Surface & Coatings Technology 201 (2007) 4711 4717 www.elsevier.

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Codeposition of micro- and nano-sized SiC particles in the nickel matrix composite coatings obtained by electroplating
Hong-Kee Lee, Ho-Young Lee , Jun-Mi Jeon
Nano-Surface Technology Team, Division of Production Technology, Korea Institute of Industrial Technology, 7-47 Songdo-Dong, Yeonsu-Gu, Incheon 406-800, Republic of Korea Received 12 June 2006; accepted in revised form 4 October 2006 Available online 13 November 2006

Abstract Micro- and nano-sized SiC particles were codeposited with nickel by electrolytic plating from a nickel sulfamate bath and the effects of plating parameters such as pH of the plating bath, SiC content in the plating bath, and stirring speed on the deposition behaviors of NiSiC composite coating layers were studied. The result revealed that the micro-sized SiC particles are more negative than the nano-sized SiC particles in the Zeta potential. The codeposition of SiC can be increased by increasing the SiC content in the plating bath and the pH of the plating bath within the present experimental range. In case of micro-sized SiC particles, increasing stirring speed always lowered the codeposition of SiC. In case of nanosized SiC particles, the codeposition of SiC showed a maximum at the stirring speed of 100 rpm. The nano-sized SiC particles are more difficult to codeposit than the micro-sized SiC particles and showed rougher plated surface compared with the micro-sized SiC particles, which may be attributable to the agglomeration of nano-sized SiC particles in the plating bath. 2006 Published by Elsevier B.V.
Keywords: SiC; Nickel; Micro; Nano

1. Introduction The electrochemical deposition of finely dispersed secondphase hard particles in a metallic matrix has the advantages of easy maintainability, low working temperatures, low cost and gives the possibility to produce composite coatings with different combination of properties, by changing the electroplating conditions [1]. The embedded second-phase hard particles impart special properties to composite coatings [2]. Uniform dispersion of the second-phase hard particles leads to the improvement of the mechanical, trobological, anti-corrosion and anti-oxidation properties of the coatings [3,4]. It is known that metal-matrix composite coating layers using micro- and nano-sized particles has lead technological interest to the production of new composite materials with improved and well-controlled properties [4,5]. Particularly, NiSiC composites, due to their high Wear resistance, have been investigated to
Corresponding author. E-mail address: hlee@kitech.re.kr (H.-Y. Lee). 0257-8972/$ - see front matter 2006 Published by Elsevier B.V. doi:10.1016/j.surfcoat.2006.10.004

the greatest extent and successfully commercialized for the protection of friction parts, combustion engines and casting molds [4,6,7]. However, the reports on the effect of SiC particle size on the properties of electroplated NiSiC composites have been rare. Garcia et al. [8] have made NiSiC composite coating using SiC particles with three different sizes (5, 0.7 and 0.3 m) and investigated the sliding wear resistance of the deposited Ni SiC composite, but the smallest particle size is 0.3 m which seems more or less big size. With the increasing availability of nanoparticles, there is a growing interest in the electrolytic and electroless codeposition of nanoparticles. In the present work, micro- (23 m in diameter) and nanosized (4555 nm in diameter) SiC particles were employed to prepare nickel matrix composite coatings by electrolytic plating and the effects of plating parameters such as pH of the plating bath, SiC content in the plating bath, current density and stirring speed on the deposition behaviors of NiSiC composite coating layers were investigated. Prior to the electrolytic codeposition of SiC with nickel, Zeta potentials of the micro- and nano-sized SiC particles were measured with pH of the solution.

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H.-K. Lee et al. / Surface & Coatings Technology 201 (2007) 47114717 Table 2 Properties of SiC particles with size Particle Size 23 m 4555 nm Property Density 3.22 g/cm 3.217g/cm3
3

