Materials and Design 65 (2015) 550–558

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Materials and Design

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

Fretting and wear behaviors of Ni/nano-WC composite coatings in dry

and wet conditions
Lidia Benea a,⇑, Sorin-Bogdan Basßa a, Eliza Dănăilă a,e, Nadège Caron b, Olivier Raquet c, Pierre Ponthiaux d,
Jean-Pierre Celis e
a
Competences Center: Interfaces-Tribocorrosion-Electrochemical Systems, Faculty of Materials and Environmental Engineering, Dunarea de Jos University of Galati,
47 Domneasca Street, RO-800008 Galati, Romania
b
Lasers and Surfaces Engineering Laboratory, CEA, Saclay F91191, France
c
CEA, Nuclear Energy Division, Physico-Chemistry Department, CEA, Saclay F91191, France
d
Laboratoire Génie des Procédées Matériaux, Ecole Centrale Paris, F-92290 Châtenay-Malabry, France
e
Department of Metallurgy and Materials Engineering, Katholieke Universiteit Leuven, Kasteelpark Arenberg 44, B-3001 Leuven, Belgium

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

Article history: The fretting and wear behaviors of Ni/nano-WC composite coatings were studied by considering the
Received 6 June 2014 effect of fretting frequency of 1 Hz during 10,000 cycles, at different applied loads in dry or wet condi-
Accepted 19 September 2014 tions. The studies were performed on a ball-on-disk tribometer and the results were compared with pure
Available online 2 October 2014
Ni coating. The nanohardness of pure Ni and Ni/nano-WC composite coatings was tested by nanoinden-
tation technique. To evaluate the wet wear (tribocorrosion) behavior the open circuit potential (OCP) was
Keywords: measured before, during and after the fretting tests at room temperature in the solution that simulates
Ni/WC nanocomposite coating
the primary water circuit of Pressurized Water Reactors (PWRs). The results show that Ni/nano-WC com-
Nanohardness
Fretting wear
posite coatings exhibited a low friction coefficient, high nanohardness and wear resistance compared
Tribocorrosion with pure Ni coatings under similar experimental conditions. Ni/nano-WC composite coatings were
Friction coefficient obtained on stainless steel support by electrochemical codeposition of nano-sized WC particles (diameter
size of 60 nm) with nickel, from a standard nickel Watts plating bath. The surface morphology and the
composition of the coatings were characterized by scanning electron microscopy (SEM) and energy dis-
persive spectroscopy (EDX) respectively.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction increased microhardness, wear and corrosion resistance, a shift

The development of new engineering process imposes metallic
materials with improved surface properties. Coatings obtained by
nickel only may not meet these requirements. Therefore research-
ers’ attention was directed to the development of composite mate-
rials with new structures and unique functions [1].
Electro-codeposition is one of the most used techniques for
obtaining metallic and non-metallic composite coatings. A metal
matrix is used to hold the dispersed phases together and to pro-
mote a good adhesion to the metal surface intended to be coated.
The dispersed phases used in electro-codeposition process are con-
sidered to be inert to the electrolyte and can be of different types
like pure metals, ceramics or organic materials [2]. The inclusion
of dispersed phase into composite coating can generate an
⇑ Corresponding author. Tel.: +40 744216277; fax: +40 236460754.
E-mail addresses: Lidia.Benea@ugal.ro, lidiabd@yahoo.com (L. Benea).
in the reduction potential of a metal ion and a markedly increase
of thermal stability.
The electrodeposition of composite coatings that have a nickel
matrix have been of much interest in recent years because of the
combination of hardness, wear and corrosion resistance, lubrica-
tion and catalytic properties [3–6]. Usually composite coatings in
which are added hard oxide such as SiO2 [7], Al2O3 [8,9], ZrO2
[10] or carbide particles like WC [5] and SiC [11–13] or even dia-
mond [14] improve the hardness and resistance to corrosion and
wear.
The phenomenon of wear in both dry and wet conditions exists
in different areas of the industry where it causes damage, for
example in nuclear power plants, some tribological issues occur
due to regular interaction between components.
It is well known that in the corrosion-wear process the material
degradation is often much larger than would be expected from a
simple summing of the mechanical wear processes and electro-
chemical and/or chemical corrosion processes determined sepa-

