Surface & Coatings Technology 258 (2014) 12021211

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Surface & Coatings Technology

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

Effect of PC electrodeposition on the structure and tribological behavior

of NiAl2O3 nanocomposite coatings
H. Gl a,, M. Uysal b, H. Akbulut b, A. Alp b
a
b

Duzce University, Gumusova Vocational School, Department of Metallurgy, 81850 Duzce, Turkey
Sakarya University, Department of Metallurgical & Materials Engineering, 54187 Sakarya, Turkey

a r t i c l e

i n f o

Article history:
Received 6 November 2013
Accepted in revised form 1 July 2014
Available online 9 July 2014
Keywords:
Nano-composite
PC and DC electro co-deposition
Wear resistance
Friction coefcient
Surface damage
Wear mechanisms

a b s t r a c t
In this study, NiAl2O3 metal matrix composite (MMC) coatings were prepared from a modied Watt's type electrolyte by pulse current (PC) plating under current densities varying between 1 and 9 A/dm2. The tribological
tests were performed with a reciprocating ball-on-disk apparatus sliding against a M50 steel ball ( 10 mm).
The wear tests were carried out at sliding velocities of 50, 100 and 150 mm/s under a constant load. The results
compared with our previously published work of DC electrodeposited coatings. The results showed that the electrodeposition method can signicantly affect the microstructure and tribological behavior of NiAl2O3 nanocomposite coatings. For the same current density, PC electrodeposition creates coatings with higher co-deposited
particle content, more homogenous particle distribution, higher wear resistance at high sliding distance and improved friction coefcients. The superior dispersion of Al2O3 nanoparticles in PC-coated materials contributed to
its increased load bearing capacity. Detailed tribological tests and characterization showed that DC- and PCcoated nanocomposite layers yielded different wear mechanisms depending on the sliding velocity.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Electrolytic co-deposition is widely used to obtain metal matrix
composites due to its ease of preparation, low-cost and versatility.
Over the past decade and a half, there has been an extensive research
concentrated on conventional direct current (DC) electroplating, pulse
plating and electroless plating, as well as on production-scale codeposition processing for nanocrystalline materials. Electrodeposition
of composite coatings containing second phase particles dispersed
throughout the metal matrix has been the objective of investigations
for industrial applications dating back to 1970 [1].
Composite coatings with incorporating different types of particles exhibit distinctly improved properties, such as higher hardness, wear resistance and corrosion resistance compared to pure metal or alloy coatings
[27]. Particle-reinforced metal matrix composites (MMCs) have a wide
range of engineering applications due to their enhanced properties [812].
Oxides, carbides, diamond particles, nitrides, oxometallates and oilcontaining microcapsules have all been incorporated into a nickel matrix
to improve the tribological properties [1323]. Research on the electrodeposition of nanocomposite coatings has mainly been focused on determining the optimum conditions for production: electrolysis conditions
(composition of the electrolytic bath, presence of additives, pH value)
and current conditions (type of imposed current and values of the current
density) [2227].
Corresponding author. Tel.: +90 380 73140 05; fax: +90 380 731 31 24.
E-mail address: harungul@duzce.edu.tr (H. Gl).

http://dx.doi.org/10.1016/j.surfcoat.2014.07.002
0257-8972/ 2014 Elsevier B.V. All rights reserved.

Pulse current (PC) plating is an established method of electrodepositing metals and alloys that signicantly affects the mechanism of
metal crystallization. The pulse parameters (such as peak current density, duty cycle and frequency) can control the adsorption or desorption of
a species in the electrolyte and the surface diffusion in more ways than
DC plating. During the off period, small grains re-crystallize because
their high surface energy makes them less thermodynamically stable
than large grains, as in bubble coalescence. Additionally, metals deposited by the PC technique have less absorbed hydrogen than those produced using a continuous current due to desorption during the off
period [15]. As a result, PC plating is a promising procedure. It can control
the microstructure, composition and properties of electrodeposits by
varying the electrical parameters [28,29] and thus, can be used to deposit
MMC coatings through co-deposition. In the co-deposition process, ne
(micro- and nanoscale) particles of metal, non-metallic compounds or
polymers in an electrolytic bath are incorporated into the electroplated
coating to improve its properties, such as hardness/strength, toughness,
wear/friction resistance, and corrosion resistance [30,31]. Under identical conditions, the microhardness of a PC-plated Nidiamond composite
(611 Hv) is reported to be higher than that of a DC-plated composite
(540 Hv) [32]. The PC-plated NiPSiC composite was also reported to
possess better tribological behavior than the DC-plated deposit [33].
The purpose of this study is to co-deposit a layer of soft Ni and hard
nanoscale Al2O3 ceramic particles by PC plating and to compare the results with our previously published work in which [27], the coatings
were deposited by DC method with same current densities. Since the
PC method was suggested to increase deposited particle content and

H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

to provide better distribution, it was assumed to determine the optimum experimental conditions to obtain best wear resistance, friction
coefcient, hardness, etc. Although there are several studies on the
wear of NiAl2O3 nanocomposite coatings and numerous reports on
DC and PC electrodeposition of metals and alloys, to the best of our
knowledge, there is no a comprehensive work to investigate the effect
of current density between DC and PC plating techniques on the tribological behaviors of NiAl2O3 nanocomposite coatings at different
sliding velocities. In the present work, Ni matrix composite coatings
containing nanoscale Al2O3 particles were prepared using a pulse
plating procedure to study their microstructure and tribological performance. The effect of current density, and thus the co-deposited percentage and distribution of Al2O3 nanoparticles, on the microstructure and
the subsequent wear performance of both DC- and PC-coated materials
were compared using reciprocating ball-on-disk tests under different
sliding speeds.