2. Experimental details The plating electrolyte was a nickel sulfamate bath of which the composition is shown in Table 1. The properties of SiC particles are shown in Table 2. Two types of SiC particles were employed to the electrolytic codeposition with nickel. The SiC particles (-SiC) with average size of 23 m in diameter were provided by Japan Pure Chemical Co. in Japan and the SiC particles (-SiC) with average size of 4555 nm in diameter were provided by N and A materials Inc. in USA. A steel plate for Hull cell test with dimension of 5 cm 3.5 cm 0.03 cm was used as a substrate with pre-treatment and a Ni plate (99.9% purity) with dimension of 5 cm 10 cm 0.3 cm was used as a cathode. Pretreatment has been conducted to eliminate Zn coating on steel plate (10 vol.% hydrochloric acid solution) and to activate surface (5 vol.% sulfuric acid). A scanning electron microscope (SEM) was used to investigate the surface and cross-sectional morphology of the coatings. Thickness of the coatings was measured directly from the SEM micrographs of the cross-section of coatings. The weight percentage of SiC in the coatings was determined using an energy dispersed X-ray micro-analyzer (EDX) coupled to the SEM. 2.1. Zeta potential Zeta potential is known to be the electrical potential that exists at the interface between a solid surface and its liquid medium, and a function of the surface charge of a particle, any adsorbed layer at the interface and the nature and composition of the surrounding medium in which the particle is suspended. The magnitude of the Zeta potential of the particles is a measure of this particle interaction, which means Zeta potential can be used to predict the long-term stability of a suspension. If the particles in a suspension have a large negative or positive Zeta potential then they will tend to repel each other and resist forming aggregates. However, if the particles have low Zeta potential values, i.e. close to zero, then there will be nothing to prevent the particles approaching each other and aggregating. The dividing line between stable and unstable suspensions is generally taken at either + 30 mVor 30 mV. Particles with Zeta potentials more positive than + 30 mV or more negative than 30 mV are normally considered stable [9]. Most materials when immersed in water exhibit a Zeta potential and the Zeta potential is affected by the pH, concentration of an additive or the ionic strength of the medium. The most important parameter that affects Zeta potential is the pH. Many chemically simple surfaces, such as a mineral oxide dispersed in a dilute salt solution, will show a common pattern when the pH is varied. As the pH increases by adding alkali, the
Table 1 Bath composition and plating condition for the electrolytic plating of nickel Bath composition Ni(NH2SO3)24H2O H3BO3 NiCl26H2O 500 g/ 40 g/ 3 g/ Plating condition Current density Temperature Time 15 A/dm2 50 C 30 min

Purity 99% 97.50%

Impurities Al, Ca, Fe, Cr, Mn, Na, Ni Si, Cl, C, O

surface will become more negative, or at least less positive and the Zeta potential will track this. If acid is added, ionization will cause the loss of hydroxyl ions which will make the surface more positive. By this simple manner, therefore, the materials are more positive at low pH and more negative at high pH. In Zeta potential vs. pH curve, there may be a point where the curve passes through zero potential called the iso-electric point. This is very important for practical purpose as it is normally the pH where the colloidal system is least stable [9]. Zeta potential was measured by ELS (Electrophoretic Light Scattering) Spectrophotometer (ELS-8000, Otsuka Electronics Co., Ltd. in Japan). The principle of determining Zeta potential is very simple. A controlled electric field is applied via electrodes immersed in a sample suspension and this causes the charged particles to move towards the electrode of opposite polarity. Viscous forces acting upon the moving particle tend to oppose this motion and equilibrium is rapidly established between the effects of the electrostatic attraction and the viscosity drag. The particle, therefore, reach a constant terminal velocity. Zeta potential is derived from measuring the mobility distribution of a dispersion of charged particles as they are subjected to an electric field. Mobility is defined as the velocity of a particle per electric field unit and is measured by applying an electric field to the dispersion of particles and measuring their average velocity. Depending on the concentration of ions in the diluent, either the Smoluchowski (for high ionic strengths) or Huckel (for low ionic strengths) equations are used to obtain the Zeta potential from the measured mobilities. Measuring Zeta potential using the ELS method is like this. Since ELS requires the use of heterodyned light, the scattered light must be properly mixed with a reference beam (split off from the incident light beam) prior to entering the detector. The software will begin a measurement by automatically adjusting the incident light intensity to optimize the mixing between the scattered light and the reference beam. Once this is completed, a reference power spectrum is measured while the electric field is off. Then the electric field is applied and another power spectrum is measured. The change in the frequency of the peak in this power spectrum when compared to the reference spectrum is the Doppler shift. The Doppler shift is used to calculate the average mobility. Using the Smoluchowski equation, the Zeta potential is determined. 3. Results and discussion 3.1. Zeta potential Zeta potential was measured prior to electro-codeposition and the results are shown in Fig. 1. In case of the SiC particles

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Fig. 1. Zeta-potential of micro- and nano-sized SiC particles with pH.

