Applied Surface Science 258 (2012) 4260–4267

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Applied Surface Science

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

Effect of particle concentration on the structure and tribological properties of

submicron particle SiC reinforced Ni metal matrix composite (MMC) coatings
produced by electrodeposition
H. Gül b,∗ , F. Kılıç a , M. Uysal a , S. Aslan a , A. Alp a , H. Akbulut a
a
Sakarya University, Engineering Faculty, Department of Metallurgical & Materials Engineering, Esentepe Campus, 54187, Sakarya, Turkey
b
Duzce University, Gumusova Vocational School, Department of Metallurgy, 81850, Duzce, Turkey

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

Article history: In the present work, a nickel sulfate bath containing SiC submicron particles between 100 and 1000 nm
Received 6 June 2011 was used as the plating electrolyte. The aim of this work is to obtain Ni–SiC metal matrix composites
Received in revised form (MMCs) reinforced with submicron particles on steel surfaces with high hardness and wear resistance for
13 December 2011
using in anti-wear applications such as dies, tools and working parts for automobiles and vehicles. The
Accepted 14 December 2011
influence of the SiC content in the electrolyte on particle distribution, microhardness and wear resistance
Available online 8 January 2012
of nano-composite coatings was studied. During the electroplating process, the proper stirring speed was
also determined for sub-micron SiC deposition with Ni matrix. The Ni films were characterized by scan-
Keywords:
Electrocodeposition
ning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The depositions were controlled to
Nano-SiC obtain a specific thickness (between 50 and 200 ␮m) and volume fraction of the particles in the matrix
Dispersion strengthening (between 0.02 and 0.10). The hardness of the coatings was measured to be 280–571 HV depending on the
Microstructure particle volume in the Ni matrix. The tribological behaviors of the electrodeposited SiC nanocomposite
Friction coatings sliding against an M50 steel ball (Ø 10 mm) were examined on a tribometer. All the friction
Wear resistance and wear tests were performed without lubrication at room temperature and in the ambient air (with
a relative humidity of 55–65%). The results showed that the wear resistance of the nanocomposites was
approximately 2–2.2 times more than those of unreinforced Ni.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction ites. Composite coatings can be prepared by techniques such as

Composite electroplating is a method of co-depositing fine
particles of metallic, non-metallic or polymeric compounds in
the plated layer to improve material properties such as wear
resistance, lubrication, or corrosion resistance [1–5]. During the
electroplating process, insoluble materials are suspended in a con-
ventional plating electrolyte and captured in the growing metal
film. The second phase material can be hard oxides (Al2 O3 , TiO2 ,
SiO2 ) [1–3], carbides particles (SiC, WC) [1,2,5], diamond, solid
lubricants (PTFE, graphite, MoS2 ) [1,5], and even microcapsules
containing liquids. In general, having second phase particles in a
co-deposited film results in a variety of improvements in film prop-
erties, such as increased microhardness [5–15], yield strength [5],
tensile strength, increased wear [4–15] and corrosion resistance
[4], self-lubrication and high temperature inertness [4], along with
chemical and biological compatibility [4,6–8]. Many preparation
techniques have been investigated to novel metal-based compos-
∗ Corresponding author. Tel.: +90 264 295 57 62; fax: +90 264 295 56 01.
E-mail address: harungul@duzce.edu.tr (H. Gül).
thermal spray, physical vapor deposition, chemical vapor deposi-
tion and electrocodeposition. Because electrocodeposition can be
conducted at normal pressure and ambient temperature with low
cost, high deposition rates and homogenous particle distribution,
it has been considered one of the most important techniques for
producing composites [3,9].
Ni matrix reinforced with silicon carbide (SiC) have been exten-
sively studied and widely used to protect against friction inside
parts of cylinders in the automotive industry [15]. Considerable
research has been focused on the impact of the electrodeposition
parameters on the electrolytic co-deposition process of SiC with Ni
and the properties of the composite coatings. These parameters
include electrolysis conditions [1,5,7,15,16] (composition of the
electrolytic bath, presence of additives, pH value), current condi-
tions [1,4,5,7,15] (such as the imposed current and current density
values) and properties of the reinforcing particles [1,4,5,7,15,16]
(such as particle size, surface properties, concentration and type of
dispersion in the bath). In general, the amount of embedded SiC
particles has been observed to increase with the concentration of
suspended SiC particles and the presence of additives in the elec-
trolyte [6,7,15,17–24]. From previous reports, decreasing the SiC

