Surface & Coatings Technology 205 (2011) 34483454

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Electrodeposition and characterization of nano-structured NiSiC composite lms

C. Cai a,b, X.B. Zhu b,c, G.Q. Zheng c, Y.N. Yuan b, X.Q. Huang b,d, F.H. Cao b, J.F. Yang a, Z. Zhang b,
a

State Key Laboratory for Mechanical Behavior of Materials, Xi'an Jiaotong University, Xi'an 710049, PR China Department of Chemistry, Yuquan Campus, Zhejiang University, Hangzhou 310027, PR China c College of Chemical Engineering and Material Science, Zhejiang University of Technology, Hangzhou 310014, PR China d Wuhan Iron & Steel Corp., Wuhan 410080, PR China
b

a r t i c l e

i n f o

a b s t r a c t
NiSiC nano-composite coating, which simultaneously composed of both nanocrystalline consecutive Ni matrix and dispersed inert SiC nano-particles, has been fabricated by ultrasonic electroplating technique from a modied Watts bath containing SiC nano-particles. The inuence of mechanical stirring and ultrasonication on the surface morphology of the nanocrystalline NiSiC nano-composite lm has also been investigated. The surface morphology, microstructure, anti-corrosion property and electrocatalytic activity for hydrogen evolution of the obtained nanocrystalline NiSiC nano-composite lm, are characterized using scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS) system, atomic force microscopy (AFM), transmission electron microscope (TEM), X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS) techniques. The results nd that, mechanical stirring mainly prevents the sedimentation of the inert particles suspended in solutions, while ultrasonication mainly prevents the particles agglomeration. In the case of only mechanical stirring to disperse the SiC nano-particles, the composite surface is cauliower alike. While in the case of both mechanical stirring and ultrasonication, the obtained NiSiC composite lm is much smoother and composes of particles with the mean diameter of 42.9 nm, and SiC particles are uniformly dispersed into Ni matrix. Meanwhile, the results obtained by polarization curves and EIS methods show that, when compared with the traditional polycrystalline Ni lm, the obtained NiSiC nano-composite lm exhibits the enhanced corrosion resistance in NaCl solutions, possesses much higher electrocatalytic activity for hydrogen evolution in KOH solutions. 2010 Elsevier B.V. All rights reserved.

Article history: Received 3 November 2009 Accepted in revised form 1 December 2010 Available online 9 December 2010 Keywords: NiSiC nano-composite lm Eletrodeposition Corrosion resistance Hydrogen evolution

1. Introduction Composite electrodeposition technology is a method to obtain functional composite coatings by adding insoluble solid particles to the electrolyte. These coatings typically contain micrometer- or nanometer-sized ceramic particles (e.g. SiC [1], TiN [2], SiO2 [3], TiO2 [4]), in an electrodeposited matrix such as nickel. The composite coatings have been extensively studied owing to their wide application in surface engineering. Previous works showed that, when compared to pure metal coatings, nano-structured composite coatings usually exhibit enhanced mechanical, magnetic and optical non-linearity properties [5]. The improvement of these properties depends mainly on the nature, amount and size of the particles, which co-deposited in the metallic matrix. For example, as a hardness covalent bond compound, SiC is used as additive particle in wear resistance coatings, e.g. NiSiC in car engines. For conventional NiSiC composite, the dimension of dispersed SiC particles is usually in the micro-range, and a lot of research has been

Corresponding author. Tel.: +86 571 85615190. E-mail address: eaglezzy@zjuem.zju.edu.cn (Z. Zhang). 0257-8972/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2010.12.002

carried out about the inuences of electroplating technological parameters on their properties and co-deposition process [612]. Meanwhile, because of the strong agglomeration trend between the nano-particles, most of the reported nickel-base nano-composite lms are not simultaneously composed of both the nanocrystalline consecutive Ni matrix and the dispersed inert SiC nano-particles actually. Owing to the superiority of nano-composite lm, ultrasonication was used to disperse the nano-particles during electrodeposition [13,14]. Nowadays, numerous works have been developed for hydrogen generation from water electrolysis [15,16], and the most widely studied electrode material is nickel, its alloys and compound. Nickel exhibits a high electrocatalytic activity towards HER (hydrogen evolution reaction) [17] and tremendous efforts have been made to enhance the electrocatalytic HER activity of Ni and Ni-based electrodes by increasing the surface area or by increasing the intrinsic activity of the material using alloys or composites [1822]. However, little literatures have documented the catalytic hydrogen characteristics of nanocrystalline NiSiC composite lms in alkaline solutions. In this paper, the NiSiC nano-composite lms (both the consecutive matrix and dispersed phase are composed of particles in the nanometer range) with an average particle size of 42.9 nm have been