(-SiC) with average size of 23 m in diameter (type-A), the iso-electric point was measured to be around 3.0 in pH. In case of the SiC particles (-SiC) with average size of 4555 nm in diameter (type-B), the iso-electric point was measured to be around 7.0 in pH. It can be seen that the A-type SiC particles are more negative than the B-type SiC particles in the Zeta potential, indicating that the A-type SiC particles were easily adsorbed by the positive ions. Various measured Zeta-potentials of the SiC particles were reported in the literature [1012], and the surface charge of the SiC particles can be changed by adding various additives into the solutions [13,14]. 3.2. Effect of pH Electrolytic codeposition of SiC particles with nickel was carried out using a plating condition shown in Table 1. The plating bath was agitated by a mechanical stirrer at 75 rpm. The concentration of SiC particle in the plating bath was 50 g/l for type-A and 15 g/l for type-B. The effect of the pH of the plating bath on the deposition behavior of the NiSiC composite coating layer was investigated. Fig. 2 shows the variation of deposition rate and the codeposition of SiC with pH of the plating bath. In both cases, the deposition rate increased with increasing pH at the initial stage, showing a maximum and then decreased. On the other hand, the codeposition of SiC is different. In case of type-A the codeposition of SiC increased with increasing pH, but in case of type-B the codeposition of SiC increased with increasing pH at the initial stage, showing a maximum and then decreased. In case of type-A, the codeposition of SiC is lower than 10 wt.% in strong acid region (pH 2.5). When the pH of the plating bath increases, the codeposition of SiC increases until pH = 3.5. Above pH = 3.5, the codeposition of SiC increases a little. In case of type-B, the codeposition of SiC increases upto pH = 5.0. Above pH = 5.0, the codeposition of SiC decreased with increasing pH. The experiment was restricted to pH = 6.0 because the composite layer loses its surface brightness and cannot form a dense layer above pH = 6.0. The deposition behavior with pH can be explained by an electrophoresis phenomenon due to the formation of an ionic cloud around the SiC particle. Many theories have been

suggested for the dispersion of inert particles into metallic matrix including the transport of particle [15]: (1) convective diffusion, (2) electrophoresis, (3) adsorption and (4) mechanical entrapment. Electrophoresis is the induced motion of colloidal particles or molecules suspended in ionic solutions that result from the application of an electric field. The electrophoretic velocity is a function of the electrostatic forces on the surface charge, the electrostatic forces on their electric double layers, and the viscous drag associated with both the motion of the colloidal particles as well as the motion of the ionic cloud the colloidal particles [16]. It is known that most colloidal particles in aqueous solution are in charged state. The charge can arise from ionization of surface groups, chemical binding or physical adsorption of ions from the liquid medium. Consequently, a charged particle suspended in an electrolyte solution tends to be surrounded by an ionic cloud. It was reported that the surface charge of the SiC can adsorb Ni2+ ions and change the polarity of the SiC from negative to positive in an aqueous solution containing Ni2+ ions [11]. In the present experiment, the adsorption of nickel ions and protons in the plating bath on the SiC particle surface may occurs, which makes the surface charge of the SiC particle more positive. This accelerates the electrophretic movement of the SiC particles towards the cathode. According to the Zeta potential result shown in Fig. 1, the type-A SiC particles are

Fig. 2. Deposition rate and codeposition of SiC with pH of the plating bath; (a) is for type-A and (b) is for type-B.

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more negative than the type-B SiC particles, thus the amount of adsorbed nickel ions and protons are smaller for the type-B SiC particles than the type-A SiC particles. This indicates the size of the ionic cloud of the type-B SiC particles is smaller than that of the type-A SiC particles. According to the Stokes model, assuming the shape of the colloidal particle is sphere, the electrophoretic velocity (VE) in an electric field (E) can be expressed as: VE lE E q E 6kgr 1