http://dx.doi.org/10.1016/j.matdes.2014.09.050
0261-3069/Ó 2014 Elsevier Ltd. All rights reserved.
 L. Benea et al. / Materials and Design 65 (2015) 550–558
rately. So it is important to consider the synergism resulting from
the coupling of mechanical and environmental effects [15]. Ponthi-
aux et al. [16] proposed several electrochemical techniques of
interest for studying in situ tribocorrosion processes which are
open circuit potential measurements, potentiodynamic polariza-
tion measurements and electrochemical impedance measure-
ments. In this work only the open circuit potential
measurements technique was used to investigate the synergistic
response between wear and corrosion.
In the literature are reported only few works on electro-codepo-
sition and characterization of Ni/WC nanocomposites [17–19],
works which are relatively new and which do not treats the fret-
ting wear behavior in dry and wet conditions of the obtained coat-
ings. The novelty of this research work is to obtain Ni/nano-WC
(60 nm mean diameter) composite coatings with good adherence
to stainless steel support, having a coating thickness of 20 microm-
eters and about 12 wt.% of tungsten carbide included into nickel
matrix, by electro-codeposition process with enhanced properties.
The Ni/nano-WC composite coatings obtained by electrodeposition
were comparatively characterized to nanohardness and wear resis-
tance in dry and wet conditions. In the tribocorrosion experiments
it was used a solution that simulates at room temperature the cor-
rosion environment from the primary circuit of PWRs in order to
consider the real impact of the coatings obtained.
2. Experimental procedures
2.1. Materials and coatings preparation
Ni/nano-WC composite coatings were electrolytically deposited
from a standard nickel Watts plating bath to which WC nanoparti-
cles with a concentration of 10 gL1 was added. The tungsten car-
bide (WC) nanopowder with a purity of 99.95%, grain size of 60 nm
was purchased from MK Impex Corp. (Ontario, Canada).
Electro-codeposition was carried out in a typical three-elec-
trode cell with double walls to keep constant temperature of the
solution, where 304L stainless steel plates with exposed surface
area of 4 cm2 were used as working electrodes (WE), a nickel plate
was used as a auxiliary electrode (AE) and a saturated calomel elec-
trode (SCE – Hg/Hg2Cl2) with KCl saturated solution (E = +244 mV
vs. normal hydrogen electrode – NHE) was used as a reference
electrode (RE). The working electrode and auxiliary electrode were
positioned vertically and parallel in the electrolytic bath having the
same distance for each measurement. Tungsten carbide as a hard
phase can be included into the Ni matrix to improve the wear resis-
tance of Ni-based coatings. Schematic presentation of the electro-
lytic cell and electro-codeposition process is shown in Fig. 1,
where (a) represent the electrolytic cell with cathode (–) as the
working electrode support for coatings to be electrodeposited,
the anode (+) or counter electrode as nickel plate in order to main-
tain an constant content of nickel ions into nickel plating bath) and
in the middle is the electrolyte or the plating solution having an
homogenous dispersion of WC nanoparticles maintained by
stirring.
The electrolyte contain nickel salts dissolved which form nickel
ions. After immersion of nano sized WC particles into nickel elec-
trolyte it is formed a dispersion of particles surrounded by ions
from the solution. Only positively charged particles (surrounded
by nickel ions or even hydrated hydrogen ions) are supposed to
migrate to the cathode together with nickel ions to form further
nickel matrix with nano WC particles included as Ni/nano-WC
composite coatings, Fig. 1(a and b).
The bath temperature was kept at 42 ± 1 °C. During electrolytic
codeposition process, the electrolytic bath was stirred using a mag-
netic stirrer at a rate of 320 rpm (resulted from preliminary tests as
551
optimum for this electrochemical set-up), in order to keep the WC
nanoparticles in suspension. Electrodeposition of the Ni/nano-WC
composite coatings was carried out galvanostatically with a poten-
tiostat/galvanostat. The applied current density and the co-deposi-
tion time were calculated so as to obtain layer thicknesses of about
20 micrometers according to the laws of electrolysis. Pure Ni
deposits were also produced under the same experimental condi-
tions for comparison.
2.2. Characterization of coatings
In this work the pure Ni coatings where used as a reference
material for comparison with the Ni/nano-WC composite coatings.
The morphology and chemical composition of the obtained coat-
ings before and after fretting wear experiments were observed
through SEM (Philips scanning electron microscope XL 30 FEG)
connected to an EDX system.
The nanohardness of the pure Ni coatings and Ni/nano-WC
composite was measured with a nano hardness tester (nanohard-
ness tester, CSM) by nanoindentation technique. Hardness and
elastic modulus were determined by the method of Oliver and
Pharr [20] applied on nanoindentation tests. These tests were per-
formed using a diamond Berkovich indenter at normal load of
50 mN. The hardness values reported are the statistical average
of 3 indentations.
2.3. Fretting wear experiments
The wear tests in dry and wet conditions of Ni/nano-WC com-
posite coatings and pure Ni coatings were performed on recipro-
cating dry and wet fretting conditions using a ball-on-plate
geometry. The fretting tests were performed against an alumina
ball, Al2O3, (10 mm diameter) at normal loads of 1 N, 2 N and
5 N, a fretting frequency of 1 Hz, linear displacement amplitude
of 200 lm and for 10,000 fretting cycles using a tribometer.
Al2O3 ball was selected as a counter body due to its high wear
resistance, high chemical inertness and high electrical resistance.
Corundum balls were cleaned with ethanol prior to fretting tests.
All the fretting tests were performed at room temperature. For
dry wear the tests were performed in ambient air with 50% relative
humidity at 23 °C in dry conditions. In the tribocorrosion tests it
was selected a solution with the following composition 5.72 gL1
LiOH and 0.4485 gL1 H3BO3, having a pH of 8.3 in order to simu-
late at room temperature the primary water of the PWRs [21]. The
electrolyte volume used in tribocorrosion tests was of 40 mL.
Experimental set-up for tribocorrosion tests consisted in a conven-
tional three-electrode cell composed of: working electrode – pure
Ni coating and Ni/nano-WC composite coatings, reference elec-
trode – Ag/AgCl microelectrode with KCl saturated solution
(E = +200 mV vs. normal hydrogen electrode – NHE) and auxiliary
electrode – Pt foil. The active surface area of the working electrode
exposed to the solution was 1 cm2. The experimental procedure
used in the tribocorrosion experiments for the tested samples is
graphically shown in Fig. 2.
During the fretting tests, the normal force, tangential force,
coefficient of friction, number of cycles as well as displacement
amplitude, were recorded.
The electrochemical protocol used for the tribocorrosion tests
consisted of two steps: (1) measuring the open circuit potential
(OCP) of the sample for 60 min before starting up the fretting tests
in order to reach a stable potential and (2) after that the Al2O3 ball
was brought in contact with the tested sample and a constant load
was applied for 10,000 s, using mechanical parameters previously
indicated. After the end of fretting tests the load was released
and for a period of 60 min the OCP was monitored in order to
observe its evolution without any load applied or fretting motion.
552 L. Benea et al. / Materials and Design 65 (2015) 550–558