1203

VMHT) and a load of 50 g for 15 s. At least 5 measurements were conducted on each sample and the results were averaged.
Wear and friction tests were performed with a reciprocating ball-ondisk CSM tribometer in accordance with DIN 50324 and ASTM G99-95a
standards at room temperature and at 5565% relative humidity under
dry sliding conditions. The counterpart was a M50 steel ball ( 10 mm)
with a hardness of 62 Rc. The system measures the friction coefcient
and time-dependent depth proles using sensitive transducers. The
depth transducer was located vertically on top of the sample. The tests
were performed at a constant applied load of 1.0 N at sliding speeds of
50, 100 and 150 mm/s. After each test, the amount of wear on the composite was calculated by measuring the wear width and depth using a
3D surface proler (KLA Tencor P6) and low magnication optical micrographs. These measurements were also compared with the vertical
transducer depth proles, and thus, the wear rate of the composite
and the steel ball was determined. Lattice distortion and grain size of
the Ni matrix were determined by calculating the lattice constants
using basic reections from the crystal planes.

2. Experimental procedure
3. Results and discussions
The plating electrolyte used for electrodeposition of the nanoparticlereinforced MMCs was a Watt's-type bath. The bath composition and electrodeposition conditions are shown in Table 1. These experimental parameters were obtained by carrying out several studies to optimize
(surfactant content, current density, Al2O3 content in the electrolyte and
stirring speed, etc.) the values before attempting to compare the microstructure and wear characteristics of DC- and PC-electroplated coatings.
The average particle size of the -Al2O3 used for the reinforcing phase
was 80 nm. Several experiments were conducted to determine the sufcient amount of surfactant to create a colloidal electrolyte. For this purpose, prior to deposition, 5 different measurements were carried out for
determining the zeta potentials of the nanoparticle-suspended solutions
with a Malvern Zetasizer Nano Series Nano-ZS.
In the electrodeposition experiments, four different current densities, 1, 3, 6 and 9 A/dm2, were studied to determine the optimum conditions for obtaining a homogeneous microstructure, thus maximizing the
improvement of wear resistance by pulse electrodeposition method.
The experimental results obtained from our previous DC coated coatings were used for comparison with PC method. Plating time was kept
constant at 2 h for each electroplating run. Before deposition, substrates
were polished with 600 mesh emery paper. Al2O3 nanoparticles were
dispersed into the plating bath electrolyte by stirring magnetically for
20 h and then treated in a high frequency homogenizator for 0.5 h. Microstructural investigations were performed with a JEOL-JSM 6060LV
instrument. The particle volume percent were calculated directly from
the 6060LV SEM image analysis program, which was based on phase
area method. The measurements were carried out from 10 different randomly chosen areas and then average particle volume percent was calculated. A Rigaku D/MAX/2200/PC model device was used for X-ray
analysis at a speed of 1/min over a range of 20100. The coating hardness was measured with a Vickers microhardness indenter (Leica
Table 1
Bath and electrodeposition conditions for nano-Al2O3 reinforced MMC production.
Nickel sulfate (Ni2SO46H2O) (g/l)
Nickel chloride (NiCl26H2O) (g/l)
Boric acid (H3BO3) (g/l)
Sodium dodecyl sulfate (g/l)
Hexadecylpyridinium bromide (HPB) (mg/l)
Alumina (Al2O3) (g/l)
pH
Temperature (C)
Current density (A/dm2)
Current type
Duty cycle
Pulse frequency
Plating time (h)