0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.12.069
 H. Gül et al. / Applied Surface Science 258 (2012) 4260–4267
particle size can also affect the wear and corrosion resistance in a
positive way. These phenomena have mainly been attributed to the
hardening of the metal matrix by finely dispersed particles, which
weakened the plowing effect, reduced adhesive wear, retarded the
grain growth in the matrix at elevated temperatures, and thereby
sustained adequate mechanical properties [7,13,15,23]. Thus, par-
ticle size plays an important role in the electrocodeposition process
and can affect the mechanical properties of the composite coatings
[7,24].
Generally, the mechanisms of strengthening of alloys and
polycrystalline metals can be described as follows: (I) grain refine-
ment strengthening from Hall–Petch relationship; (II) dispersion
strengthening due to Orowan mechanism; (III) solid solution
strengthening and (IV) crystal orientation. The wear resistance and
hardness of composite coatings are related to each other as well
as to the particle content of the deposit. With increasing the vol-
ume fraction of particles in the deposited layer, wear resistance
increases and thus, the weight of the removed material due to wear
is decreased [25,26].
The problem of agglomeration can be greatly reduced by adding
the surfactant cetyltrimethylammonium bromide (CTAB) [15].
It has been confirmed that suitable surfactants could not only
improve the stability of a suspension by increasing the wettabil-
ity and the surface charge of suspended particles, but they can also
enhance the electrostatic adsorption of suspended particles on a
cathode surface by increasing their positive charge [15,16]. Hou
et al. [15] demonstrated by the dynamic light scattering method
that inert SiC particles formed large agglomerates in the plat-
ing bath. When CTAB was added, the SiC particle agglomerates
decreased, and a high percentage of uniformly distributed, sub-
micron SiC particles were deposited. Increasing the amount of
surfactants adsorbed on the surface of the inert particles would
enhance the possibility of the weak and strong adsorption effect
[15].
The aim of this work is to deposit Ni-MMCs reinforced with
submicron-sized SiC particles on steel surfaces to improve surface
hardness and wear resistance. Introducing high amount of sub-
micron ceramic particles is one of the main targets to increase
wear resistance of Ni based coatings and in general, it is difficult
to deposit sub-micron particle over 10 vol.% content by electrode-
position, since poor wettability causes a detrimental effects for
the properties. Therefore, the process parameters of stirring speed
and particle content in the electrolyte were extensively studied
to deposit high amount of sub-micron particles by using a con-
stant amount of surfactant. In this work, it was aimed to deposit
as high as 10 vol.% SiC and systematically to investigate the effect
of the particle volume fractions on the wear performances of the
electrodeposited Ni coatings.
2. Experimental procedure
The plating electrolyte used in the fabrication process was a
nickel sulfate bath. The composition and the range of experimen-
tal process parameters are shown in Table 1. The range of SiC
particle size used in the experiment was 0.1–1 ␮m. A Ni plate of
30 mm × 35 mm was used as an anode, and a stationary iron sub-
strate was used as a cathode. The bath was heated to 45 ◦ C with a
fixed pH of 4 and stirred with a magnetic stirrer at a stirring speed
value of 250 and 650 rpm, respectively. The amount of surfactant,
CTAB was fixed at 300 mg/L, since agglomeration free sub-micron
SiC particle depositing was provided in this concentration.
