a r t i c l e
i n f o
Article history:
Received 6 June 2014
Accepted 19 September 2014
Available online 2 October 2014
Keywords:
Ni/WC nanocomposite coating
Nanohardness
Fretting wear
Tribocorrosion
Friction coefcient
a b s t r a c t
The fretting and wear behaviors of Ni/nano-WC composite coatings were studied by considering the
effect of fretting frequency of 1 Hz during 10,000 cycles, at different applied loads in dry or wet conditions. The studies were performed on a ball-on-disk tribometer and the results were compared with pure
Ni coating. The nanohardness of pure Ni and Ni/nano-WC composite coatings was tested by nanoindentation technique. To evaluate the wet wear (tribocorrosion) behavior the open circuit potential (OCP) was
measured before, during and after the fretting tests at room temperature in the solution that simulates
the primary water circuit of Pressurized Water Reactors (PWRs). The results show that Ni/nano-WC composite coatings exhibited a low friction coefcient, high nanohardness and wear resistance compared
with pure Ni coatings under similar experimental conditions. Ni/nano-WC composite coatings were
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 dispersive spectroscopy (EDX) respectively.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
The development of new engineering process imposes metallic
materials with improved surface properties. Coatings obtained by
nickel only may not meet these requirements. Therefore researchers attention was directed to the development of composite materials 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 promote a good adhesion to the metal surface intended to be coated.
The dispersed phases used in electro-codeposition process are considered 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
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2. Experimental procedures
The wear tests in dry and wet conditions of Ni/nano-WC composite coatings and pure Ni coatings were performed on reciprocating 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 simulate 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 conventional three-electrode cell composed of: working electrode pure
Ni coating and Ni/nano-WC composite coatings, reference electrode 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,
coefcient 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.
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Fig. 1. Schematic representation of the electro-codeposition process: (a) electrolytic cell with anode, cathode and plating solution; (b) SEM surface micrograph of Ni/nanoWC composite obtained; (c) SEM micrograph of Ni/nano-WC coating in cross section showing a good adherence to stainless steel support; (d) SEMEDX spectrum of Ni/nanoWC 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 examined 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 electron microscopy (SEM). Fig. 3(a and b) shows the SEM morphologies 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 constituted 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 morphology of Ni/nano-WC composite coating also reveals a reduction
of Ni crystallites grain size due to the presence of WC nanoparticles
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Fig. 3. SEM morphologies of (a) pure Ni coating and (b) Ni/nano-WC composite
coating, both prepared under the same conditions.
Fig. 4. SEMEDX analyzes for wt.% determination of W element in the Ni/nano-WC composite coating surface: (a and b) SEM surface morphology at different magnication
and (c) EDX elemental analyze of the entire surface corresponding to (a) SEM micrograph.
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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
hardness (H)
(GPa)
Vickers
hardness
(Hv)
Elastic
modulus
(GPa)
H/E ratio
(GPa)
Pure Ni
Ni/nano-WC composite
3.07
3.91
230.41
406.84
181.87
194.51
0.0169
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 Matthews [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 sufciently high hardness
in order to resist at plastic deformation and simultaneously with a
low elastic modulus (similar to, or slightly below, that of the substrate material).
The higher nanohardness value (Table 1) of Ni/nano-WC composite 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 HallPetch equation [24]
and the increased relative contribution of the Orowan strengthening effect with decreasing size of particles [25]. The same observation 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 renement of grains. Thus, the grain boundaries expand and hinder motion of dislocations; as a result, hardness 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 tribology based application is to impart both smoothness and hardness 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 dened as the coefcient of friction (l) [27].
FT
FN
In Fig. 5(ac) are presented the coefcients of friction monitored 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 displacement amplitude corresponding to pure Ni coating and Ni/WC
nanocomposite coating.
It can be see from Fig. 5(ac) that, under dry conditions, the friction coefcient of Ni/nano-WC composite coatings is smaller than
that of electrodeposited pure Ni coatings for all three normal forces
applied. For Ni/nano-WC composite coatings, this behavior can be
assigned to the hard nano-scale reinforcements embedded in
nanocomposite coatings, which reduce the direct contact between
metal matrix and abrasive surface. On other hand, the WC
(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 composite coating.