300
50
40
0.1
200
20
4
45
1, 3, 6 and 9
PC
50%
50 Hz
2

3.1. Effect of current density on deposition

Figs. 1 and 2 show the effect of current density on the volume percentage of Al2O3 in the deposited layers. The microstructures in Fig. 1
show cross-sections of DC and PC co-deposited nanocomposites whereas, Fig. 2 presents the relationship between current type and current
density on the co-deposited Al2O3 content. The microstructures produced by PC electrodeposition, shown in Fig. 1, exhibit more homogeneous particle distribution than those produced by the DC method.
Similar results were reported by different researchers and explained
by less agglomerated nano-ceramic particles in the case of PC current
application [34]. During the Ton time the applied pulse current resulted
in a high driving force to tend the ceramic particles to adsorb on the
cathode surface. However, during the Toff time the loosely adsorbed
nano-Al2O3 particles de-attached from the agglomerated state and
moved into the electrolyte. The volume percentage of Al2O3 in the DCplated coatings increased signicantly with current densities up to
3.0 A/dm2 (approximately 9 vol.%). Above 3.0 A/dm2, there was no
measureable particle content increase in the deposited layer (shown
in Figs. 1 and 2a). This maximum in the current density versus Al2O3
volume percentage curve can be attributed to the transition from
activation-controlled metal deposition to diffusion-controlled particle
transfer [27]. As shown in Fig. 2a, for PC electrodeposition, however,
the co-deposited particle content increased linearly with current density. It has been reported that PC coating is a more efcient deposition
process for nanocrystalline NiAl2O3 composite coatings than that of
DC deposition and that it produces less agglomeration of the alumina
nanoparticles embedded in nanocrystalline Ni matrix [28].
The application of PC technique results in the production of composite coatings with higher percentages of incorporation, and a more uniform distribution of ceramic particles in the Ni matrix than those
attained under DC regime [35]. The reason can be explained in terms
of electro recrystallization. Electro crystallization occurs via two competing processes (i.e. the buildup of existing crystals and the formation
of new ones) which are inuenced by different factors. The major ratedetermining steps have been revealed to be charge transfer at the electrode surface and surface diffusion of adions on the crystal surface. Grain
growth is favored at low current density and high surface diffusion
rates, while high current density (overpotential) and low surface diffusion rates promote the formation of new nuclei. If the average current
density is similar, PC plating can satisfy the latter two requirements
since it permits considerably higher overpotentials than the limiting
DC current density [36]. However, in the current work the peak current
densities in the PC technique were chosen as equal with the current
densities in the DC technique. Since the duty cycle in the PC technique

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H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

a) 1 A/dm2 DC

b) 3 A/dm2 DC

c) 9 A/dm2 DC

d) 1 A/dm2 PC

e) 3 A/dm2 PC

f) 9 A/dm2 PC

Fig. 1. Cross sectional SEM micrographs of MMC co-depositions showing distribution of Al2O3 particles coated with current densities; a) 1 A/dm2 DC, b) 3 A/dm2 DC, c) 9 A/dm2 DC, d) 1 A/dm2
PC, e) 3 A/dm2 PC and f) 9 A/dm2 PC.

was 50%, this causes to apply lower current densities during the
electroplating compared with DC technique. Because of this reason,
surface diffusion rate in the presence of PC is decreasing and causes to
obtain coarser Ni grains. Therefore, the nucleation and growth mechanisms become surface diffusion dominant deposition [34]. On the
other hand, in the PC technique, during the Ton the applied similar current density PC provides more powerful effect to transfer the Al2O3 particle through cathode. Therefore, at the Ton peak density application
time, PC permits higher overpotentials and increased entrapment of
the Al2O3 particles [37]. The decrease in the concentration gradient in
the DC method prevents to insert into cathode from the electrolyte cathode interface, which is a type of Nernst boundary layer. As it is known,
Nernst boundary layer is formed because of the concentration difference at very close section of the cathode electrode [38]. In the case of
PC technique, the negative effect of the Nernst boundary layer against
nano-particle entrapment on the cathode can easily be overcome.
Therefore, similar results reported by many researchers about advantages of using PC technique. Karathanasis et al. [39] reported that
there is a strong dependence of the percentage of the embedded particles on the type of the applied current for composite coatings and they
found PC is more dominant than DC technique. In our present study,
specically the imposition of the PC regime leads to higher incorporation percentage of particles compared to DC condition. Therefore, it
seems that there is a proper combination of Ton and Toff at a given
duty cycle of 50%, which permits a sufcient replenishment of the
catholyte enriched in particles during Toff and adequate deposition
time Ton that allows the total engulfment of particles in the matrix. Additionally, Sheu et al. [37] also showed that pulse plating leads to higher
co-deposition percentage of particles compared to DC, regardless of the
current density. This could be associated with prolonged relaxation time
Toff that permits a satisfactory replenishment of Al2O3 particles in the
catholyte and therefore, leads to the increase in the particle incorporation in the matrix.
Fig. 2b compares the XRD patterns of selected nanocomposites created by both current types at 9 A/dm2. These XRD results agree with
the SEM microstructures and quantitative analysis; the nano-Al2O3

content is increased with PC electrodeposition. Co-deposition of Al2O3

also affected the relative intensity of certain crystal planes in the XRD
patterns. An unreinforced Ni coating, deposited for comparison, exhibited preferential growth along the (111) crystal plane. The growth orientations of co-deposited NiAl2O3 composite coatings were not randomly
oriented for both DC and PC coated materials. For DC-deposited nanocomposite coatings, the (220) peak was faint, and the (311) peak became stronger with increasing Al2O3 content. The dominant planes are
(111) and (200) for Ni in the DC coated materials and it seems that
the DC deposit exhibits a mixed [211] + [100] orientation, with a
more profound [211] orientation. zkan et al. [40] and Sohrabi et al.
[41] reported the same results that, introducing the nano-ceramic
particles into the Ni coatings promoted to obtain high intensity (111)
diffraction lines and thus, dispersion at the [211] direction. We have
previously reported that the XRD patterns of nickel nanocomposite
coatings reect textural changes dependent on the particle content of
the deposited layer [27]. The crystallographic orientation of the PCdeposited coatings was somewhat different from that of the DCcoated samples. The PC-deposited nanocomposites exhibited obvious
preference for the (200) and (111) planes. This comprise the PC deposit
exhibits a mixed [100] + [211] orientation with a more profound
[100] orientation. PC deposition is seen to produce a preferred orientation more easily than DC deposition. This provides evidence that PC
coating provided preferential texture and the nano-Ni grains in the PC
technique grown through the (200). Since the PC technique provided
higher preferential nucleation and growth along the (200) compared
with DC technique, PC technique yielded coarser Ni grains.
High frequency effect can be an alternative reason to obtain coarse
grains in the PC coated materials. According to the experimental results
from the work of Lajevardi and Shahrabi [42], the [100] orientation becomes dominant when the frequency is decreased. They can only obtain
that at the frequency level of 100 Hz, the (200) line produced very low
intensity. Since the applied frequency in this study is 50 Hz, we have attributed that the high orientation at [100] direction for PC coated materials can be another reason. On the other side, Kollia and Spyrellis [43]
have investigated the effect of pulse parameters on the textural and