After co-deposition, a scanning electron microscope (SEM,
model JEOL – JSM 6060 LV) was used to observe the surface and
the cross-sectional microstructures of the deposits. XRD analy-
sis was carried out with a Rigaku D/MAX/2200/PC model X-ray
4261
Table 1
Bath compositions and electrodeposition conditions for MMC reinforced with SiC
submicron particles.
Nickel sulfate (Ni2 SO4 ·6H2 O) (g/L) 300
Nickel chloride (NiCl2 ·6H2 O) (g/L) 50
Boric Acid (H3 BO3 ) (g/L) 40
Sodyumdodecyl sulfate (g/L) 0.2
Cetyltrimethylammonium bromide (CTAB) (mg/L) 300
Silicon carbide (SiC) (g/L) (0.1–1 ␮m) 5, 10, 20, 30
pH 4
Temperature (◦ C) 45
Current density (A/dm2 ) 3
Stirring Speed (rpm) 250, 650
Plating time (h) 2
diffractometer scanning at a speed of 1◦ /min in the 2 range
of 10–100◦ . The hardness of the coatings was measured using
a Vicker’s microhardness indenter (Leica VMHT) with a load of
50 g. The reciprocating tribological behaviors of the coatings sliding
against an M50 steel ball (Ø 10 mm) were examined on a Tribome-
ter (CSM Instruments) designed according to DIN 50 324 and ASTM
G 99-95a in a ball-on-disk configuration. The wear tests were per-
formed at a constant applied load of 1.0 N with a sliding speed of
50 mm/s. The SEM and energy dispersive X-ray spectroscopy (EDS)
was used to study the morphologies of the wear tracks. The parti-
cle volume fractions were calculated directly from the 6060 LV SEM
image analysis program, which was based on phase area method.
3. Results and discussions
3.1. Effects of the stirring speed on co-deposited SiC particles
In this study, two different stirring speeds initially were applied
to observe the effect of stirring speed in the course of electrode-
position. Hence, it was chosen one low speed (250 rpm) and one
high speed (650 rpm). Fig. 1 shows SEM micrographs of coatings
which performed to observe the effect of stirring speed on the
deposited SiC vol.% in the electroplated Ni matrix. The volume frac-
tion of co-deposited SiC was 2.54 vol.% increasing the stirring speed
to 650 rpm increased the amount of co-deposited SiC to 10.05 vol.%.
Because stirring at 650 rpm produced layers with a large amount of
SiC particles without segregation, the stirring speed for all coatings
was fixed at this level. It is known that in micron-sized parti-
cle reinforced composite coatings vigorous stirring is necessary to
obtain homogenous distribution [27]. This effect also supported in
our present work (Fig. 1). It is also best known decreasing second
phase particle size leads to increase yield strength and hardness
of the resultant composite whereas, coarse particles improve wear
resistance. In this work, it was also aimed to obtain hard and wear
resistant Ni matrix coatings and therefore, high stirring speed was
chosen.
3.2. Effect of particle concentrations in electrolyte on
deposition/deposits
The effect of SiC concentration in the electrolyte on the content
of co-deposited SiC can be observed in Fig. 2. The volume fraction of
co-deposited SiC appeared to increase with the SiC concentration
in the electrolyte (Fig. 3a). The volume fraction of the co-deposited
SiC can be increased up to approximately 10 vol.% by increasing the
concentration of SiC in the electrolyte to 20 g/L. The experimental
data shown in Fig. 3a revealed the relationship between the concen-
tration of SiC in the electrolyte and dispersed SiC particle content
in the deposited layer. It is clear that the amount of co-deposited
SiC increased with the SiC content in the electroplating bath up to
a certain SiC concentration. The amount of co-deposited SiC par-
ticles was reached to a maximum value at 20 g/L particle content
4262 H. Gül et al. / Applied Surface Science 258 (2012) 4260–4267

