Surface & Coatings Technology 200 (2006) 3438 3445 www.elsevier.

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Deposition of electroless NiP graded coatings and evaluation of their corrosion resistance
T.S.N. Sankara Narayanana,*, I. Baskaranb, K. Krishnavenia, S. Parthibanc
b a National Metallurgical Laboratory, Madras Centre CSIR Complex, Taramani, Chennai-600 113, India Materials Science Division, Department of Nuclear Physics University of Madras, Guindy Campus, Chennai-600 025, India c Department of Physics, Anna University, Chennai-600 025, India

Received 3 August 2004; accepted in revised form 8 October 2004 Available online 13 November 2004

Abstract Electroless NiP coatings provide high hardness and excellent resistance to wear and abrasion. The present work aims to study the formation of electroless NiP graded coatings, with varying nickel and phosphorus contents of the individual layers and to evaluate their corrosion resistance by polarization and electrochemical impedance spectroscopic studies. The possibility of preparing electroless NiP graded coatings by sequential immersion in three different plating baths is discussed. The study reveals that electroless NiP graded coatings offer better corrosion resistance than non-graded NiP coatings. D 2004 Elsevier B.V. All rights reserved.
Keywords: Electrodes; Graded coatings; Corrosion; Resistance

1. Introduction Electroless plating is a well established surface engineering process that involves deposition of a metal-metalloid alloy coating on various substrates. Although a variety of metals can be electrolessly plated, electroless NiP coating has received widespread acceptance as it provides high hardness and excellent resistance to wear, abrasion and corrosion [15]. Electroless NiP coatings are widely used for corrosion protection application in a variety of environments [15]. It is a barrier coating, protecting the substrate by sealing it off from the corrosive environments, rather than by sacrificial action. However, in this respect, only electroless Nihigh P coating is effective in offering an excellent protection whereas electroless NiLow P and Ni medium P coatings are not recommended for severe environments [15].

* Corresponding author. Tel.: +91 44 2254 2077; fax: +91 44 2254 1027. E-mail address: tsnsn@rediffmail.com (T.S.N. Sankara Narayanan). 0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2004.10.014

In recent years, multilayer and graded coatings have received much attention as they could provide considerable improvement in the desired characteristics of the coatings. Electrodeposition is a proven technique to prepare multilayer and graded coatings [68]. Since the composition of the individual layers could be altered easily by varying the concentration of the metallic ions, current density, speed of agitation, etc., much work on multilayer and graded coatings was explored using electrodeposition technique. Pulsed current electrodeposition still makes it more amenable for the deposition of a variety of coatings [9,10]. On the contrary, electroless plating baths are quite sensitive to variations in temperature, pH, etc., to make them amenable for preparing multilayer coatings with periodicity. However, it is possible to prepare graded coatings by sequential immersion in two or more electroless plating baths. In our earlier work, we have prepared electroless NiP/NiB duplex coatings, with both NiP and NiB as outer layers, using acidic hypophosphite-and alkaline borohydridereduced electroless plating baths [11]. The corrosion resistance of NiP/NiB duplex coatings is better for the coating that has NiP as the outer layer than the one with

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NiB as the outer layer. Hence it is possible to manipulate the corrosion resistance of graded coatings depending on the type of coatings selected as the inner and outer layers. In a similar attempt, the present work aims to study the formation of electroless NiP graded coatings, with varying nickel and phosphorus contents of the individual layers by sequential immersion in three different hypophosphitereduced electroless plating baths and to evaluate their corrosion resistance by polarization and electrochemical impedance spectroscopic studies.

2. Experimental details Mild steel was used as the substrate material for the preparation of non-graded as well as graded electroless NiP coatings. The mild steel substrates were surface ground to a roughness of 0.45 Am and electrolytically cleaned using an alkaline solution containing sodium carbonate, sodium hydroxide and sodium lauryl sulphate. The bath composition and operating conditions used for preparing non-graded as well as graded electroless NiP coatings were given in Table 1. The electroless NiP non-graded coatings were prepared using their respective baths (Table 1) whereas electroless NiP graded coatings were prepared by sequential immersion in the three plating baths. During plating, the plating bath was agitated using a magnetic stirrer at 600 rpm; the pH and temperature of the plating baths were maintained at F0.2 units and F1 8C, respectively. The phosphorous contents of the non-graded NiP coatings were analyzed by atomic absorption spectrophotometer (GBCAvanta). The nickel content was analyzed gravimetrically after precipitating nickel as NiDMG complex. The plating rate was assessed by measuring the gain in weight after plating and using the density of the deposit. Using the plot of thickness of the deposit vs. time, electroless NiP graded coatings with similar thickness of individual layers were prepared. The structure of the electroless NiP coatings, both in as-plated and heat-treated conditions, was assessed by X-ray diffraction (XRD). The surface morphology of the
Table 1 Bath composition and operating conditions of the baths used to prepared non-graded and graded electroless NiP coatings Bath constituents and operating conditions Nickel sulphate hexahydrate (g/l) Sodium hypophosphite (g/l) Lactic acid (ml/l) Propionic acid (ml/l) Tetrasodium pyrophosphate (g/l) Ammonium hydroxide (38%) (ml/l) Thiourea (ppm) Temperature (8C) pH Plating rate (Am/h) Ni content (wt.%) P content (wt.%) Bath A 21.2 24 28 2.2 0.8 90F1 4.5 25F1 86.70 13.30 Bath B 21.2 12 28 2.2 0.8 90F1 4.5 19F1 93.30 6.70 Bath C 50 100 100 45 65F1 10 16F1 96.66 3.34