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prepared by ultrasonic electrodeposition. The surface morphology, corrosion resistance in 3.5 wt.% (mass fraction, hereinafter) NaCl solutions, and hydrogen evolution activity in 30 wt.% KOH solutions of the NiSiC nano-composite lms were investigated. For comparison, the pure Ni lms have also been prepared under the same electroplating conditions but without the addition of the nano-sized SiC ceramic particles. 2. Experimental 2.1. Preparation of NiSiC nano-composite lm The compositions of the solution and operating parameters for electrodeposition are shown in Table 1. To solve the agglomeration problem, SiC nano-particles (mean diameter 40 nm, Alfa, Beijing) were rstly chemically modied with 0.1 g/L sodium dodecyl-glycol prior to their addition into electroplating solution [23]. Analytical reagents and double-distilled water were used to prepare the plating solution. Before deposition, the electrolyte was stirred by ultrasonication for 24 h to ensure a good dispersion. A double-electrode cell was utilized to carry out electroplating experiments. Cathode, made of pure copper with an exposed area of 0.50 cm2, was positioned in vertical plane with anode. A large bright platinum foil was used as the anode. The distance between cathode and anode was xed at 4 cm. Schematic illustration of the electrochemical cell for deposition is shown in Fig. 1. The platinum foil was xed to make sure that it remained stable during the intensive stirring of the bath solutions. Prior to plating, the copper cathode was polished with emery papers and velvet, rinsed in double-distilled water and acetone. The electrolyte was stirred by mechanical impeller or ultrasonication in a couple of mechanical impeller while electroplating in order to prevent particles sedimentation. For comparison, nickel lms were also deposited with the same electroplating conditions but without addition of SiC nano-particles. The surface morphology of the composite coatings was investigated using a scanning electron microscopy (SEM, HIAACHIS-4700 for Fig. 2, SIRION for Fig. 3). The microstructure was observed by an atomic force microscopy (AFM, SPI3800N) and an transmission electron microscope (TEM, JEM-2010). The composition of the composite lms was analyzed by energy dispersive spectroscopy (EDS) system attached to the TEM. The crystal property was evaluated by X-ray diffraction (XRD, D8 Advance Bruker). 2.2. Electrochemical characterization of the corrosion and catalyzing properties of NiSiC nano-composite lms The electrochemical measurements were performed in a threeelectrode cell in the solutions containing 3.5 wt.% NaCl (pH 7, adjusted by diluted HCl and NaOH) and 30 wt.% KOH respectively at 25 C. A saturated calomel electrode (SCE) coupled with a Luggin
Table 1 Operating parameters for NiSiC nano-composite electroplating. Deposition parameters NiSO46H2O NiCl26H2O H3BO3 SiC Sodium dodecyl-glycol 1,4-butynediol Para toluene sulfonamide pH Temperature Current density Stirring speed Plating time Amount 100 g/L 40 g/L 30 g/L 6 g/L 0.1 g/L 0.4 g/L 0.8 g/L 4.5 40 C 10 mA/cm2 1000 rpm 30 min Fig. 1. Schematic illustration of electrochemical cell to obtain deposition.