Fig. 1. Cross-sectional SEM micrographs of the composite coatings, showing the distribution of SiC particles deposited at the stirring speeds of (a) 250 rpm and (b) 650 rpm.

Fig. 2. Cross-sectional SEM micrographs of SiC particle distributions in the composite coatings. The electrolyte used to prepare the coatings has SiC concentrations of (a)
5 g/L, (b) 10 g/L, (c) 20 g/L and (d) 30 g/L.

a 12 b
o Nickel
Volume fraction of SiC (vol. %)

SiC
10
(111)

(200)

(311)
(220)

(222)

o o o
Ni o o
8
Intensity

5 g/l SiC
6
10 g/l SiC
4
20 g/l SiC

2
30 g/l SiC

0
5 10 20 30 20 40 60 80 100

Particle concentration in electrolyte (g/l) 2θ

Fig. 3. (a) The volume fraction of SiC particles deposited at various SiC concentrations in the electrolyte, (b) effect of various SiC concentrations in the electrolyte on XRD
patterns.
 H. Gül et al. / Applied Surface Science 258 (2012) 4260–4267
in the electrolyte and then decreased when the concentration was
further increased to 30 g/L.
Lee et al. [24] showed that the maximum amount of co-
deposited SiC corresponded to steady-state equilibrium, where the
number of co-deposited SiC particles equals the number of SiC
particles approaching the cathode surface. When the SiC content
exceeded the maximum amount of co-deposited of SiC at equilib-
rium, suspended SiC particles agglomerated in the plating bath, and
the amount of particles incorporated into the Ni matrix decreased.
In addition, the agglomerates themselves can resist being incor-
porated into the Ni matrix when the SiC content in the plating
bath is high, thereby shielding the surface of the cathode from
the flux of incoming SiC particles, as reported by Abdel et al. [25].
The decrease in particle content in the electrolyte beyond 20 g/L
was taken place because of two reasons: (i) it is believed that a
SiC particle concentration above 20 g/L in the electrolyte can lead
to a shielding effect for the particles co-deposited in the Ni layer.
During the co-deposition of the Ni and SiC, the SiC particles were
suspended in the electrolyte. Not all the SiC submicron particles
were expected to tend to the cathode and be deposited in the Ni
layer. Because of the elastic collision of the SiC particles inside the
electrolyte, some of the SiC particles were backscattered from the
interface between electrolyte and substrate where the particle den-
sity is highest. If a high amount of SiC particles were present in
the electrolyte, they could backscatter at the cathode–electrolyte
interface, since the SiC particles were directed to the cathode sub-
strate. (ii) The decrease can take place according to the Guglielmi
two-step adsorption model [28]. Increasing particle concentration
in the electrolyte increases the adsorption, thus resulting in a higher
volume percent of SiC submicron particles in composite coatings,
while the decrease in the volume percent of the SiC submicron par-
ticles at a concentration of SiC particles above 20 g/L is attributed to
the agglomeration of the SiC submicron particles in the electrolyte
owing to their poor wettability.
The amount of co-deposited SiC particles increased significantly
up to a SiC concentration of 20 g/L, likely because more particles
were present in the plating bath. Only particles that clung to the
cathode surface for a sufficient period of time can be successfully
incorporated into the Ni matrix. Therefore, the entrapment of the
SiC particles into the growing Ni matrix depended on both the rate
of SiC particles approaching the cathode surface and the rate of Ni
deposition. Although the number of SiC particles approaching the
cathode surface increased with the SiC content in the plating bath,
the capturing capacity of the growing metal remained virtually the
same [24]. Consequently, only a limited amount of SiC particles was