H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

18

particles' surface charge by absorbed molecules or ions, thereby promoting electrophoretic migration of the suspended particles.

PC
DC

a)

1205

% Vol. Al2O3 in coatings

15

3.2. Microhardness of composite coatings

12

20 g/l Al2O3
200 mg/l HPB

0
1

Current Density (A/dm2)

b)

30

c)
Zeta Potential (mV)

20

10

Fig. 3 compares the microhardness of unreinforced Ni and NiAl2O3

composite coatings produced by both DC and PC methods. The microhardness generally increased with nanoparticle content. This increase
is related to the dispersion hardening effect; the presence of Al2O3
nanoparticles obstructs the movement of dislocations in the nickel matrix [44]. From Fig. 3, it can be seen that the microhardness of NiAl2O3
nanocomposite coatings created with both DC and PC methods was
higher than that of the pure Ni coating and increased with increasing
nano-Al2O3 content. There are three reasons behind this increase [14,
18,24,27]: particle strengthening, dispersion strengthening and grain
rening. Particle strengthening is related to the incorporation of hard
particles at a volume percent above 20%. Dispersion strengthening is associated with the incorporation of ne particles (b1 m) at a volume
fraction less than 15%; the matrix carries the load while the small particles hinder dislocation motion. The third mechanism involves the nucleation of small grains on the surface of incorporated particles, resulting in
a general structural renement. The presence of these smaller grains
impedes dislocation motion and increases microhardness. The results
observed in this study can be explained by the second and third mechanisms. The ne particles incorporated within the Ni matrix restrain the
growth of Ni crystals and impede the motion of dislocations by way of
grain rening and dispersive-strengthening effects.
In general, the hardness of coatings produced by DC deposition improved less than that produced by PC deposition. As discussed before,
PC-deposited coatings contain more reinforcing nanoparticles; thus, improved hardness seems to be due to the increased concentration of the
reinforcing hard particles in the coatings. The increase in hardness observed in PC-deposited coatings, however, is not as high as the increased
nanoparticle content in such coatings would lead us to expect. This result can be attributed to the smaller Ni matrix grain size and random
crystallographic orientation in DC-deposited coatings.
3.3. Grain size and lattice distortion of composite coatings

-10

-20

-30
0

100

200

300

400

Concentration of surfactant (HPB) (mg/l)

Fig. 2. a) The volume percentage of co-deposited Al2O3 particles in various current densities for each current type, b) XRD patterns of composite coatings produced with DC and PC
current types at a constant current density (9 A/dm2), and c) the relationship between
amount of surfactant and zeta potential.

The matrix grain sizes of nanocomposites deposited via both DC

(studied previously) and PC methods were calculated from the XRD
data using Scherer's formula [27]. Fig. 4 shows the effect of current density on the matrix grain size for the DC and PC methods. Fig. 4 clearly indicates that the Ni grains were smaller in DC- than in PC-deposited
coatings. Although the electro co-deposited particle content was higher
in the PC-coated materials and matrix grains are expected to be rened
by such an increase in particle content, the DC method yielded ner
700
DC
PC

microstructural modications of the nickel electrodeposits. Based on

their results, they deduced that at high duty cycles [211] is the preferred
orientation and decreasing the duty cycle resulted in [100] orientation.
To ease the comparison of microstructural and tribological analytics,
the same electrolyte was used for both the PC and DC methods. As seen
in Fig. 2c, the zeta potential of the electrolyte is very close to 0 mV when
100 mg/l HPB is added to the electrolyte. Any additional surfactant beyond the baseline 100 mg/l would increase the zeta potential. It is
known that a high positive or negative zeta potential is critical for
suspending nanoparticles and preventing agglomeration during electrodeposition. Other authors studying electrodeposition in different systems reported similar results. For example, Chen et al. [6] demonstrated
that enhanced deposition results are associated with modication of the

Microhardness (Hv)

600

500

400

300

200
Ni

Current Density (A/dm2)

Fig. 3. Effect of current density on microhardness produced with direct and pulse current
composite coatings.

