function of deposition
the particle content because of increasing the reduction rate of current density. In order to study the chemical composition and
metallic cations. Furthermore, the size of agglomerated particles particle distribution uniformity across the nanocomposite coating
is approximately comparable in all studied coatings. Fig. 7 shows thickness, the elemental line scans of Ni, Co, Si and Cu elements
the surface morphologies and Si dot-map patterns of the Ni–Co/SiC are represented on a cross sectional SEM image (Fig. 8). There is
nanocomposite coatings deposited at different current densities. a fairly uniform distribution of the elements approving the SiC
The dot-map patterns confirm that SiC nano-particles have a uni- nano-particle distribution uniformity through the thickness of the
form distribution over the surface of the nanocomposite coatings. nanocomposite coatings. Moreover, the SEM image of a Ni–Co/SiC

Fig. 7. The dot-map and spectra patterns of the Ni–Co/SiC nanocomposite coatings deposited at different deposition current densities of (a, e and i) 1 A/dm2 , (b, f and j)
2 A/dm2 , (c, g and k) 3 A/dm2 , and (d, h and l) 4 A/dm2 .

Please cite this article in press as: B. Bakhit, et al., Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrode-
posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037
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Fig. 8. Line scan element curves of the Ni–Co/SiC nanocomposite coating (3 A/dm2
and 5 g/l particle concentration).
Fig. 9. Cross sectional image of the Ni–Co/SiC nanocomposite coating (3 A/dm2 and
15 g/l particle concentration).

3.2.4. Corrosion properties


nanocomposite coating electrodeposited in the electrolyte contain-
The potentiodynamic polarization measurements were carried
ing 15 g/l SiC at 3 A/dm2 (Fig. 9) indicates that the distribution of
out precisely after attaining the open circuit potential (Eocp ). In
SiC agglomerates is uniform throughout the coating cross section.
order to obtain the Eocp , the specimens were immersed into the
3.5% NaCl corrosive medium to reach a plateau. Fig. 11 shows the
variation of the open circuit potential for a Ni–Co/SiC nanocompos-
3.2.3. Phase structure ite coating and the Ni–42Co alloy coating as a function of time. The
Fig. 10 depicts the X-ray diffraction (XRD) patterns of Ni–42Co Eocp for the Ni–Co/SiC nanocomposite coating was achieved after
alloy and Ni–Co/SiC nanocomposite coatings deposited at different 20 min immersing with a suitable electrochemical stability, while it
current densities. In comparison with the alloy coatings, there is was achieved after 35 min immersing for the Ni–42Co alloy coating.
not a considerable change in peak positions of the nanocomposite These results indicate that the Eocp is shifted towards more posi-
coatings; as a result, all the verified peaks belong to the Ni–Co alloy tive values by incorporation of SiC nano-particles into the Ni–Co
matrix. Hence, the matrix of the studied coatings is composed of a alloy matrix. In other words, the electrochemical stability of the
single-phase Ni–Co solid solution with an fcc phase structure, and Ni–Co/SiC nanocomposite coatings is much better than the Ni–Co
it is not changed by the variation of the deposition current density. alloy coatings in the 3.5% NaCl corrosive medium.
In addition, the absence of SiC peaks in the patterns can be related The effect of deposition current density on the potentiodynamic
to the small size (∼20 nm), low amount, and homogeneous distri- polarization curves of the Ni–Co/SiC nanocomposite coatings is
bution of the particles. Although the intensity of (2 0 0) and (2 2 0) illustrated in Fig. 12. Table 3 gives information extracted from
peaks is not changed markedly in the nanocomposite coatings by the potentiodynamic polarization measurements. According to
increasing the deposition current density, the intensity of (1 1 1), this data, the corrosion current density (icorr ) of the Ni–Co/SiC
(3 1 1) and (2 2 2) peaks is increased probably due to the variation nanocomposite coatings is reduced from 0.125 ␮A/cm2 at 1 A/dm2
of matrix chemical composition. to 0.05 ␮A/cm2 at 3 A/dm2 by raising the deposition current

800
Intensity (cps)

(111)
600

400
(220)

(200)
200
(311)
(222)
Ni-42Co
-2
Ni-Co/SiC, 1 A.dm
-2
Ni-Co/SiC, 2 A.dm
-2
Ni-Co/SiC, 3 A.dm
-2
Ni-Co/SiC, 4 A.dm

30 40 50 60 70 80 90 100 110 120


2 theta (°)

Fig. 10. X-ray diffraction patterns of the Ni–42Co alloy and the Ni–Co/SiC nanocomposite coatings deposited at different current densities.

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posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037
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Table 3
Electrochemical data extracted from the potentiodynamic polarization curves of the Ni–Co/SiC nanocomposite coatings as a function of the deposition current density.