co-deposited when the concentration was beyond 20 g/L.
Fig. 3b shows the XRD patterns of pure Ni and Ni–SiC nanocom-
posites. The (2 0 0) diffraction peak of Ni in the nanocomposite
coating has a lower peak intensity and broader peak width than that
of the Ni coating (see Fig. 3b) as also evidenced by many researchers
[28,29]. This was attributed to the decrease in the grain size of the
Ni–SiC nanocomposite coating with the addition of SiC submicron
particles in the plating bath. The submicron particles provided more
nucleation sites and retarded crystal growth, resulting in a smaller
crystal size for the Ni matrix in the composite coating [17].
Pure Ni exhibited two intense reflection peaks of (2 0 0) and
(1 1 1), introducing SiC particles led to change the predominant
reflection peak to (1 1 1). This means mixed (2 0 0) and (1 1 1) planes
changed to predominant diffraction in (1 1 1) plane. Srivastava et al.
[29] reported same results from sulfamate bath. The reason was
attributed to change surface morphology of the Ni grains. They
reported that the incorporation of nano-SiC has altered the Ni–Co
matrix from a dense spherical smooth surface to rough nodular
morphology. As stated by Gyftou et al. [7], the preferred orienta-
tion and texture of the Ni growth were also influenced by changing
duty cycle percent at constant applied current density. Here, it can
4263
600 10,05% 9,32%
500
Microhardness (HV)
400 4,54%
4,1%
300
200
100
0
Ni 5 10 20 30
Particle concentration in electrolyte (mg/l)
Fig. 4. Effect of particle concentration in the electrolyte on microhardness of the
coating.
be suggested that introducing different amount of SiC particles into
Ni matrix resulted to change nucleation and growth kinetics of
the Ni matrix deposited. The change is expected to cause lattice
distortion and hence, increment in the matrix hardness. Increas-
ing particle content in the electrolyte and thus, in the deposited
layer promoted the intensity of the reflections of (2 0 0) and (3 1 1).
Accordingly, the Ni–SiC composite exhibited increased (2 2 2) and
(3 1 1) diffraction planes and attenuated (2 0 0) plane with increas-
ing SiC content. As stated in Fig. 2, increasing particle content in the
electrolyte resulted in increasing the co-deposited SiC. However,
this effect is not clear in Fig. 3b. The intensity of SiC peak for the
composite deposited at 5.0 g/L particle content in the electrolyte
is 442.0 and gradually increased by increasing particle content in
the electrolyte and reached to 782.0 for the composite deposited at
30 g/L SiC.
3.3. Effect of particle concentration on microhardness
The hardness values of the unreinforced Ni coating and the
Ni-MMCs co-deposited with submicron-SiC are shown in Fig. 4.
The improved hardness due to the increased SiC content in the
deposited layer was highly correlated to the volume fraction of
SiC. The microhardness of the Ni–SiC composite coating containing
10.05 vol.% SiC was 571 HV, whereas the microhardness of a pure Ni
coating was only 280 HV. The enhanced hardness of the composite
can be attributed to the contribution from the soft matrix and to
some extent, from the SiC particulates. The relation between hard-
ness and crystallite size is in accordance with the Hall–Petch effect
[29].
3.4. Lattice distortion of nickel matrix
Lattice distortion of the Ni matrix for unreinforced alloy and
Ni–SiC composite matrix was determined by calculating their lat-
tice constants using basic reflections of the crystal planes. For
comparison, the lattice constant for unreinforced Ni coatings was
also calculated and compared with co-deposited Ni matrix reflec-
tions. The deviation in the lattice constants of the unreinforced Ni
coatings and composite matrices was assessed as the lattice dis-
tortion. For a fcc system, the lattice constant can be calculated as
follows [30]:
 