capillary was used as the reference electrode and a large bright platinum foil as the auxiliary electrode. The corrosion resistance and hydrogen evolution properties of the obtained NiSiC nano-composite lms were evaluated by the polarization measurement and electrochemical impedance spectroscopy (EIS). The polarization measurements were performed using the electrochemical workstation (CH I660A, China). The Tafel curves were recorded by sweeping the potential from 0.45 to 1.20 V versus EOCP (open circuit potential) in neutral NaCl solutions at a scan rate of 0.001 V/s for corrosion characterization, and from EOCP to the potential more negative than 2.0 V at a scan rate of 10 mV/s for hydrogen evolution characterization. The EIS measurements were conducted in a frequency range from 60 k to 0.01 Hz with 10 mV sinusoidal signal amplitude using an impedance measurement unit (IM 6e, Australia). Each experiment was repeated at least three times to verify the reproducibility of the results. The repeatability of the

Fig. 2. Surface morphologies of composite lms prepared under different conditions: (a) mechanical dispersion and (b) mechanical and ultrasonication dispersion.

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number of nickel crystal nucleation (due to their polarization effects), and inhibit the growth rate of the already formed nickel crystal grains (due to their special impeding effects) [23]. The above reasons result in different surface morphology of Ni and NiSiC nano-composite lms.

3.2. Characterizations of the obtained NiSiC nano-composite lm The obtained NiSiC nano-composites are much hard (ca. 580 HV), possess much smooth surface with silvery white luster visible to the naked eye, and show good adherence to the copper substrates (the deposits are difcult to be removed by abrasive paper or le). To analyze the microstructure of the NiSiC nano-composite lm, especially the size of the composite grains, the lms are rstly observed by AFM (Fig. 4) and XRD (Fig. 5). Fig. 4 clearly indicates that the composite grains (including SiC nano-particles if they indeed exist in the lm) are uniformly distributed in the nanometer range, which can also be demonstrated by XRD technique (Fig. 5) by using Scherrer equation (the calculated nickel grain diameter is ca. 42.9 nm in average). The root mean square roughness of the nano-composite obtained by AFM is ca. 7.6 nm. In Fig. 5, the diffraction peaks of the copper substrate are also visible, which may be attributed to the fact that Pt but sacricial nickel was used as anode when performing electroplating. Generally, under the same electroplating conditions, sacricial nickel anode can make the deposit much thicker than the chemically stable Pt anode.

Fig. 3. SEM surface morphology of Ni lm.

results was judged according to the shape of the identical samples, and the value differences (for example, EOCP and corrosion current for polarization measurements, while lm/charge transfer resistance and CPE for EIS measurements) between Ni lm and NiSiC nanocomposite lm. In this paper, the reported plots are those with the middle results, and the scatter of all measured results was less than 100 20.

3. Results and discussion 3.1. The inuence of ultrasonication on NiSiC nano-composite lms Fig. 2(a) and (b) are the surface morphologies of composite lms prepared by mechanical stirring, both mechanical stirring and ultrasonication dispersion, respectively. The gure reveals that after dispersed only by mechanical stirring, the lm surface is cauliower alike and the SiC nano-particles (if they indeed exist in the lm) are not dispersed well and conglobe obviously, whereas after dispersed by both the mechanical stirring and ultrasonication dispersion, the lm surface is much more smooth and the particles are welldistributed. Therefore, it can be inferred that mechanical stirring mainly prevents the particles sedimentation, while ultrasonication mainly prevents the particles agglomeration. Fig. 3 shows the surface morphology of Ni lm obtained in the same operating conditions but without addition of SiC nano-particles in the electroplating bath. Compare Figs. 2 and 3, it can be concluded that the nano-particles can destroy the preferential growth of nickel crystals, which is characterized by the linear ravines or trenches (Fig. 3), and rene the crystal grains remarkably. Yeh S.H. et al. [24] took the stirring effect into account and put forward a so-called stirring model. According to Yeh's model, the transmission process of the particles into the cathode is the control process of composite electrodeposition. For mechanical dispersion, it involves agitation to suspend particles in the electrolyte, but which is less effective once the particles are in suspension (on the other words, it cannot prevent their agglomeration). The reason for this is that the gravitation sediments the larger suspended SiC nanoparticles (or particle groups), which makes the transmission process of the SiC particle groups more difcult and synchronously decreases their adsorption onto electrode surface more effectively. In comparison, ultrasonication not only prevents the particles sedimentation, but also shatters the aggregated particle groups into smaller parts due to its high-pressure waves and violent vibrations. Consequently, ultrasonication leads particles to further homogenization on a microscopic level [2] and makes the transmission process of the well-dispersed SiC particles much easier. Meanwhile, the SiC nano-particles dispersed in the composite coatings increase the

Fig. 4. AFM image of NiSiC nano-composite lm.