The Fig. 6(ac) keeps the same general behavior which was
observed also for the dry conditions, namely that the friction coefcient recorded under wet condition of Ni/nano-WC composite
coatings is smaller than that of pure Ni coatings for all three normal forces applied. For instance, the average value of friction coefcient for Ni/nano-WC composite coating at the normal force of
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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.
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/nanoWC 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.
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Acknowledgements
The investigations were nancial supported by the research
projects IFA-CEA C2-02/(20122015) NanoSurfCorr, PN II
702/30-04-2013 CorBioMat and CPE PN II 10/(20132015)
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 (CCITES) from Dunarea 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 departmental research equipments.
References
[1] Wang P, Cheng Y-L, Zhang Z. A study on the electrocodeposition processes and
properties of NiSiC nanocomposite coatings. J Coat Technol Res
2011;8:40917.
[2] Hovestad A, Janssen LJJ. Electrochemical codeposition of inert particles in a
metallic matrix. J Appl Electrochem 1995;25:51927.
[3] Jugovic B, Stevanovic J, Maksimovic M. Electrochemically deposited Ni + WC
composite coatings obtained under constant and pulsating current regimes. J
Appl Electrochem 2004;34:1759.
[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:
59106.
[5] Boonyongmaneerat Y, Saengkiettiyut K, Saenapitak S, Sangsuk S. Effects of WC
addition on structure and hardness of electrodeposited NiW. Surf Coat
Technol 2009;203:35904.
[6] Marinovic V, Stevanovic J, Jugovic B, Maksimovic M. Hydrogen evolution on Ni/
WC composite coatings. J Appl Electrochem 2006;36:10059.
[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;43:10706.
[8] Chen L, Wang L, Zeng Z, Xu T. Inuence of pulse frequency on the
microstructure and wear resistance of electrodeposited NiAl2O3 composite
coatings. Surf Coat Technol 2006;201:599605.
[9] Ciubotariu AC, Benea L, Lakatos-Varsanyi M, Dragan V. Electrochemical
impedance spectroscopy and corrosion behaviour of Al2O3Ni nano
composite coatings. Electrochim Acta 2008;53:455763.
[10] Benea L. Electrodeposition and tribocorrosion behaviour of ZrO2Ni composite
coatings. J Appl Electrochem 2009;39:167181.
558
[23] Leyland A, Matthews A. On the signicance of the H/E ratio in wear control: a
nanocomposite coating approach to optimised tribological behaviour. Wear
2000;246:111.
[24] Carlton CE, Ferreira PJ. What is behind the inverse HallPetch effect in
nanocrystalline materials? Acta Mater 2007;55:374956.
[25] Zhang Z, Chen DL. Contribution of Orowan strengthening effect in particulatereinforced metal matrix nanocomposites. Mater Sci Eng A 2008;483
484:14852.
[26] Sahoo P, Das SK. Tribology of electroless nickel coatings a review. Mater Des
2011;32:176075.
[27] Bonny K, De Baets P, Vleugels J, Huang S, Lauwers B. Dry reciprocating sliding
friction and wear response of WCNi cemented carbides. Tribol Lett
2008;31:199209.
[28] Berradja A, Bratu F, Benea L, Willems G, Celis JP. Effect of sliding wear on
tribocorrosion behaviour of stainless steels in a Ringers solution. Wear
2006;261:98793.
[29] Mardare E, Benea L, Celis J-P. Importance of applied normal loads on the
tribocorrosion behaviour of Ti6Al4V alloy in bio-simulated environment.
Optoelectron Adv Mater 2012;6:4748.
[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;50:454450.
[31] Lekka M, Kouloumbi N, Gajo M, Bonora PL. Corrosion and wear resistant
electrodeposited composite coatings. Electrochim Acta 2005;50:45516.
[32] Pavlatou EA, Stroumbouli M, Gyftou P, Spyrellis N. Hardening effect induced by
incorporation of SiC particles in nickel electrodeposits. J Appl Electrochem
2006;36:38594.
[33] Caldern JA, Henao JE, Gmez MA. Erosioncorrosion resistance of Ni composite
coatings with embedded SiC nanoparticles. Electrochim Acta 2014;124:1908.