2 2
a = (h2 + k2 + l2 ) (1)
4 sin2 
4264 H. Gül et al. / Applied Surface Science 258 (2012) 4260–4267
0,5
0,4
0,3
% Distortion
0,2
0,1
0,0 (111)
(200)
(311)
0 5 10 15 20 25 30
SiC in electrolyte (g/l)
Fig. 5. Effect of particle concentration in the electrolyte on the lattice distortion of
the Ni matrix.
The deviation in the lattice constant depending on the particle
content and deposition parameters was calculated with the follow-
ing equation:
 (a − a ) 
0 1
distortion% = 100
a0
where a0 is the lattice constant of the unreinforced Ni coating, and
a1 is the lattice constant of the Ni matrix for composites produced
at different conditions.
Fig. 5 shows the relationship between lattice distortion and
particle content in the electrolyte. The initial introduction of SiC
particles at a concentration of 5 g/L into the electrolyte led to a
negative lattice distortion at all crystal planes. However, a parti-
cle concentration of higher than 5 g/L in the electrolyte gradually
increased lattice distortion. The reason for the initial negative and
subsequent positive lattice distortion with increasing particle con-
tent in the electrolyte is not yet clear. It is thought that up to
10 g/L SiC addition into the electrolyte is not effective to change
the growth structure of the Ni matrix. As stated in XRD results
increasing particle content result in changing predominant growth
planes. However, there should be some other reasons for this pos-
itive lattice distortion related with the surfactant additions. As
known surfactant CTAB is a hydrocarbon type chemical compound.
Another possible reason is thought that during electrodeposition,
the surfactant was ionized for constituting a negative charge at the
particle surfaces. C–Ni equilibrium diagram showed a 1.6 wt.% sol-
ubility of C at 1025 ◦ C but the diagram does not give information if
Ni solves C at 45 ◦ C at which the coating processes were carried out.
It is supposed that the ionized surfactant leads the C ions diffuse
into Ni matrix and behave as an interstitial element and so causes
a positive distortion in the Ni lattice [1].
3.5. Wear and friction
3.5.1. Effect of particle concentration on the wear and friction
properties
Fig. 6 shows the SEM images of the worn surfaces at a low
magnification that indicates the effect of particle concentration
in the electrolyte. As evidenced in the figure, the amount of wear
decreased in the deposited layer when the SiC particle content in
the electrolyte increased up to 20 g/L because the width of the wear
tracks decreased. From the low magnification micrographs, a high
level of plastic deformation was seen on the surface of the com-
posites produced with a 5 g/L and 10 g/L particle content in the
electrolyte. The composite deposited at a particle content of 30 g/L
also showed a large amount of plastic deformations and seizure of
Ni on the sliding surfaces. Depending on the particle content in the
deposited layer the amount of wear decreased by 170% (Fig. 7a).
The wear resistances of MMCs are strongly related to the
particle content in the metallic matrix. Fig. 7a shows the relation-
ship between the particle concentration in the electrolyte, which
depended on the volume fraction of SiC and wear rate. The results
indicate that the wear resistance increased with the volume frac-
tion of SiC in the deposited layer. The wear rates of composite layers
depended mainly on the particle concentration in the electrolyte.
The composite that exhibited the highest wear resistance has the
maximum volume fraction of SiC (10.05 vol.%). Several authors
[13,15,28,31,32] described that the addition of hard microceramic
particles into the metal matrix can improve its hardness and wear
resistance. These phenomena are mainly attributed to the harden-
35 ing of the metal matrix by finely dispersed ceramic particles. These
dispersed ceramic particles weaken the plowing effect and adhe-
sive wear, and they retard the grain growth in the matrix at elevated
temperatures to sustain good mechanical properties. However, as
reported by several authors the particles need to be smaller than
1 ␮m in diameter and uniformly dispersed to exhibit the dispersion
hardening effect [25,26,33].
The amount and size of the particles define two kinds of
reinforcing mechanisms in MMC materials, namely dispersion
strengthening and particle strengthening. When the dispersed par-
(2) ticle size is higher than 1 ␮m the strength of the metallic matrix
is increased predominantly due to load carrying capacity of the
reinforcement phase. A dispersion strengthened composite is char-
acterized by a dispersion of fine particles with a particle diameter
ranging from 0.01 to 1 ␮m through a dislocation–particle inter-
action or an Orowan hardening mechanism [32]. In this case,
the matrix carries the load, and the fine particles impede the
motion of dislocations [34]. Thus, for the Ni–SiC nanocomposite
in this experiment, the enhancement was related to the disper-
sion strengthening effect caused by SiC particles that impeded
the motion of dislocations in the metallic matrix of the compos-
ite coatings [15,35]. During the friction process, the co-deposited
SiC submicron particles that carried the loads transferred from
the matrix gradually protruded out of the matrix. As a result, the
amount of thermal plastic deformation and scuffing wear in the
sliding was reduced. The protrusion of the SiC particles was also
the reason why the friction coefficient of the Ni–SiC nanocomposite
was more than the as-deposited Ni film.
In the alloys that reinforced with submicron particles (smaller
than 1 ␮m) another possible effect are the differences thermal mis-
match between constituents, and matrix grains size refinement. As
increasing in the second phase content the grain size was reduced
of the Ni matrix was reported [36]. Therefore, the increase in the
microhardness values of the Ni–SiC nanocomposites may be due to
smaller grain size of the Ni matrix favored by the submicron-sized
SiC particles.
In the deposited layer with the 5 g/L particle concentration,
the wear rate was approximately 12 × 10−4 mm3 /Nm. However,
the wear rate decreased to 5.5 × 10−4 mm3 /Nm when the parti-
cle concentration in the electrolyte increased to 20 g/L, indicating
approximately a 2.2-fold increase in the wear resistance. This is
because of the increased amount of SiC particles resulted in increas-
ing matrix strength and also load carrying capacity of SiC particles,
especially the particles that their sizes are close to 1 ␮m.
The friction coefficient of pure Ni is 0.2. Introducing 5 g/L and
10 g/L SiCp into the electrolyte resulted in an effective increase
in the friction coefficient of the Ni matrix. Introducing SiCp into
Ni resulted in increasing friction coefficient. Introducing 5 g/L SiCp
into the electrolyte increased friction coefficient to 1.22. As seen
in Fig. 7b, the friction coefficient increased to 1.38 for the com-
posite produced with a particle concentration of 10 g/L, which
 H. Gül et al. / Applied Surface Science 258 (2012) 4260–4267 4265