non-graded NiP coatings and the cross-sectional micrograph of electroless NiP graded coatings were obtained using a scanning electron microscope (SEM). The corrosion resistance of non-graded and graded electroless NiP coatings in 3.5% sodium chloride solution was assessed by potentiodynamic polarization and electrochemical impedance spectroscopic studies performed using a potentiostat/galvanostat/frequency response analyzer (Gill AC; ACM Instruments, UK). The thickness of the nongraded as well as the graded electroless NiP coatings used for corrosion studies was of the order of 24F1 Am. A flat cell (Fig. 1) (Wear and Friction Tech, Chennai, India) was used for evaluating the corrosion resistance of the coated substrates so that only 1 cm2 area was exposed to the electrolyte solution. A saturated calomel electrode was used as the reference electrode whereas a platinum electrode served as the counter electrode. The corrosion potential (E corr) and corrosion current density (i corr) were determined using the Tafel extrapolation method. The charge transfer resistance (R ct) and double layer capacitance (C dl) were determined from the corresponding Nyquist plots by fitting the data using Boukamp software.

3. Results and discussion Electroless Nihigh, medium and low P coatings obtained using baths A, B and C (Table 1), respectively, are uniform and highly adherent. Among them, the plating rate is very high for electroless Nihigh P coating. Plating rate as a function of time for coatings obtained from baths A, B and C is given in Fig. 2. Based on the amount of coating formed in a given time from each plating bath, the time of deposition for each layer of electroless NiP graded coatings is decided so that layers of similar thickness could be deposited. The total thickness of each type of coatings for evaluating the corrosion resistance is chosen as 24F1 Am. Hence for depositing electroless NiP (LMH) graded coatings, the substrate has to be coated for 23, 15 and 10 min in bath C, B and A, respectively. One important aspect of depositing electroless NiP graded coatings is the application of a nickel strike between each layer, so that the deposition proceeds when the substrate is sequentially immersed in electroless plating baths. In the absence of nickel strike, deposition of subsequent layers is delayed. This effect is well pronounced in graded coatings with Nihigh P as the first layer (adjacent to the substrate) due to its ability to form an intact passive film [12]. The XRD patterns of non-graded electroless NiP coatings, obtained from bath A, B and C, in their as-plated and heat-treated (400 8C/h) conditions, are given in Figs. 3, 4 and 5, respectively. In as-plated condition, the electroless Nihigh P coating is amorphous in nature (Fig. 3(a)) whereas the Nimedium P (Fig. 4(a)) and Nilow P (Fig. 5(a)) coatings are respectively microcrystalline and crystal-

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Fig. 1. Schematic diagram showing the arrangement of the flat cell used for evaluating the corrosion resistance of electroless NiP coatings.

line in nature. Upon heat-treatment (400 8C/h), all the three types of NiP coatings become crystalline with the formation of f.c.c Ni and b.c.t Ni3P phases (Figs. 3(b), 4(b) and 5(b)). However, the extent of Ni3P phase formation is higher for electroless Nihigh P coating (Fig. 3(b)), in which the intensity of Ni3P orientation is higher than that of Ni (111) orientation. In the case of electroless Nimedium and low P coatings (Figs. 4(b) and 5(b)), the extent of Ni3P

Fig. 2. Plating rate as a function of time for coatings obtained from baths A, B and C.