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H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

80
PC
DC

Grain Size (nm)

75
70
65
60
55
50
45
1

Current Density (A/dm2)

Fig. 4. Effect of current density on grain size of the nickel matrix for each current type (direct and pulse current).

matrix grains. This is because the surface diffusion is dominant in nucleation and growth in the PC coating compared with DC technique [34].
Increasing the current density results in increasing the ner grains.
Lajevardi and Shahrabi [42] found that in the (200) plane when the current density increased from 2 A/dm2 to 8 A/dm2 the grain size of Ni was
reduced from 34 nm to 31 nm. The reason for this decrease in the particle size is due to the changing of the preferred crystalline orientation
and/or embedded particles content in the coating [42]. Same results reported by many authors. Beltowska-Lehman et al. [45] reported that the
addition of larger Al2O3 particles results in a slight decrease of the average matrix grain size with increasing current density. The presence of
nano-particles provides more nucleation sites by increasing the surface
area of cathode in accordance with perturbing matrix growth and
consequently results in ner grain size [46]. In this study, increasing
the current density for both PC and DC caused to increase the codeposited particle content and therefore, the grain size of matrix becomes to be ner.
The colloidal particles in aqueous solution are in charged state.
Consequently, a charged particle suspended in an electrolyte solution
tends to be surrounded by an ionic cloud. It was reported that the
nano-ceramic particles could adsorb Ni2+ ions. There are two types of
species that include Ni2+ cations and Ni2+/ceramic particle clouds in
electrolyte. At high current densities, nickel ions and Ni2+/Al2O3 are accelerated to deposit on the cathode surface. This mechanism is valid until
high amount of hydrogen evolution causes a reduction in the current efciency as well as hindering the adsorption of nanoparticles to the metal
surface [35].
Lattice distortion of the Ni matrix for both the DC and PC techniques
was calculated using basic reections from the crystal planes as dened
by Misbah-Ul et al. [47]. The calculated lattice distortions demonstrated
that the composite matrix lattice constants depend on current density
and current type, as shown in Fig. 5. Increasing current density caused
negative lattice distortions in the Ni matrix for both the DC and PC
methods (Fig. 5a and b). In general, these lattice distortions were higher
in DC- than in PC-deposited coatings. As previously discussed in the
XRD analysis, PC electro co-deposition does not have a profound effect
on the texture and, therefore, crystallographic orientation. Despite the
decreased (200) plane intensity, no signicant orientation change was
observed in coatings deposited by PC nanoparticle co-deposition. In
contrast, DC electro co-deposition decreased the intensity of the main
crystal plane, (200), and increased the intensity of the (111) plane.
Moreover, the intensity of other subsidiary crystal planes also increased
in the DC method. Therefore, it was inferred that the DC method exhibited smaller matrix grains. The origins of negative lattice distortion in
nanoparticle-reinforced MMCs can be summarized by three types of
stresses, as reported by El-Sherik and co-workers [48]; these three
stresses are (1) lattice mist stresses resulting from distortion caused

Fig. 5. Effect of current density on lattice distortion of the nickel matrix produced with direct (a) and pulse current (b) composite coatings.

by lattice parameter mismatch at the coating and substrate interface,

(2) thermal stresses arising from differing thermal expansion coefcients at the substrate and coating interface, and (3) residual or intrinsic
stress from particular plating conditions and bath composition.

3.4. Wear and friction properties

3.4.1. Effect of current density on wear and friction properties
The relationships between wear rate and current density in DC and
PC-plated nanocomposites are illustrated in Fig. 6. Fig. 6a clearly shows
that increasing current density, resulted in a signicant decrease in the
wear rate for DC-plated nanocomposites. Increasing sliding speed caused
sharp increments in the wear rate for the coatings deposited with DC
method. As evident from Fig. 6b, PC-deposited NiAl2O3 composite coatings withstood wear better than DC-deposited coatings, this can be attributed to the increased alumina particle content and homogenous
particle distribution. The higher Ni matrix grain size is another advantageous factor for increasing wear resistance in the PC coated materials. As
discussed before, increasing the intensity of (002) plane results in higher
ductility in the Ni based coatings and this caused to increase plastic deformation energy absorbability which prevents microcrack formation
and subsequent delamination. As stated by zkan et al. [40] increasing
the intensity of the (002) plane deposition of Ni resulted in the growth
in the [100] direction. The combined high ductility and higher amount
of Al2O3 particle content resulted in better tribological properties providing both resistance to deformation hardening and load carrying capacity.
However, increasing particle content in the deposited layer with current
density no signicant change observed in the wear rate of PC-plated
nanocomposites (Fig. 6b). This was attributed to the increasing the particle content in the deposited coatings and this may result in decreasing
plastic deformation capability, which causes to reveal fatigue wear