Fig. 6. SEM morphologies of the wear tracks of composite coatings prepared with different particle concentrations in the electrolyte, shown at low magnifications: (a) 5 g/L
SiC (4.1 vol.% SiC), (b) 10 g/L SiC (4.54 vol.% SiC), (c) 20 g/L SiC (10.05 vol.% SiC) and (d) 30 g/L SiC (9.32 vol.% SiC).

subsequently decreased as the particle concentration exceeded coating surfaces. At the particle concentration of 20 g/L, the worn
10 g/L in the electrolyte. The reason of this increment in the fric- surfaces were fairly smooth. However, the worn surfaces demon-
tion coefficient with increasing particle content in the electrolyte strated a predominantly abrasive mechanism when the particle
from 5 g/L to 10 g/L is not so clear. The reason of this increment concentration was 30 g/L. Increasing particle content in the elec-
is believed to be caused from insufficient load carrying effect of trolyte and thus, increasing particle content in the electrodeposited
SiC particles. High interparticle spacing between co-deposited SiC layer resulted in decreasing amount of the surface cracks which
particles is thought was not enough to create effective dispersion shows the wear takes place also by abrasive type of mechanisms.
hardening. During the sliding process, the stress is concentrated Formations of the surface cracks are main evidence of the wear
between the Ni and SiC particles and resulted in particle pull out, product smearing on the worn surface and then subsequent delam-
which deteriorated friction coefficient due to abrasive effect. ination type of the wear.
Fig. 8 shows the SEM morphologies of worn surfaces at high EDS analysis of the coatings showed formation of an inhomoge-
magnifications, demonstrating different wear mechanisms on the neous transfer layer as the SiC particle content increased; however,
composites. At low particle concentrations, the worn surfaces the formation of this layer was dependent on the CTAB and SiC
showed seizure of the wear debris on the sliding surface and particle content in the electrolyte. From the EDS spectra, it was
subsequent plastic deformation hardening evidenced by microc- concluded that increasing the particle content led to the forma-
racks on the surface. Increasing the charge concentration resulted tion of a transfer layer that consisted of a mixture of iron debris,
in fewer deformation hardenings. The wear mechanism transited which comes from counterpart steel ball, Ni matrix and fragments
from adhesive to abrasive, as evidenced by small grooves on the of second phases on the sliding surfaces.