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1400
Ni (111)

1200

800 600 400 200 0 30

Cu (111)

1000

40

50

60

70

80

2-Thata(degree)
Fig. 5. XRD pattern of the obtained NiSiC nano-composite lm.

Suppose the added SiC nano-particles are truly entrapped into the obtained composite, then it can be inferred that the incorporated SiC nano-particles modify the surface to particulate-like crystals (Fig. 4), and result in that both the consecutive nickel matrix and dispersed SiC

phase are composed of particles in the nanometer range, i.e. the obtained NiSiC composites possess the nanostructure. However, it is difcult to distinguish the dispersed SiC nanoparticles from the consecutive Ni crystal matrix from Fig. 4. Fig. 5 also reveals nickel diffraction peaks only, which seems difcult to demonstrate that SiC is included in the lm (if they indeed exist in the lm). For this reason, the microstructure of samples is further characterized by TEM (Fig. 6). Fig. 6(a) shows the bright-eld TEM micrograph of NiSiC nanocomposite lm. It can be seen that the dark SiC nano-particles (pointed by arrow) dispersed well into the nickel matrix (white), and few agglomeration phenomenon can be observed. The mean SiC content in the composite lm is ca. 0.98 wt.% as determined by EDS, while the dark part pointed by arrow (Fig. 6(a)) possesses much higher SiC content (ca. 14.80 wt.%). The selected-area electron diffraction (SAD) pattern of the same sample is shown in Fig. 6(c), where the arrow-pointed (220) feeble diffraction rings that corresponds to the SiC crystal parameter, is isolated from the visible Ni crystal parameter with (111), (200), (311), and (400) diffraction rings. Meanwhile, the element distributing map of Si (white points) of NiSiC nano-composite lm (Fig. 6(d)) also obviously reveals the uniform distribution of Si element in the composite. According to the above TEM and EDS results simultaneously (Fig. 6), it can be concluded that SiC nano-particles are indeed dispersed well into the obtained nickel matrix under the ultrasonic

Intensity(Counts)

Fig. 6. (a) TEM bright-eld image of NiSiC nano-composite lm, (b) EDS analysis of the dark part pointed by arrow in (a), (c) SAD pattern of the same sample, and (d) element distributing map of Si (white points) on NiSiC nano-composite lm.

Cu (200)

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electroplating conditions. Consequently, the absence of SiC diffraction peak in XRD pattern must be due to the facts that, either the content of SiC in the composite lm is too low (much less than 14 wt.%) to be detected by XRD [25], or the size of SiC particles is very small [26]. The XRD pattern of the used SiC particles has been taken in Fig. 7. It shows SiC particles are in the polycrystalline nature of the coatings. Comparing to the standard card, SiC particles was t to No. 29-1129 exactly. Therefore, the absence of SiC diffraction peak in Fig. 5 cannot be attributed to their amorphous state in nature. Based on the above analyses, under experimental conditions, the obtained NiSiC nano-composite lms truly possess the nanostructure, i.e., both the consecutive nickel matrix and dispersed SiC phase are composed of particles in the nanometer range. 3.3. Corrosion resistance of NiSiC nano-composite lm in NaCl solutions The potentiodynamic polarization curves of nickel and NiSiC nano-composite lm in neutral 3.5 wt.% NaCl solution is shown in Fig. 8. Both of them show an activepassive transition, but the polarization curve of NiSiC nano-composite lm shows a wider passive region and slight more positive corrosion potential than that of nickel lm (may be due to their difference in structure, nanocrystalline nickel is much easier to be oxidized in the air than traditional polycrystalline counterpart). For NiSiC nano-composite lm, the corrosion current density is deep to 6.645E7 A/cm2, which is much smaller than that of nickel lm with 2.039E5 A/cm2. This indicates that NiSiC nano-composite lm has better corrosion resistance than nickel lm. The results also infer that SiC nanoparticles change the structure of the electrodeposited nickel lm, or act as inter physical barriers to the initiation and development of defect corrosion, hence improve the corrosion resistance of the lm [27]. The much higher corrosion resistance of NiSiC nano-composite lm than that of Ni lm can also be conrmed by EIS results of Ni and NiSiC nano-composite lms immersed in the same neutral 3.5 wt.% NaCl solutions for 1 h at open circuit potential (Fig. 9). Two EIS plots in Fig. 9 are similar. Each plot contains only one high frequency capacitive loop, but the capacitive loop of NiSiC coating is much bigger than that of Ni obviously. The results show that the reaction resistance (or lm resistance) of NiSiC coating is larger than Ni. It also infers that the corrosion resistance of the former is much higher than the latter. 3.4. Hydrogen evolution activity of NiSiC nano-composite lm in 30 wt.% KOH solutions To produce hydrogen by water electrolysis, there are two kinds of active cathode materials. The rst is platinum, the second is nickel and
350 300