Where E is the electrophoretic mobility, q is the charge of the particle, r is a radius of the particle, and is the viscosity of the suspension. The Stokes model informs that the particles with high q faster than the particles with low q in the electrophoretic velocity under that same condition. According to the Eq. (1), it is evident that the electrophoretic velocity of the type-A SiC particles is higher than that of the type-B SiC particles. This may cause higher deposition rate and codeposition of SiC for type-A SiC particles than for type-B SiC particles. In addition, according to the Zeta-potential result shown in Fig. 1, the Zeta-potential of the type-A SiC particles decreases with increasing pH. And as a result of it, the size of the ionic cloud the type-A SiC particles increases with increasing pH. Accordingly, the codeposition of type-A SiC particles increases with increasing pH. In case of type-B, the Zeta-potential decreases with increasing pH as shown in Fig. 2. Thus the size of the ionic cloud the type-B SiC particles also increases with increasing pH as in the case of type-A, and consequently the codeposition of type-B SiC particles increases with increasing pH. 3.3. Effect of SiC contents in plating bath Electrolytic codeposition of SiC particles with nickel was carried out using a plating condition shown in Table 1. The plating bath was agitated by a mechanical stirrer at 75 rpm and the initial pH of the plating bath was 4.0. The effect of the SiC content in the plating bath on the deposition behavior of the Ni SiC composite coating layer was investigated. Fig. 3 shows the influence of SiC content in the plating bath on the deposition rate and the codeposition of SiC. In case of type-A, the deposition rate and the codeposition of SiC increased with increasing SiC content in the plating bath at the initial stage. Both of them reached certain maxima and then decreased with increasing SiC content in the plating bath. It seems that the deposition rate is concerned with the codeposition of SiC in trend. The SiC content causing maximum codeposition of SiC and may correspond to steady state equilibrium, where the number of codepositing SiC particles equals that number SiC particles approaching the cathode surface. Above the SiC content corresponding maximum codeposition of SiC, suspended SiC particles may agglomerate in the plating bath. Accordingly, the decreasing trend of incorporation of SiC particles into the nickel

matrix was observed. A similar trend has been reported elsewhere: at high SiC content in the plating bath, the agglomerates themselves will be resistant to incorporate into the nickel matrix and shield the surface of the cathode from the flux of incoming SiC particles [17]. In case of type-B, the codeposition of SiC particles with the nickel matrix increased up to around 5 g/l of SiC content in the plating bath and the deposition rate appears to be related to the codeposition of SiC in trend. Beyond 5 g/l of SiC content in the plating bath, the SiC particle codeposition hardly increased. This increasing trend might be due to the increase in the number of approaching SiC particle with the increasing SiC content in the plating bath. Only those particles that come to cling to the cathode surface for a sufficient period of time might be successfully incorporated into the nickel matrix. Therefore, the entrapment of the SiC particles into the growing nickel matrix depends on both the rate of SiC particles approaching to the cathode surface and the rate of nickel deposition. Although the number of approaching SiC particles to the cathode surface increases with the increasing SiC content in the plating bath, the capturing capacity of the growing metal remains virtually the same. Consequently, this is the reason for limited SiC codeposition beyond 5 g/l [18]. A similar trend for codeposition of hydrophilic silica with aluminum was reported previously [19,20].

Fig. 3. Deposition rate and codeposition of SiC with SiC content in the plating bath; (a) is for type-A and (b) is for type-B.

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et al. [25] quantitatively predicted the correlation of the concentration of PE particles engulfed in copper matrix on a rotational disc electrode based on trajectory analysis. According to their model, the quantity required to codeposit 5 m particles was calculated to be 10 times smaller than that of 20 m particles. 3.4. Effect of stirring speed Electrolytic codeposition of SiC particles with nickel was carried out using a plating condition shown in Table 1. The initial pH of the plating bath was 4.0. The concentration of SiC particle in the plating bath was 50 g/l for type-A and 15 g/l for type-B. The effect of stirring speed on the deposition behavior of the NiSiC composite coating layer was investigated and the results are shown in Fig. 4. The deposition rate increased with increasing stirring speed, showing a maximum, and then decreased for both type-A and type-B cases. The trend of deposition rate of type-A and type-B may be closely related to the codeposition of SiC and the deposition rate of nickel. The deposition rate of type-A is higher

Fig. 4. Deposition rate and codeposition of SiC with stirring speed; (a) is for type-A and (b) is for type-B.

It was reported that the codeposition of SiC particles smaller than 100 nm were more difficult than that of 0.8 m [21], and it was confirmed later that the smaller the particle size, the more difficult the codepositing the particle [22]. The more the SiC particle content in the plating bath, the higher the viscosity of the plating bath. Therefore, the experiment was restricted to the SiC content in the plating bath =50 g/l for type-B. Considering deposition rate at 50 g/l of the SiC content in the plating bath, type-A is about 85 m/30 min and type-B is about 71 m/30 min. This is mainly due to the difference in the codeposition of SiC particles caused by different electrophoresis rate. As mentioned before, the adsorption of nickel ions and protons in the plating bath on the SiC particle surface occurs, which forms the ionic cloud around the SiC particles. The size of the ionic cloud affects the electrophretic behavior, i.e. the more adsorption of nickel ions and protons, the faster the electrophoresis rate. There has been much research showing that the reduction of particle size will decrease the codeposition of the particles [23]. Maurin and Lavanant [24] showed that the concentration of 0.1 m of SiC powder incorporation in rotating disc experiments in a nickel sulfate solution was less than 0.7 mass% which was closed to the detection threshold of EDX analysis. On the contrary, the concentration can reach 2 mass% with SiC in size of 0.8 m and 5 mass% with 2.8 m. Fransaer

Fig. 5. SEM images of NiSiC composite coating layer formed by using type-A SiC particle; (a) top view and (b) cross-section view.