Fig. 1. Schematic representation of the electro-codeposition process: (a) electrolytic cell with anode, cathode and plating solution; (b) SEM surface micrograph of Ni/nano-
WC composite obtained; (c) SEM micrograph of Ni/nano-WC coating in cross section showing a good adherence to stainless steel support; (d) SEM–EDX spectrum of Ni/nano-
WC coating proving the WC inclusion into nickel matrix by tungsten element.

Fig. 2. Schematic view of the experimental set up for fretting wear and tribocorrosion tests.

After wet fretting tests the samples with wear tracks were exam-
ined ex-situ on SEM for morphology considerations.
3. Results and discussion
3.1. SEM surface morphology of electrodeposited coatings
Surface morphology of coatings was studied by scanning elec-
tron microscopy (SEM). Fig. 3(a and b) shows the SEM morpholo-
gies of both types of deposited coatings. SEM micrograph of the
pure Ni coating represented in Fig. 3(a) exhibit a homogeneous
metallic structure with regular pyramidal shape, typical for nickel
crystallites [17]. The surface morphology of pure Ni coating is con-
stituted by a very well formed crystallites with grain size which
may exceed few microns. From Fig. 3(b) which shows the SEM
micrographs of nanocomposite deposits it can be seen that the
WC nanoparticles are homogeneously dispersed in the Ni matrix.
This means that nickel ions from the electrolyte are adsorbed on
WC nanoparticles and then are reduced on the WC surface and
their deposition on the surface is totally uniformly. The SEM mor-
phology of Ni/nano-WC composite coating also reveals a reduction
of Ni crystallites grain size due to the presence of WC nanoparticles
reinforced compared with those of pure Ni coating prepared under
similar conditions. The same tendency of crystallite sizes reduction
was observed also by Gyftou et al. [4] for Ni/SiC deposit when it
was compared with pure Ni deposit. This crystallite sizes reduction
can be explained by the incorporation of WC nanoparticles at the
borders and the edges of the nickel crystallites due to their very
small size. The size of WC particles is so small that it is difficult
to clearly distinguish the interface between Ni matrix and WC par-
ticles. An additional argument that can sustain that the codeposit-
ed WC nanoparticles were uniformly distributed in the Ni matrix of
nanocomposite coating is that the Ni/nano-WC composite coating
shows more smoothed surface, uniform and compact in appear-
ance compared to that of pure Ni coating.
3.2. Chemical composition
The elemental composition of the coatings was carried out
using energy dispersive X-ray system (EDX), attached to the SEM.
In Fig. 4(a–c) are shown the SEM morphologies and their corre-
sponding EDX analyzes for the weight percentage (wt.%) determi-
nation of W element in the nanocomposite coating surface.
Thereby in Fig. 4(a) it is indicated the SEM surface morphology of
 L. Benea et al. / Materials and Design 65 (2015) 550–558
Fig. 3. SEM morphologies of (a) pure Ni coating and (b) Ni/nano-WC composite
coating, both prepared under the same conditions.
Fig. 4. SEM–EDX analyzes for wt.% determination of W element in the Ni/nano-WC composite coating surface: (a and b) – SEM surface morphology at different magnification
and (c) EDX elemental analyze of the entire surface corresponding to (a) SEM micrograph.
553
Ni/nano-WC composite coating and in Fig. 4(c) it is observed the
corresponding EDX elemental analyze collected from the entire
scan area of the samples. The incorporation percentage of WC into
Ni matrix was determined by transformation of W wt.% in molec-
ular mass of WC. The standard atomic weight of W element has a
value of 183.84. The weight percentage for W element included
into Ni matrix (Fig. 4(c)) as was determined by EDX analyses is
equal to 11.26 wt.%. Therefore the wt.% of WC compound in the
Ni/nano-WC composite coating has the value of 11.99, being
approximately equal to 12, percentage that is expected to improve
the properties of the coating.
In Fig. 4(b) is presented the SEM surface morphology of
Ni/nano-WC composite coating at higher magnification and the
corresponding tungsten wt.% value, collected by punctual analysis.
The wt.% of W element in the nanocomposite coating surface
extracted by punctual analysis (Fig. 4(b)) is equal to 13.50, thus
confirming once again the inclusion of WC nanoparticles which,
being very small, are difficult to see on SEM micrographs.
The EDX analyzes have proved that WC nanoparticles were suc-
cessfully incorporated into nanocomposite coating surface and
change the nickel matrix morphology as it was also demonstrated
by SEM micrographs, Fig. 3.
3.3. Nanohardness before fretting tests
Nanoindentation as a measurement technique for determining
mechanical properties near to interface can provide important data
for studies the deformation and fracture properties of composites
which experiencing wear.
The values of nanoidentation results, as indentation hardness
(H), Vickers (HV) nanohardness (Hv), Elastic modulus (E) and H/E
ratio for Ni/nano-WC composite coating and pure Ni coating
obtained under the same experimental conditions are indicated
in Table 1 as statistical average of 3 indentations.
The nanohardness testing of the obtained coatings were done in
order to get the values of hardness (H) and elastic modulus (E).
Hardness is commonly regarded to be a significant mechanical
property for evaluating wear resistance [22]. However, several
554 L. Benea et al. / Materials and Design 65 (2015) 550–558