H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

1207

causes wear debris formation in the form of delamination failures,

which reveals ne wear debris.
Fig. 7a and b shows the friction coefcient variation in DC- and PCplated nanocomposites depending on sliding speed and current density.
In general, it can be concluded that increasing sliding speed decreased
the friction coefcient for both DC- and PC-plated nanocomposite coatings. DC and PC-plated nanocomposites have very similar friction coefcients for all current densities at sliding speeds of 100 mm/s and
150 mm/s, except in the DC-plated coatings, small increments in the friction coefcient values have been observed with increasing current density. The increment in the friction coefcient in the DC plated coatings
can be explained in terms of poor interfacial bonding between Ni and
Al2O3 when compared with PC coated materials. The friction coefcient
at 50 mm/s, however, exhibited signicantly different characteristics
with increasing current density. The friction coefcient for DC-plated
coatings were extremely high (approximately 0.7) at the 1 A/dm2 and
3 A/dm2 current densities. A further increase in the current density resulted in a sharp decrease in the friction coefcient. In contrast, coefcients for the PC-plated nanocomposite coatings remained around
0.430.52, and no signicant variation have been observed by changing
the current density. As stated in the experimental section, the deposition
process was carried out with a constant 200 mg/l surfactant and 20 g/l
particle concentration in the electrolyte. The interfacial bond between
Al2O3 nanoparticles and the Ni matrix is thought to be one of the most
inuential factors in sliding wear resistance. It is known that PC deposition provides not only a higher concentration of second phase nanoparticles in the electrodeposited layer but also better interface properties
between the matrix and ceramic particles [51]. It is also evident from
our SEM micrographs that PC deposition promotes more homogenous
distribution and segregation free particle distribution. Thus, increasing
sliding speed caused the wear rate of DC-coated materials to increase,

Fig. 6. Effect of sliding speed on the wear rate of NiAl2O3 composite coatings prepared
with different current types and densities, a) DC and b) PC.

occurred because of microcrack formation. On the other hand, the effect

of sliding speed on the wear rate of PC-produced composites is more interesting and impressive. Increasing sliding speed in the PC-plated nanocomposites resulted in a remarkable decrease in the wear rate. When the
wear rates of DC- and PC-coated nanocomposites are compared in the
case of 1 A/dm2 current density deposition condition, remarkably high
wear resistance is observed for the PC-plated nanocomposites. For example, for the sliding speed of 150 mm/s, the wear rate was recorded as 17
104 mm3/Nm in the DC-plated material whereas the wear rate was
measured as 2 104 mm3/Nm in the PC-produced nanocomposite.
Therefore, the wear rate of PC-deposited coating was found to be approximately 8 times lower than that of DC-plated material for 1 A/dm2 current density deposition condition. In the sliding wear, the decrease in
the wear rate by increasing sliding wear have been observed by several
authors, studied in the dry wear conditions [49, 50]. Therefore, the decrease in the wear rate by increasing the sliding distance is an expected
feature in the electrodeposited Ni coatings. The unusual result here is
the increase in the wear rate with sliding distance in the DC coated materials. This increase can be attributed to the insufcient interfacial interface bonding and inhomogeneous distribution of nano-Al2O3 nanoparticles in the DC coated materials that could result in decreasing load
bearing capacity. As explained and discussed in the microstructure of
the PC and DC deposited materials, the entrapment of the nano-Al2O3
particles on the cathode is more effective in the PC technique since
pulse effect result in overcoming the Nernst boundary layer and provides
more homogenous particle distribution. In the DC coated layers, the particle de-attachment from the surface during sliding occurs because of the
Al2O3 particle agglomeration. Increasing sliding speed result in increasing the stress concentration around the agglomerated particles and

Fig. 7. Effect of sliding speed on friction coefcient of NiAl2O3 composite coatings prepared with different current types and densities, a) DC and b) PC.

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H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

but PC-coated materials exhibited the opposite; increasing sliding speed

decreased the wear rate. This result implies that optimizing the load carrying capacity depends on tribo-oxide formation, which governs the
wear phenomena and, thus, decreases the wear rate.
Fig. 8 illustrates the worn surfaces of DC and PC-produced nanocomposite samples tested at a sliding speed of 50 mm/s. Fig. 8ac shows the
morphology of the worn surfaces of nanocomposite coatings deposited
at different DC current densities. The worn surface of the 1 A/dm2 DC
coated Ni/Al2O3 nanocomposite sliding against M50 steel ball is relatively smooth but displays a few debris (Fig. 8a), indicating that the
coating experienced predominantly adhesive wear character associated
with fatigue crack. Increasing current density from 1 A/dm2 to 9 A/dm2
resulted in decrease in the plastic deformation of the coatings due to the
increased quantity of co-deposited nanoparticles. Increasing current
density also increased the ne debris areas that are evidence for the delamination wear, which occurred because of microcrack formation. The
nano-particle agglomeration in the DC coated materials activated to
start micro crack formation and subsequent delamination with ne
debris.
The worn surfaces of the PC-deposited nanocomposites tested at the
sliding speed of 50 mm/s, shown in Fig. 8df. It is evident from the worn
micrographs, delamination cracks and smeared wear debris were observed, conrming that the wear process of NiAl2O3 composites is
governed by a combination of abrasion and adhesion mechanisms.
Since the PC coated materials showed coarse Ni matrix grains and preferential growth at (200) plane, there are much more plastic deformation
evidences compared with DC coated materials. At low current density,
the worn surface (Fig. 8d) exhibited predominantly adhesive wear characteristics caused by detachment of the smeared matrix after plastic deformation and, later, deformation hardening (showed with the arrow).
The extensive deformation and wear of samples tested at sliding speeds
of 50 mm/s is attributed to the low quantity of co-deposited particles. As
can be seen from Fig. 8e and f, increasing the current density leads to decrease the soft phase smearing on the worn surfaces and therefore, the
amount of plastic deformation decrease. The width of the abrasive
wear scar of the PC deposited Ni/Al2O3 nanocomposite coating is much
more higher than that of the DC deposited Ni/Al2O3 coatings, which