a 20 b 1,6
19
Wear Rate ( x10-4 mm3/Nm)

18
17 1,4
Coefficient of Friction (μ)

16
15 1,2
14 Ni 4,1%
13
12 4,54% 1,0
11
10
9 0,8
8 9,32%
7 0,6
6
5 10,05%
4 0,4
3
2 Ni
1 0,2
0
-5 0 5 10 15 20 25 30 35 -5 0 5 10 15 20 25 30 35

SiC concentration in electrolyte (g/l) SiC concentration in electrolyte (g/l)

Fig. 7. Effect of the particle concentration in the electrolyte on: (a) wear rate and (b) the friction coefficient of the Ni–SiC composite coatings.
4266 H. Gül et al. / Applied Surface Science 258 (2012) 4260–4267
Fig. 8. SEM morphologies of the wear tracks of composite coatings prepared with different particle concentrations in the electrolyte, shown at high magnifications: (a) 5 g/L
SiC (4.1 vol.% SiC), (b) 10 g/L SiC (4.54 vol.% SiC), (c) 20 g/L SiC (10.05 vol.% SiC) and (d) 30 g/L SiC (9.32 vol.% SiC).
As seen from the above results, introducing SiC submicron parti-
cles (between the sizes of 100–1000 nm) in the matrix can improve
the hardness and wear performance of Ni–SiC nanocomposite
coatings. Increasing surface hardness and therefore, poor surface
deformation ability is arising from the hardness of the resultant
composite.
4. Conclusions
1. Ni MMCs reinforced by submicron-sized (100–1000 nm) SiC par-
ticle were successfully co-deposited by D.C. electroplating with
up to 10.05 vol.% particle concentration.
2. The electrodeposited coatings reinforced with submicron-SiC
particles yielded hardness values as high as 571 HV because of
unique dispersion effect, whereas the hardness value of the unre-
inforced Ni matrix hardness was 280 HV.
3. Increasing the particle content in the electrolyte resulted in an
increase of particle concentration of the co-deposited coatings,
up to a maximum of 20 g/L. Further increase in the particle con-
tent in the electrolyte decreased the particle concentration in
the coating.
4. Increasing the particle content in the electrolyte resulted in the
lattice distortion of the Ni matrix.
5. Wear resistance of the coatings increased with SiC particle
content up to 20 g/L in the electrolyte. However, the wear resis-
tance began to decrease beyond this concentration. Pure Ni
showed adhesive type of the wear mechanisms whereas Ni–SiCp
composites exhibited an abrasive type of wear which its predom-
inance increases with increasing SiCp.
6. The co-deposited Ni–SiC nanocomposite coatings showed higher
friction coefficients and better wear resistance compared to
the as-deposited Ni film. This was attributed to the incorpora-
tion of submicron-sized SiC particles in the deposit that greatly
increased the hardness of the composite coating through grain
refinement strengthening and dispersion strengthening.
Acknowledgments
This work was supported by the Scientific and Technical
Research Council of Turkey (TUBITAK) under the contract number
106M253. The authors thank the TUBITAK MAG workers for their
financial support.
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