Table 1
Nanoidentation results as hardness, elastic modulus and H/E ratio for Ni/nano-WC
composite and pure Ni coatings.

Type of coating Indentation Vickers Elastic H/E ratio

hardness (H) hardness modulus (GPa)
(GPa) (Hv) (GPa)
Pure Ni 3.07 230.41 181.87 0.0169
Ni/nano-WC composite 3.91 406.84 194.51 0.0201

authors have recognized that the ratio between the hardness and
the elastic modulus is a more adequate guideline for predicting
wear resistance than the hardness itself [23]. This H/E ratio is
related to the elastic strain to failure [22,23]. Leyland and Mat-
thews [23] have assumed that the most durable coatings can be
obtained if the elastic strain to failure has a high value and this
can be done by obtaining coatings with sufficiently high hardness
in order to resist at plastic deformation and simultaneously with a
low elastic modulus (similar to, or slightly below, that of the sub-
strate material).
The higher nanohardness value (Table 1) of Ni/nano-WC com-
posite coating compared with pure Ni coating can be accounted
by the incorporation of WC nanoparticles in the Ni matrix which
limits the growth of the Ni grains, results which were in good
accord with the observation on SEM morphologies. At the same
time this behavior can be explained by the increased yield stress
for smaller grain sizes according to the Hall–Petch equation [24]
and the increased relative contribution of the Orowan strengthen-
ing effect with decreasing size of particles [25]. The same observa-
tion was reported also by Mohajeri and his collaborators [17] for
pure Ni and Ni/nano-WC composite coatings. Also, they explained
that WC nanoparticles generate new locations of nucleation on
surface resulting in refinement of grains. Thus, the grain bound-
aries expand and hinder motion of dislocations; as a result, hard-
ness increases [17].
Maximum depth penetration of the indenter for pure Ni layer
has reached a value of 900 mN and for the composite layer of
Ni/nano-WC it reached 668 mN at the same applied normal force
of 50 mN. This demonstrates once again that the composite layer
of Ni/nano-WC has a higher hardness and resistance to wear than
pure Ni layer.