0 -1

Current Density log (i, A)

-2 -3 Ni -4 -5 -6 -7 -8 -9 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 Ni-SiC

Potential(V vs.SCE)
Fig. 8. Potentiodynamic polarization curves of Ni and NiSiC nano-composite lm in neutral 3.5 wt.% NaCl solutions.

its alloys. People mainly took researches on nickel and its alloys because of the exorbitant cost of platinum. Consequently, the obtained NiSiC nano-composite lms are characterized for their electrocatalytic activity for hydrogen evolution in 30 wt.% KOH solutions. Fig. 10 shows the cathode polarization curves of Ni and NiSiC nano-composite lms in 30 wt.% KOH solutions, where the drastic uctuations in the curves indicate the hydrogen evolution. Compare the current for hydrogen evolution at the same anodic potential, it can be concluded that the electrocatalytic activity for hydrogen evolution of the latter is much higher than that of the former. Based on the plots shown in Fig. 10, the Tafel solpes of both NiSiC nano-composite lm (ca. 502 mV/dec) and pure Ni lm (ca. 455 mV/dec) are calculated. The results show that, the HER activity of NiSiC nano-composite lm is much better than the pure Ni lm. The result is in good agreement with the SEM results (Fig. 2a), where an increase in the real surface area of NiSiC nano-composite lm is evident, which may be one reason that results in a larger Tafel solpe. Fig. 11 shows the typical EIS plots (including Nyquist and Bode plots) of Ni and NiSiC nano-composite lms in 30 wt.% KOH solutions for 1 h at open circuit potential. Two EIS plots are similar, each plot simultaneously contains a high- and low frequency capacitive semicircles. The time-constant numbers of the EIS results have been determined through the EIS diagrams (including Nyquist and Bode

-30000

Impedance R/ohm

Intensity (Counts)

250 200 150 100

-20000 Ni-SiC -10000 Ni

Ni-SiC Ni

0 50 0 0 10000 20000 30000 40000

20

30

40 50 60 2-Theta (degree)

70

80

Impedance I/ohm
Fig. 9. Nyquist plots of Ni lm and NiSiC nano-composite lm immersed in neutral 3.5 wt.% NaCl solutions for 1 h at open circuit potential.

Fig. 7. XRD pattern of the SiC particles.

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0.35 0.30 0.25 Ni-SiC Ni

Current/A

0.20 0.15 0.10 0.05 0.00 -0.05 0.0 -0.5 -1.0

Ni-SiC

Ni

-1.5

-2.0

-2.5

Potential/V
Fig. 10. Cathode polarization curves of Ni and NiSiC nano-composite lms in 30 wt.% KOH solutions.