a) 1A/dm2 DC

Debris

b) 3A/dm2 DC

corresponds to the higher amount of particle co-deposition in the PC

method. At high current densities, the discrepancy in deformation of
the nanoscale reinforcement phase and the matrix leads to stress concentrations at the edges of the reinforcement phase, fueling the formation of small debris. Thus, increasing the particle content leads to an
increase in debris (Fig. 8e and f).
In Fig. 9, the surfaces of DC- and PC-produced nanocomposites worn
at the sliding speed of 150 mm/s are presented. The worn surfaces of
both DC and PC coated materials show mixed type of wear mechanisms
of adhesive and abrasive. The wear of DC-coated materials starts with
predominantly abrasive mechanisms and continues with plastic deformation of wear debris leading surface hardening of smeared ductile Ni
matrix; thereafter, followed by fatigue, which produces very small
wear debris associated with some particle agglomeration, most likely
by delamination (Fig. 9ac). Increasing the current density resulted in
decreased formation of ne debris because increased co-deposited particle content increases the load bearing ability. As seen in Fig. 9df, the
worn surfaces of PC-produced coatings are different from those of DCcoated samples. Taking into account all the current density conditions,
the surfaces of PC-coated materials were smoother than those of DCcoated samples. Moreover, signicantly larger quantities of very small
debris were detected on PC-coated materials than on DC samples. For
PC-coated materials, increased current density resulted in decreased
ne debris formation and increased surface smoothness. As shown in
Fig. 9df, the worn surfaces of the PC coated Ni/Al2O3 nanocomposites
sliding against steel ball is not only smooth and show the signs of slight
fatigue and adhesion wear, which indicates that the coating is slightly
damaged by the counterpart steel compared with DC coated materials.
As shown in Fig. 9d, some ne plows and scratches are observed on
the worn surface for the coating deposited at 1 A/dm2 current density,
indicating the abrasive wear also occurred besides the adhesion and fatigue wear. The mixed mode of wear mechanism in the PC coated materials is attributed to the ductile structure of the Ni matrix because of the
coarser grain size and higher particle co-deposition compared with DC
coated materials. Homogeneous distribution of the particles resulted
in decreasing microcrack formation contrary to the DC coated materials.
Therefore, the worn surfaces of the PC coated nanocomposites featured

Microcrack

c) 9A/dm2 DC

Microcrack

Debris

d) 1 A/dm2 PC Deattachment

Abrasive groove

e) 3 A/dm2 PC

f) 9 A/dm2 PC

Abrasive groove

Fig. 8. SEM morphology of the wear tracks of composite coatings prepared with different current types and current densities for 50 mm/s sliding speed; a) 1 A/dm2 DC, b) 3 A/dm2
DC, c) 9 A/dm2 DC d) 1 A/dm2 PC, e) 3 A/dm2 PC and f) 9 A/dm2 PC.

H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

a) 1A/dm2 DC Debris

1209

b) 3A/dm2 DC

c) 9A/dm2 DC

e) 3 A/dm2 PC

f) 9 A/dm2 PC

d) 1 A/dm2 PC

Abrasive groove

Abrasive groove

Fig. 9. SEM morphology of the wear tracks of composite coatings prepared with different current types and current densities for 150 mm/s sliding speed; a) 1 A/dm 2 DC,
b) 3 A/dm 2 DC, c) 9 A/dm 2 DC d) 1 A/dm 2 PC, e) 3 A/dm2 PC and f) 9 A/dm 2 PC.

with less scufng, small plowing and some extend of abrasion. This result indicates that some polishing took place, most likely by pull out of
alumina particles or material transfer during the sliding process. This
phenomenon was also observed by Houa and Chen [28] in pulse electrodeposited NiW/Al2O3 composite coatings and was considered when
assessing the increased load bearing capacity. Because comparatively
lower friction coefcients were obtained for PC-coated samples compared with DC-coated nanocomposite materials by increasing the current density, another reason for the surface smoothness could be
oxidation, which produces tribo-oxide layers.
The surfaces of nanocomposites worn out at the sliding speeds of
50 mm/s and 150 mm/s were also analyzed by EDS facility. Increasing
sliding speed in DC-coated materials showed increased amount of Al
and other components transferred from the steel ball. After the
50 mm/s wear test, EDS analysis performed from several regions along
the wear scar of DC- and PC-coated materials and conrmed the absence of signicant oxygen content. This result shows that the sliding
speed was insufcient to generate heat at the interface between the
steel ball and nanocomposite surface. The PC-coated worn surfaces
after the 150 mm/s test exhibited a thick oxide transfer layer over the
majority of the wear scar with the metallic coating exposed in large localized regions within the scar. Similar results were also reported by
Lekka et al. [52]; at high sliding speeds, Ni-based composite coatings
underwent tribo-oxidative wear, and localized EDS analysis revealed
the wear tracks to be partially covered by a nickel oxide layer (light
gray zone). The scars along the sliding direction were attributed to
third body abrasion caused mainly by detachment of nickel oxide akes
that interpose themselves between the deposit and the counter material. Since the particle distribution is not homogenous in the DC coated
materials compared with PC produced coatings, the oxidized regions
can easily undergo delamination crack and the ne wear debris occurred. The delamination in the form of ne debris in the DC coated materials prevented to form an effective tribo-oxidation layer.
Fig. 10ac depicts the original diagram of friction coefcient and
steel ball penetration (wear depth) changes versus sliding distance in

DC- and PC-produced composites tested at different sliding speeds.