3.4. Fretting wear behavior in dry condition

The general purpose of applying coating to a surface for any tri-

bology based application is to impart both smoothness and hard-
ness to the surface so that friction and wear be reduced as much
as possible [26]. Friction is the resistance force encountered when
surfaces in contact move relative to each other. The forces ratio
between tangential frictional force (FT) and the applied normal
force (FN) is defined as the coefficient of friction (l) [27].
FT
l¼ ð1Þ
FN Fig. 5. Evolution of the friction coefficient of Ni/nano-WC composite and pure Ni
coatings during fretting tests performed in dry conditions at 1 Hz, 200 lm,
In Fig. 5(a–c) are presented the coefficients of friction moni- 10,000 cycles for the normal forces of: (a) 1 N, (b) 2 N and (c) 5 N.
tored in dry conditions as a function of normal forces of 1 N
(Fig. 5a), 2 N (Fig. 5b) and 5 N (Fig. 5c), at the fretting frequency
of 1 Hz, for number of cycles equal to 10,000 and 200 lm displace- nanoparticles, separated from matrix due to abrasion, act as solid
ment amplitude corresponding to pure Ni coating and Ni/WC lubricants between two wear surfaces. Also from Fig. 5(a–c) it
nanocomposite coating. can notice that, the friction coefficient of both pure Ni and
It can be see from Fig. 5(a–c) that, under dry conditions, the fric- Ni/nano-WC composite coatings decreases gradually with increas-
tion coefficient of Ni/nano-WC composite coatings is smaller than ing the normal force.
that of electrodeposited pure Ni coatings for all three normal forces
applied. For Ni/nano-WC composite coatings, this behavior can be 3.5. Fretting wear (tribocorrosion) behavior in wet conditions
assigned to the hard nano-scale reinforcements embedded in
nanocomposite coatings, which reduce the direct contact between Fig. 6(a–c) provides the coefficients of friction monitored in wet
metal matrix and abrasive surface. On other hand, the WC conditions as a function of normal forces of 1 N (Fig. 6a), 2 N
 L. Benea et al. / Materials and Design 65 (2015) 550–558
(Fig. 6b) and 5 N (Fig. 6c), at the fretting frequency of 1 Hz, for a
number of cycles equal to 10,000 and 200 lm displacement
amplitude corresponding to pure Ni coating and Ni/nano-WC com-
posite coating.
The Fig. 6(a–c) keeps the same general behavior which was
observed also for the dry conditions, namely that the friction coef-
ficient recorded under wet condition of Ni/nano-WC composite
coatings is smaller than that of pure Ni coatings for all three nor-
mal forces applied. For instance, the average value of friction coef-
ficient for Ni/nano-WC composite coating at the normal force of
Fig. 6. Evolution of the friction coefficient of Ni/nano-WC composite and pure Ni
coatings during fretting wear tests performed in wet conditions at 1 Hz, 200 lm,
10,000 cycles for the normal forces of: (a) 1 N, (b) 2 N and (c) 5 N.
555
5 N is equal to 0.204 and with 0.240 respectively for pure Ni
coating.
Also it can be seen in Fig. 6(a–c) that, under wet conditions, the
friction coefficient of both pure Ni and Ni/nano-WC composite
coatings decreases gradually with increasing the normal force.
For example in the case of Ni/nano-WC composite coating the coef-
ficient of friction has the average value of 0.23 for 2 N normal force
and 0.204 according to 5 N normal force.
Comparing the coefficients of friction in dry conditions with
those registered in wet conditions to the same applied normal
force, it is concluded that the latter have lower values, correspond-
ing to each system. The reason of decrease in coefficient of friction
may be the presence of electrolyte which may act as lubricant.
The open circuit potential (OCP) data recorded on the pure Ni
and Ni/nano-WC coatings before, during and after fretting tests in
the solution are shown in Fig. 7. The fretting tests where done at
the normal forces of: 1 N (Fig. 7a), 2 N (Fig. 7b) and 5 N (Fig. 7c),
at 1 Hz fretting frequency with displacement amplitude of
200 lm, for 10,000 cycles. In the time interval preceding the start-
ing of corrosion-wear fretting, a large increase of the open circuit
potential for both pure Ni and Ni/nano-WC composite coatings is
noticed. It can be observed also that before start of the fretting tests,
the potential of the samples is quite stable. Also should be men-
tioned that the potential measured before fretting tests of Ni/
nano-WC composite coatings is more ennobled than that of pure
Ni coatings, thus leading to a significant increase of anticorrosion
effect. This means that an ennoblement of the coating surface
occurs when WC nanoparticles are incorporated into the electrode-
posited nickel layer. According to Fig. 7(a), at the onset of fretting,
the potential of the pure Ni coatings drops suddenly to a more neg-
ative value, its leap being of around 0.15 V vs. Ag/AgCl (from 0.016
to 0.166 V vs. Ag/AgCl) for normal force of 1 N. Similar observa-
tions were made earlier by Ponthiaux et al. [16] for stainless steel
disk immersed in 0.5 M H2SO4, by Berradja et al. [28] for stainless
steel during sliding in Ringer’s solution and by Mardare et al. [29]
for Ti–6Al–4V alloy during sliding in bio-simulated environment.
The suddenly shift in the cathodic domain at the moment when
the normal force was loaded on the Ni/nano-WC composite coat-
ings surface took a much slower leap of 0.018 V vs. Ag/AgCl (from
0.046 to 0.028 V vs. Ag/AgCl) for 1 N normal force (Fig. 7a). This
potential sudden shift in the negative direction favors the damage
and partial or complete removal of the passive film induced by fret-
ting, suggesting an increase in its susceptibility for corrosion [16].
These observations indicate that pure Ni coatings exhibit more
cathodic values of the open circuit potential before and with the
onset of fretting than Ni/nano-WC composite coatings. This
improved behavior of nanocomposite coatings could be attributed
to the presence in the nickel matrix of WC nanoparticles.
From Fig. 7(a–c) it can also be seen that the open circuit poten-
tial drop increases with the normal force, for both studied systems
concerned, as was already revealed by Mardare et al. [29] for Ti–
6Al–4V alloy during sliding in bio-simulated environment. The
highest drop in potential for all applied forces is observed for pure
nickel as compared with Ni/nano-WC composite.
During fretting-corrosion, the potential fluctuates, these being
attributed to the depassivation and repassivation processes that
occur in the wear track area on the tested pure Ni and Ni/nano-
WC samples. For Ni/nano-WC composite coatings, the repassiva-
tion process is more pronounced even during fretting than that
of pure Ni coatings, as it can be seen on Fig 7(a), where open circuit
potential for Ni/nano-WC composite has a very small drop at
imposed applied force and reach the initial value before the end
of fretting cycles, once again suggesting the beneficial effect of
WC nanoparticles incorporated into Ni matrix.
At the end of the fretting -corrosion test, the potential of both
types of coatings studied exhibit an anodic shift, reaching again
556 L. Benea et al. / Materials and Design 65 (2015) 550–558