plots) and the method developed by Wit [28,29]. The results show that each EIS plot contains two capacitive loops above the real axis. The high frequency capacitive loop may be caused by the resistance of the lm, while the low frequency capacitive loop is correlated with the charge transfer resistance for the lm reacting with KOH solutions (to generate hydrogen). Meanwhile, in order to discriminate the Nyquist plots of Ni and NiSiC nano-composite lms clearly, the high frequency capacitive loops are enlarged and re-plotted as an insert in Fig. 11(a). Fig. 11(a) clearly shows that both the centers of the low

frequency capacitive loops are below the real axes, which indicate that both the reactions of Ni and NiSiC nano-composite lms with KOH solutions are mainly actively controlled [30]. Based on the above analysis, the EIS plots shown in Fig. 11 are analyzed using two-time constants electrochemical equivalent circuit (EEC) model (Fig. 12) and Boukamp program. In Fig. 12, Rs is the electrolyte resistance, Rc and Rct represent respectively for the resistances of nickel/NiSiC nano-composite lms and charge transfer, CPEc and CPEdl for electrode surface capacitance (including deviation from ideal capacitive behavior) and the double layer capacitance respectively. Table 2 lists the tted EIS parameters (corresponding to the EIS data in Fig. 10). It can be seen that n1 for NiSiC nano-composite lm (0.94) is larger than that for Ni lm (0.89), while CPEc of the latter is about two times high than the former. CPEc is the electrode surface capacitance, which is the osculate area between coating and solution. The larger the CPEc value, the more contact area of coating and solution. The results indicate that the lm surface of the former is much smoother than the latter, and agree well with the SEM results (Figs. 23). The lm resistance (Rc) of NiSiC nano-composite is about three times higher than that of Ni deposit, which conrms the corrosion results of the same kind lms in neutral 3.5 wt.% NaCl solutions (Figs. 89), and indicates that the former possesses much higher anticorrosion ability. Meanwhile, the charge transfer resistance (Rct) of the former is slightly lower than that of the latter, which indicates that the electrocatalytic reaction activity of the former in KOH solutions (to generate hydrogen) is higher than that of the latter, and tallies with the cathode polarization results (Fig. 10) of Ni and NiSiC nanocomposite lms in 30 wt.% KOH solutions very well. 4. Conclusions

(a)
-15000
Impedance R/ohm

-1200 -1000 -800 -600 -400 -200 0 0 100 200 300 400 500

Ni Ni-SiC

-10000

Ni

Impedance I/ohm

-5000 Ni-SiC 0 0 5000 10000 15000 20000

Impedance I/ohm

(b)

5 -80 4

(1) NiSiC nano-composite coating composed of both the nanocrystalline consecutive Ni matrix and the dispersed inert SiC nano-particles, has been fabricated by using ultrasonic electroplating technique from a modied Watts bath containing SiC nano-particles. The addition of inert SiC nano-particles into nickel electroplating solutions can destroy the preferential growth of nickel crystals. (2) The mechanical stirring mainly prevents the sedimentation of the inert SiC particles suspended in the composite electroplating solutions, while the ultrasonication mainly prevents the particles agglomeration. (3) When compared with the traditional polycrystalline nickel coatings, the obtained NiSiC nano-composite lm exhibits lower corrosion current density (6.645E7 A/cm2) in neutral 3.5 wt.% NaCl solutions, and possesses much higher electrocatalytic hydrogen evolution activity in 30 wt.% KOH solutions. Acknowledgements

Impedance R/ohm

Phase angle

-60 3

Lg Z

Ni-SiC -40 2 Ni 1 -20

The authors wish to acknowledge the nancial supports of the National Natural Science Foundation of China (Project 50771092, J0830413), The Ministry of Science and Technology of China (Project 2005DKA10400-Z15) and The Doctoral Fund of Ministry of Education of China (Project 200803351092).

-2

Lg(Frequence,Hz)
Fig. 11. EIS plots of Ni and NiSiC nano-composite lms in 30 wt.% KOH solutions for 1 h at open circuit potential: (a) Nyquist plots and (b) Bode plots. Fig. 12. Equivalent circuit for Ni and NiSiC lms in 30 wt.% KOH solutions.