For ease of comparison, only the diagrams for nanocomposites deposited at 3 A/dm2 are presented. As seen from the diagrams for DCproduced nanocomposites, increasing sliding speed decreased the friction coefcient and increased the amount of wear. Fig. 10b clearly
shows that the steel ball penetration sharply increased with increasing
sliding distance, where the friction coefcient remained nearly stable by
increasing the sliding distance. In fact, the continuous increase in wear
(ball penetration) with sliding distance is because of the wear characteristics of the nanocomposite. As stated previously, the predominant
wear mechanism of the DC-coated materials for the 50 mm/s sliding
speed was delamination caused by rstly, adhesive plastic deformation
and continuing surface hardening and then fatigue that produce very
small wear debris. Since poor homogeneous distribution of nanoAl2O3 particles were produced in the DC method composite coatings a
high wear rate obtained compared with PC method coated nanocomposites tested under similar conditions. The PC deposited nanocomposite tested at 50 mm/s sliding speed, exhibit the high friction coefcient
since the smeared wear debris and a combining effect of abrasion and
adhesion mechanisms. Increasing the sliding speed, the surfaces of the
PC coated materials revealed smooth nature because of oxidation of
the matrix phase leading signicant decrease in the friction coefcient.
Therefore, this decrease at the high sling speeds was attributed to the
tribo-oxides formation on the worn surfaces and surface smoothness
combined with good load bearing capacity in the PC produced nanocoatings.
To reveal and make a better comparison between the wear mechanisms of the DC and PC coated materials some selected worn nanocomposite surfaces were scanned with 3D prolometry. The results are
presented in Fig. 11. For brevity, only the nanocomposites tested at
50 mm/s are chosen. It can be seen from Fig. 10a which represents the
worn surface of the DC plated composite produced at 1.0 A/dm2 that
there is a very rough surface and that a severe surface damage occurred,
revealing a large, deep valley. The rough surface is evidence that significant amounts of wear products were smeared on the surface, including

1210

H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

a) 3A/dm2 DC/50mm/s

b) 3A/dm2 DC/150 mm/s

c) 3A/dm2 PC/50 mm/s

d) 3A/dm2 PC/150 mm/s

Fig. 10. Variation of friction coefcient and wear track depth for NiAl2O3 nanocomposites in different sliding speeds: (a) DC, 50 mm/s; (b) DC, 150 mm/s; (c) PC, 50 mm/s; and (d) PC,
150 mm/s.

agglomerated Al2O3 nano-particles (Fig. 11a). In the case of PC coated

worn surface a very smooth surface was obtained (Fig. 11b). Increasing
current density resulted in decreasing, smearing and scufng on the
wear surface. It is probably because of increasing particle content in
the deposited layer made possible by the increasing current density in
DC method (Fig. 11c). Applying PC deposited samples with a current
density of 9.0 A/dm2 yielded a smoother surface and fewer protruded
areas than the sample produced by DC plating. These results also

prove that PC plating produces better interfaces between nanocomposite constituents and results in better tribological behavior (Fig. 11d).
4. Conclusions
Several electrodeposited NiAl2O3 nanocomposite coatings were prepared by DC and PC electrodeposition methods with the same current
density and similar experimental parameters. A detailed comparison

Fig. 11. 3D prolometry results of composite coatings prepared with different current types and current densities and wear tested at 150 mm/s; a) 1 A/dm2 DC, b) 1 A/dm2 PC, c) 9 A/dm2
DC d) 9 A/dm2 PC.

H. Gl et al. / Surface & Coatings Technology 258 (2014) 12021211

revealed the effect of electrodeposition method and current density on

the co-deposited nanoparticle content, particle distribution, matrix microstructure, hardness, wear rate and friction coefcient. The following
conclusions can be drawn from this study:
1. Nanocomposites produced with PC electrodeposition contain higher
quantities of Al2O3 nanoparticles and more homogeneous particle
distribution than those produced with DC deposition. At a current
density of 9.0 A/dm2, the volume percent of Al2O3 was found to be
8.81% and 12.7% for DC and PC deposition, respectively.
2. The microhardness of the coatings increased with dispersed nanoparticle content. The nano-Al2O3 reinforced electrodeposited coatings yielded hardness values as high as 641 Hv with the DC method
and 656 Hv with the PC plating method.
3. Increasing current density decreased the wear rate in DC-plated
nanocomposites. However, increasing current density did not show
signicant change in the wear rate of PC-plated nanocomposites.
4. Increasing sliding speed in DC-plated nanocomposite materials increased their wear rate. Contrary to the DC-plated nanocomposites,
increasing sliding speed resulted in a remarkable decrease in the
wear rate of PC-plated materials and decreased the friction coefcient for both DC- and PC-plated materials.
Acknowledgments
This work is supported by the Scientic and Technical Research
Council of Turkey (TUBITAK) under contract number 106M253. The authors thank the TUBITAK MAG workers for their nancial support.
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