Fig. 7. Evolution of the open circuit potential recorded before, during and after
fretting tests of pure Ni and Ni/nano-WC composite coatings in the boric acid and
lithium hydroxide solution at 1 Hz, 200 lm, 10,000 cycles for the normal forces of:
(a) 1 N, (b) 2 N and (c) 5 N.

to its original values, indicating the progressive repassivation of

the worn surface. In the present study, after the fretting motion
is stopped, pure Ni coatings tends to reach the steady state poten-
tial before the onset of fretting, whereas nanostructured Ni/WC the
protective coatings go far beyond the steady state potential
reached before the onset of fretting.
Fig. 8. SEM micrographs of the entire wear tracks (a and c) and a zoom in the
central region of the wear tracks (b and d) of pure Ni coating (a and b), and Ni/nano-
WC composite coating (c and d) after reciprocating fretting tests in LiOH and H3BO3
solution. Fretting test parameters: 1 N, 1 Hz, 200 lm and 10,000 cycles.
 L. Benea et al. / Materials and Design 65 (2015) 550–558
3.6. Worn surface analysis
The scanning electron micrographs of the wear tracks and the
surrounding areas of pure Ni coating and Ni/nano-WC composite
coating after 10,000 fretting cycles by using a normal force of 1 N
in LiOH and H3BO3 solution are shown in Fig. 8(a) and (c) respec-
tively. The magnified views of the central region of the wear tracks
of pure Ni coating and Ni/nano-WC composite coating are shown
in Fig. 8(b and d) respectively.
Fig. 8(c and d) shows the surface of the Ni/nano-WC composite
coating with a smaller wear track without cracks than that of pure
Ni one (Fig. 8(a)). This last one has suffered severe damage due to
the ploughing action of the alumina ball and shows small cracks
and wears debris, Fig 8(b). From the SEM micrograph of the entire
wear track corresponding to Ni/nano-WC composite coating
(Fig. 8c) it can be seen that the damage suffered is insignificant,
practically took place only the flattening of the surface roughness.
From the high magnification micrographs, a high level of plastic
deformation was seen on the worn surface of the pure Ni coatings,
evidenced by microcracks and wears debris (Fig. 8b). In contrary
the amount of plastic deformation and scuffing wear in the fretting
was reduced for the Ni/nano-WC composite coating. The reduction
of plastic deformation corresponding to Ni/nano-WC composite
coating was related to the dispersion strengthening effect caused
by WC nanoparticles that impeded the motion of dislocations in
the metallic matrix of the composite coatings.
The wear tracks on both types of coatings had a dark gray to
black appearance and scratches parallel to the direction of motion
were detected, which are typical for abrasive wear as it was also
concluded for Ni/SiC composite [30].
Under dry and wet wear conditions the two types of coatings
show differences as far as the friction coefficients being smaller
for Ni/nano-WC composite. The friction coefficients recorded
under dry and wet condition of Ni/nano-WC composite coatings
prove the enhancement of surface properties compared to pure
Ni coatings. This could be attributed to the presence of WC nano-
particles into nickel matrix which impedes the damage of the
nickel oxides passive film formed above the pure nickel coating.
This conclusion was also stipulated for Ni/SiC nanostructured com-
posite coating [31].
The ennoblement of OCP corresponding to the Ni/nano-WC
composite coating surface may be related to the modification of
the structure of the crystalline Ni electrodeposits, caused by the
WC nanoparticle incorporation [32,33]. This is due the electro-
chemical properties of nickel deposits which are dependent on their
crystalline structures [33]. The decrease in the OCP with the onset
of fretting is more accentuated for the pure Ni coatings than that
of Ni/nano-WC composite coatings, and the best performance (most
positive OCP) was observed in the Ni/nano-WC composite coatings.
4. Conclusions
Ni/WC nanocomposite coatings with improved nanohardness
and enhanced resistance to wear in dry and wet conditions com-