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than that of type-B, which may be due to higher codeposition of SiC. In case of type-A, the codeposition of SiC decreased with increasing stirring speed. However, in case of type-B, the codeposition of SiC increased, showing a maximum, and then decreased with increasing stirring speed. These may result from hydrodynamic effect and particle characteristics. The reason for the decreasing trend of the codeposition of SiC with increasing stirring speed in type-A case can be explained as follows. High stirring speed gives rise to high impinging velocity of the SiC particles towards the cathode, and high impinging velocity does not provide SiC particles with sufficient time to be fixed on the cathode, causing bouncing off. Hence the probability of incorporating SiC particles into the nickel matrix decreases with increasing stirring speed. In case of type-B, since it is the nano-sized SiC particle, the particles are prone to agglomerate together [26]. At very low stirring speed, the stirring energy is so weak to reduce the agglomerate to powder. It was observed during the experiment that the typeB SiC particles showed strong tendency to settle to the bottom of the plating bath at very low stirring speed. As the stirring speed increases, the stirring speed becomes strong enough to float the type-B SiC particles. So the codeposition of SiC

increases as the stirring speed increases up to a certain stirring speed. As the stirring speed increases more, high impinging velocity of the SiC particles towards the cathode is induced. Thus the probability of incorporating SiC particles into the nickel matrix decreases with increasing stirring speed as in the case of type-A. 3.5. Morphology Electrolytic codeposition of SiC particles with nickel was carried out using a plating condition shown in Table 1. The plating bath was agitated by a mechanical stirrer at 75 rpm and the initial pH of the plating bath was 4.0. The concentration of SiC particle in the plating bath was 50 g/l for type-A and 15 g/l for type-B. The surface and cross-section morphology were investigated using SEM and are shown in Fig. 5 (type-A) and Fig. 6 (type-B). The surface images of type-A (Fig. 5(a)) shows that the SiC particles are uniformly distributed on the composite coating layer. However, the cross-section view of type-A (Fig. 5(b)) shows that the SiC particles are not uniformly distributed along the surface normal direction, i.e. the codeposition of SiC is low near the substrate and high nears the surface of the composite coating layer. This is mainly due to preferential deposition of nickel during the initial stage of electrolytic plating without incorporating SiC particles. The surface images of type-B (Fig. 6(a)) shows that the SiC particles are not uniformly distributed on the composite coating layer and agglomerated. The cross-section view of type-B (Fig. 6(b)) also shows that the agglomerated SiC particles and rough surface. The rough surface may be attributable to the agglomeration trend of nano-sized SiC particles. Some researchers studied codeposition of nano-sized particles by electrolytic deposition and found that there is a strong agglomeration trend among nanoparticles due to their high activity [26]. Once the nano-sized particles are not dispersed well within the plating bath, the nano-sized particles are apt to be incorporate into metal matrix as aggregates. This triggers rough surface and the weak mechanical performance of the coatings [27]. 4. Conclusions Micro- and nano-sized SiC particles were codeposited with nickel by electrolytic plating from a nickel sulfamate bath and the effects of plating parameters such as pH of the plating bath, SiC content in the plating bath, current density and stirring speed on the deposition behaviors of NiSiC composite coating layers were studied. The following conclusions are derived from the present study. 1. The micro-sized SiC particles are more negative than the nano-sized SiC particles in the Zeta potential. 2. The codeposition of SiC can be increased by increasing the SiC content in the plating bath and the pH of the plating bath within the present experimental range. 3. Increasing stirring speed always lowered the codeposition of SiC for micro-sized SiC particles. On the other hand, the

Fig. 6. SEM images of NiSiC composite coating layer formed by using type-B SiC particle; (a) top view and (b) cross-section view.

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codeposition of SiC showed a maximum at the stirring speed of 100 rpm in case of nano-sized SiC particles. 4. The nano-sized SiC particles are more difficult to codeposit than the micro-sized SiC particles and showed rougher plated surface compared with the micro-sized SiC particles, which may be attributable to the agglomeration of nanosized SiC particles in the plating bath. 5. The codeposition behavior is influenced by the SiC particle size. Consequently, the choice of particle size and proper plating conditions could lead to the production of composite deposits with enhanced properties. References
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