Deposition current density (A/dm2 ) Co (wt.%) SiC (vol.%) Eocp (mV) ˇa (mV/dec) ˇc (mV/dec) Ecorr (mV) icorr (␮A/cm2 ) Rp (k.cm2 )

1 59.2 6.5 −266 126.6 143.8 −233 0.125 234.36


2 62.4 7.9 −206 84.8 133.5 −207 0.062 362.34
3 55 8.1 −201 71.2 176.5 −199 0.050 439.46
4 43.7 5.6 −214 85.9 255.2 −241 0.078 359.12

-160 100
Ni-Co/SiC 0 g/l nano SiC
Ni-42Co 5 g/l nano SiC
-200 0 10 g/l nano SiC
15 g/l nano SiC
-240 20 g/l nano SiC
-100

Potential (mV)
Potential (mV)

-280
-200
-320
-300
-360
-400
-400
-500
-440
-4 -3 -2 -1 0 1 2 3 4
-480
0 10 20 30 40 50 60 70 logi (i in µA.cm-2)

Time (min) Fig. 13. The potentiodynamic polarization curves of the Ni–Co/SiC nanocomposite
coatings as a function of the particle concentration in the electrolyte.
Fig. 11. The open circuit potential (Eocp ) variation of a Ni–Co/SiC nanocomposite
coating and Ni–42Co alloy coating in the 3.5% NaCl corrosive medium.
coatings containing 55 wt.% Co and 8.1 vol.% SiC nano-particles.
Therefore, the Ni–Co/SiC nanocomposite coatings electrodeposited
200 at 3 A/dm2 exhibits better corrosion resistance.
2
1 A/dm
2 Fig. 13 shows the potentiodynamic polarization curves of the
100 2 A/dm
3 A/dm
2 Ni–Co/SiC nanocomposite coatings electrodeposited at different
4 A/dm
2 particle concentrations in the electrolyte. Based on the electro-
0
chemical data extracted from these curves (Table 4), the icorr for
Potential (mV)

-100 the Ni–Co/SiC nanocomposite coatings is substantially lower than


the icorr for the Ni–42Co alloy coatings. However, the icorr for the
-200 Ni–Co/SiC nanocomposite coatings is increased from 0.05 ␮A/cm2
to 0.218 ␮A/cm2 , and the Rp is decreased from 439.46 k. cm2 to
-300 83.66 k. cm2 by increasing the particle concentration in the elec-
trolyte from 5 g/l to 20 g/l.
-400 The performance of the Ni–Co/SiC nanocomposite coatings in
a corrosive medium can be linked to four major parts: electrode-
-500 position process, matrix properties, related factors to reinforcing
particles, and service conditions.
-4 -3 -2 -1 0 1 2 3 4
The chemical composition, phase structure, grain size and
logi (i in µA.cm-2) preferred orientation of matrix are factors which have effective
influences on the corrosion properties of composite coatings. In
Fig. 12. The potentiodynamic polarization curves of the Ni–Co/SiC nanocomposite
coatings as a function of the deposition current density.
terms of the chemical composition influence of the Ni–Co alloy
matrix on the corrosion behavior of the nanocomposite coatings,
there are two distinct concepts. As it is mentioned above, an
density. After falling to its lowest amount at 3 A/dm2 , the icorr increase in the cobalt content leads to an increase in the electro-
is increased to 0.078 ␮A/cm2 at 4 A/dm2 . Studying the corrosion chemical activity of the Ni–Co alloy matrix and hence, a decrease
resistance (Rp ) variation of the Ni–Co/SiC nanocomposite coatings in the corrosion resistance although mechanical properties are
shows that the highest Rp is obtained for the nanocomposite enhanced [38]. However, increasing the cobalt concentration in the

Table 4
Electrochemical data extracted from the potentiodynamic polarization curves of the Ni–Co/SiC nanocomposite coatings as a function of the particle concentration in the
electrolyte.

SiC particle concentration (g/l) Co (wt.%) SiC (vol.%) Eocp (mV) ˇa (mV/dec) ˇc (mV/dec) Ecorr (mV) icorr (␮A/cm2 ) Rp (k.cm2 )

0 42 0 −368 180.2 98.6 −372 8.33 3.32


5 55 8.1 −201 71.2 176.5 −199 0.050 439.46
10 54.8 7.5 −208 78.4 188.9 −232 0.127 189.35
15 52.3 6.1 −216 48.9 114.4 −225 0.190 78.03
20 44.0 5.7 −209 52.2 213.9 −216 0.218 83.66

Please cite this article in press as: B. Bakhit, et al., Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrode-
posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037
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APSUSC-27637; No. of Pages 9 ARTICLE IN PRESS
8 B. Bakhit et al. / Applied Surface Science xxx (2014) xxx–xxx

electrolyte enhances particle incorporation, and it causes improv- enhanced significantly the corrosion resistance of the Ni–Co alloy
ing the properties of nanocomposite coatings [21]. Therefore, coatings. The highest corrosion resistance was obtained for the
the chemical composition of the Ni–Co matrix has two different Ni–Co/SiC nanocomposite coatings containing 8.1 vol.% SiC nano-
detrimental and beneficial effects on the corrosion resistance of particles. The corrosion properties of the nanocomposite coatings
Ni–Co/SiC composite coatings. Besides the chemical composition, were discussed based on the chemical composition of the coatings,
phase structure is also another considerable factor affecting the particle content, formation of corrosion micro-cells, diminishing
corrosion properties of composite coatings. The XRD patterns show of the effective metallic area, and increasing and hindering of the
that the phase structure of the alloy matrix is not changed by parti- corrosion paths.
cle incorporation. Accordingly, a part of the corrosion resistance of
the studied coatings can be related to the single-phase fcc structure
of the Ni–Co matrix. Moreover, the most major impact of matrix in
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Please cite this article in press as: B. Bakhit, et al., Corrosion resistance of Ni–Co alloy and Ni–Co/SiC nanocomposite coatings electrode-
posited by sediment codeposition technique, Appl. Surf. Sci. (2014), http://dx.doi.org/10.1016/j.apsusc.2014.04.037

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