pared with pure Ni coatings have been successfully obtained by
electro-codeposition of nano sized WC dispersed particles with
nickel. The obtained Ni/nano-WC coatings were comparatively
characterized to wear in dry and wet conditions. For wet condi-
tions it was selected a solution with LiOH and H3BO3 to simulate
the primary water of the PWRs.
– SEM–EDX analyzes proved that WC nanoparticles were success-
fully incorporated into Ni matrix. Presence of WC nanoparticles
in the nickel matrix transforms surface morphology from regu-
lar pyramidal to irregular global and changes the crystalliza-
tions of nickel matrix to smaller and thinner crystallites.
557
– By comparatively nanoidentation it was found that Ni/nano-WC
composite coatings exhibit improved nanohardness as com-
pared with pure nickel coatings.
– The friction coefficient of Ni/nano-WC composite coating is
smaller in both wet and dry conditions at all applied normal
forces as compared with pure nickel coatings, proving an
enhancement of fretting wear resistance.
– The open circuit potential measured before fretting tests of
Ni/nano-WC composite coatings is more ennobled than that of
pure Ni coatings, thus leading to a significant anticorrosion
effect of WC nanoparticles embedded into nickel matrix.
– The shift of potential in the cathodic domain with the onset of
fretting is smaller for Ni/nano-WC composite coatings than for
pure Ni coating, due to the presence of WC nanoparticles. For
Ni/nano-WC composite coatings, the repassivation process is
more pronounced even during fretting as compared with pure
Ni coatings.
– The dimension of the wear track corresponding to Ni/nano-WC
composite coating is smaller than that of the pure Ni one.
Over all conclusions is that WC nanoparticles have good effects
on Ni/nano-WC coatings revealing improved nanohardness and
enhanced resistance to wear in dry and wet conditions as com-
pared with pure nickel coating.
Acknowledgements
The investigations were financial supported by the research
projects IFA-CEA C2-02/(2012–2015) – NanoSurfCorr, PN II
702/30-04-2013 – CorBioMat and CPE– PN II 10/(2013–2015) –
HyBioElect. Also the preparation of this paper would not have been
possible without the support provided by the Bilateral Research
Agreement between Research (Competences) Centre Interfaces –
Tribocorrosion and Electrochemical Systems (CC–ITES) from Dun-
area de Jos University of Galati and Department of Metallurgy
and Materials Engineering (MTM) from Katholieke Universiteit
Leuven. The authors express their sincere thanks to technical staff
from Department of Metallurgy and Materials Engineering (MTM),
Katholieke Universiteit Leuven for giving the permission to do the
necessary research work, for the support offered and to use depart-
mental research equipments.
References
[1] Wang P, Cheng Y-L, Zhang Z. A study on the electrocodeposition processes and
properties of Ni–SiC nanocomposite coatings. J Coat Technol Res
2011;8:409–17.
[2] Hovestad A, Janssen LJJ. Electrochemical codeposition of inert particles in a
metallic matrix. J Appl Electrochem 1995;25:519–27.
[3] Jugović B, Stevanović J, Maksimović M. Electrochemically deposited Ni + WC
composite coatings obtained under constant and pulsating current regimes. J
Appl Electrochem 2004;34:175–9.
[4] Gyftou P, Pavlatou EA, Spyrellis N. Effect of pulse electrodeposition parameters
on the properties of Ni/nano-SiC composites. Appl Surf Sci 2008;254:
5910–6.
[5] Boonyongmaneerat Y, Saengkiettiyut K, Saenapitak S, Sangsuk S. Effects of WC
addition on structure and hardness of electrodeposited Ni–W. Surf Coat
Technol 2009;203:3590–4.
[6] Marinović V, Stevanović J, Jugović B, Maksimović M. Hydrogen evolution on Ni/
WC composite coatings. J Appl Electrochem 2006;36:1005–9.
[7] Yu SR, Liu Y, Li W, Liu JA, Yuan DS. The running-in tribological behavior of
nano-SiO2/Ni composite coatings. Compos Part B 2012;43:1070–6.
[8] Chen L, Wang L, Zeng Z, Xu T. Influence of pulse frequency on the
microstructure and wear resistance of electrodeposited Ni–Al2O3 composite