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C. Cai et al. / Surface & Coatings Technology 205 (2011) 34483454 [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] A.F. Zimmerman, D.G. Clark, K.T. Aust, U. Erb, Mater. Lett. 52 (2002) 85. F.F. Xia, et al., Curr. Appl Phys. 9 (2009) 44. H.Y. Zheng, M.Z. An, J. Alloy. Compd. 459 (2008) 548. J. Divisek, H. Schmitz, B. Steffen, Electrochim. Acta 39 (1994) 1723. L.A. Kibler, Chemphyschem 7 (2006) 985. F. Rosalbino, S. Delsante, G. Borzone, E. Angelini, Int. J. Hydrogen Energy 33 (2008) 6696. K.L. Jae, Y. Youngmi, J.L. Hye, U. Sunghyun, L. Jaeyoung, Catal. Today 146 (2009) 188. R.K. Shervedani, A.R. Madram, Int. J. Hydrogen Energy 33 (2008) 2468. M. Popczyk, A. Budniok, A. Lasia, Int. J. Hydrogen Energy 30 (2005) 265. B. Losiewicz, A. Budniok, E. Rowinski, E. Lagiewka, A. Lasia, Int. J. Hydrogen Energy 29 (2004) 145. R.K. Shervedani, A.R. Madram, Electrochim. Acta 53 (2007) 426. Z.X. Niu, F.H. Cao, W. Wang, Z. Zhang, J.Q. Zhang, C.N. Cao, Trans. Nonferrous Met. Soc. China 17 (2007) 9. S.H. Yeh, C.C. Wan, Plat. Surf. Finish. 84 (3) (1997) 54. D. Gierlotka, E. Rowinski, A. Budniok, E. Lagiewka, J. Appl. Electrochem. 27 (12) (1997) 1349. H.B. Temam, L. Zeroual, A. Chala, S. Rahmane, C. Nouveau, Plasma Process. Polym. 4 (2007) 618. M.R. Vaezi, S.K. Sadrnezhaad, L. Nikzad, Colloids Surf. Physicochem. Eng. Aspects 315 (13) (2008) 176. D.H. Van Der Weijde, E.P.M. Van Westing, J.H.W. de Wit, Corros. Sci. 36 (2004) 643. P. Campestrini, E.P.M. Van Westing, J.H.W. de Wit, Electrochim. Acta 46 (2001) 2631. S.G. Wang, C.B. Shen, K. Long, T. Zhang, F.H. Wang, Z.D. Zhang, J. Phys. Chem. B 110 (2006) 377.

Table 2 Parameters of corresponding equivalent circuit for Ni and NiSiC nano-composite lms. t/h Rs/ m2 CPEc/F cm2 n1 Rc/ m2 Rt/ m2 CPEdl/F cm2 n2 NiSiC 2.199 9.4054 0.94 2.543E+3 1.576E+4 38.163 0.69 Ni 1.392 21.872 0.89 7.488E+2 1.759E+4 22.959 0.83

References
[1] L. Benea, P.L. Bonora, A. Brello, S. Martelli, F. Wenger, P. Ponthiaux, J. Galland, Solid State Lonics 152 (2002) 89. [2] F.F. Xia, M.H. Wu, F. Wang, Z.Y. Jia, A.L. Wang, Curr. Appl Phys. 9 (2009) 44. [3] B.S. Xu, H.D. Wang, S.Y. Dong, B. Jiang, W.Y. Tu, Electrochem. Commun. 7 (2005) 572. [4] J. Li, Y. Sun, X. Sun, J. Qiao, Surf. Coat. Technol. 192 (2005) 331. [5] Y. Zhou, H. Zhang, B. Qian, Appl. Surf. Sci. 253 (2007) 8335. [6] R.P. Socha, K. Laajalehto, P. Nowak, Colloids Surf. Physicochem. Eng. Aspects 208 (2002) 267. [7] I. Garcia, A. Conde, G. Langelaan, J. Fransaer, J.P. Celis, Corros. Sci. 45 (2003) 1173. [8] F.H. Stott, D.J. Ashby, Corros. Sci. 18 (1978) 183. [9] L. Liu, H.J. Zhao, W.B. Hu, B. Shen, Mater. Lett. 59 (2005) 3014. [10] H.Z. Wang, S.W. Yao, S.J. Matsumura, J. Mater. Process. Technol. 145 (2004) 299. [11] K.K. Sun, J.Y. Hong, Surf. Coat. Technol. 108109 (1998) 564.