coatings. Surf Coat Technol 2006;201:599–605.
[9] Ciubotariu AC, Benea L, Lakatos-Varsanyi M, Dragan V. Electrochemical
impedance spectroscopy and corrosion behaviour of Al2O3–Ni nano
composite coatings. Electrochim Acta 2008;53:4557–63.
[10] Benea L. Electrodeposition and tribocorrosion behaviour of ZrO2–Ni composite
coatings. J Appl Electrochem 2009;39:1671–81.
558 L. Benea et al. / Materials and Design 65 (2015) 550–558
[11] Benea L, Wenger F, Ponthiaux P, Celis JP. Tribocorrosion behaviour of Ni–SiC
nano-structured composite coatings obtained by electrodeposition. Wear
2009;266:398–405.
[12] Benea L, Ciubotariu A, Sand W. Biofilm formation and corrosion resistance of
Ni/SiC nanocomposite layers. Int J Mater Res 2013;104:489–97.
[13] Bratu F, Benea L, Celis J-P. Tribocorrosion behaviour of Ni–SiC composite
coatings under lubricated conditions. Surf Coat Technol 2007;201:6940–6.
[14] Huang W, Zhao Y, Wang X. Preparing a high-particle-content Ni/diamond
composite coating with strong abrasive ability. Surf Coat Technol
2013;235:489–94.
[15] Wood RJK. Tribo-corrosion of coatings: a review. J Phys D: Appl Phys
2007;40:5502–21.
[16] Ponthiaux P, Wenger F, Drees D, Celis JP. Electrochemical techniques for
studying tribocorrosion processes. Wear 2004;256:459–68.
[17] Mohajeri S, Dolati A, Rezagholibeiki S. Electrodeposition of Ni/WC nano
composite in sulfate solution. Mater Chem Phys 2011;129:746–50.
[18] Dalfard VM. Effect of particle size of tungsten carbide on weight percent of
carbide in Ni–WC nano-composite. Int J Electrochem Sci 2012;7:3537–42.
[19] Wu Z, Chen J, Piao N, Yang M. Synthesis and passive property of
nanocomposite Ni–WC coating. Acta Metall Sin 2013;49:1185–90.
[20] Oliver WC, Pharr GM. Measurement of hardness and elastic modulus by
instrumented indentation: advances in understanding and refinements to
methodology. J Mater Res 2004;19:3–20.
[21] Ionescu C, Ponthiaux P, Abrudeanu M, Wenger F, Constantin F. A comparative
study on tribocorrosion of two Ni–Cr model alloys in solution of boric acid and
lithium hydroxide. Rev Chim (Bucharest) 2011;62:1077–84.
[22] González S, Pellicer E, Fornell J, Blanquer A, Barrios L, Ibáñez E, et al. Improved
mechanical performance and delayed corrosion phenomena in biodegradable
Mg–Zn–Ca alloys through Pd-alloying. J Mech Behav Biomed 2012;6:53–62.
[23] Leyland A, Matthews A. On the significance of the H/E ratio in wear control: a
nanocomposite coating approach to optimised tribological behaviour. Wear
2000;246:1–11.
[24] Carlton CE, Ferreira PJ. What is behind the inverse Hall–Petch effect in
nanocrystalline materials? Acta Mater 2007;55:3749–56.
[25] Zhang Z, Chen DL. Contribution of Orowan strengthening effect in particulate-
reinforced metal matrix nanocomposites. Mater Sci Eng A 2008;483–
484:148–52.
[26] Sahoo P, Das SK. Tribology of electroless nickel coatings – a review. Mater Des
2011;32:1760–75.
[27] Bonny K, De Baets P, Vleugels J, Huang S, Lauwers B. Dry reciprocating sliding
friction and wear response of WC–Ni cemented carbides. Tribol Lett
2008;31:199–209.
[28] Berradja A, Bratu F, Benea L, Willems G, Celis JP. Effect of sliding wear on
tribocorrosion behaviour of stainless steels in a Ringer’s solution. Wear
2006;261:987–93.
[29] Mardare E, Benea L, Celis J-P. Importance of applied normal loads on the
tribocorrosion behaviour of Ti–6Al–4V alloy in bio-simulated environment.
Optoelectron Adv Mater 2012;6:474–8.
[30] Gyftou P, Stroumbouli M, Pavlatou EA, Asimidis P, Spyrellis N. Tribological
study of Ni matrix composite coatings containing nano and micro SiC particles.
Electrochim Acta 2005;50:4544–50.
[31] Lekka M, Kouloumbi N, Gajo M, Bonora PL. Corrosion and wear resistant
electrodeposited composite coatings. Electrochim Acta 2005;50:4551–6.
[32] Pavlatou EA, Stroumbouli M, Gyftou P, Spyrellis N. Hardening effect induced by
incorporation of SiC particles in nickel electrodeposits. J Appl Electrochem
2006;36:385–94.
[33] Calderón JA, Henao JE, Gómez MA. Erosion–corrosion resistance of Ni composite
coatings with embedded SiC nanoparticles. Electrochim Acta 2014;124:190–8.