(231) phase formation is relatively lower, and Ni (111) is the preferred orientation. The surface morphology of non-graded electroless NiP coatings is shown in Fig. 6 (ac). The variation in surface morphology of these coatings suggests a definite dependence on their phosphorus content, supporting the observations made by Lu and Zangari [13]. Electroless Nihigh P and Nimedium P coatings (from baths A and B) exhibit a smooth surface with uniform particle size (Fig. 6(a) and (b)) whereas a relatively rough surface composed of spherical particles of varying sizes is observed for electroless Nilow P coating (from bath C) (Fig. 6(c)). The appearance of cauliflower-like nodules (at higher magnifications), which is typical of amorphous materials, is observed for electroless Nihigh P coatings. The cross-sectional micrograph of the graded electroless NiP (LMH) is shown in Fig. 7. It is evident from Fig. 7 that the graded electroless NiP coatings are uniform and the compatibility between the three layers is good. The polarization curves obtained for non-graded as well as graded electroless NiP coatings, in 3.5% sodium chloride solution, are shown in Fig. 8. The corrosion potential (E corr) and corrosion current density (i corr) calculated using Tafel extrapolation method are given in Table 2. Among the non-graded electroless NiP coatings, the corrosion resistance offered by electroless Nihigh P coating is higher than that of the other two types of coatings, supporting the results of earlier studies [1319]. Between the two types of graded NiP coatings, the coating that has Nihigh P as the outer layer offers better corrosion

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chemical impedance behaviour of electroless NiP coatings in 1 M NaOH at 1.2 V and in 3.5% NaCl solution at 0.32 V, respectively. The occurrence of a single semicircle in the Nyquist plots indicates that the corrosion process of electroless NiP coatings involves a single time constant. The appearance of a single inflection point in the plot of df vs. log ZT and a single phase angle maximum in the plot of df vs. phase angleT (figure not shown), further confirm that the process involves only a single time constant. Balaraju et al. [16], Zeller III [17], Lo et al. [18] and Van Der Kouwe [19] have also reported the existence of a single time constant for the corrosion behaviour of electroless NiP coatings in sodium chloride and sodium hydroxide solutions. Hence it is evident that the electroless NiP coating 3.5% sodium chloride solution interface exhibit charge transfer behavior. The charge transfer resistance (R ct) and double layer capacitance (C dl) values, derived after fitting the data (Nyquist plot) using Boukamp software, for non-graded as well as graded electroless NiP coatings are compiled in Table 2. The results of electrochemical impedance studies also indicate a similar trend in the corrosion resistance that

Fig. 3. X-ray diffraction pattern of electroless Nihigh P coatings obtained from bath A (a) as-plated condition; and (b) heat-treated at 400 8C for 1 h.

resistance. A comparison of the corrosion resistance of all the coatings studied is of the following order: EL graded Ni P L M H N EL Ni high P N EL Nimedium P N EL graded Ni P H M L N EL Nilow P The Nyquist plots obtained for non-graded as well as graded electroless NiP coatings, in 3.5% sodium chloride solution, at their respective open circuit potentials, are shown in Fig. 9. The Nyquist plots of all the coatings studied exhibit a single semicircle in the frequency range studied (10 KHz to 0.01 Hz). However, the curves differ considerably in their size. This indicates that the same fundamental process is occurring on all the types of NiP coatings, but over a different effective area in each case. To account for the corrosion behavior of electroless NiP coatings, at their respective open circuit potentials, an equivalent electrical circuit model (Fig. 10) consists of solution resistance (R s), double layer capacitance (C dl) and charge transfer resistance (R ct), in which the C dl and R ct are parallel to each other, has been utilized to simulate the metal/solution interface. Lo et al. [18] and Balaraju et al. [16] have also used a similar model to study the electro-

Fig. 4. X-ray diffraction pattern of electroless Nimedium P coatings obtained from bath B (a) as-plated condition; and (b) heat-treated at 400 8C for 1 h.

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sodium chloride solution. The C dl values are related to the porosity of the coatings. Hence based on the C dl values it can be inferred that electroless Nihigh P coating of the present study is relatively less porous compared to electroless Nimedium P and lowP coatings. In general, the corrosion resistance of electroless NiP coatings with varying phosphorus content is of the order: EL

Fig. 5. X-ray diffraction pattern of electroless Nilow P coatings obtained from bath C (a) as-plated condition; and (b) heat-treated at 400 8C for 1 h.

is observed by potentiodynamic polarization studies. The high values of charge transfer resistance (R ct) obtained for electroless Nihigh P and graded (LMH) electroless NiP coating, of the order of 3738 kV cm2, imply a better corrosion protective ability of these coatings compared to the other types of coatings studied. Balaraju et al. [16] have reported that the R ct value of electroless Ni11 wt.% P coating in 3.5% sodium chloride solution is 35 kV cm2. Van Der Kouwe [19] recommended that an intact electroless Ni P coating should have a charge transfer resistance above 45 kV cm2. The capacitance values obtained for electroless Ni high P and electroless NiP graded (LMH) coatings are also very low, 49.10 and 36.70 AF/cm2, respectively. These values are highly comparable to those obtained for similar coatings reported elsewhere [1619]. Zeller III [17] reported a value of 28 AF/cm2 for electroless NiP (1011 wt.% P) coating having a thickness of 5060 Am in 5% sodium chloride solution. Lo et al. [18] reported that the C dl values are in the range of 100120 AF/cm2 for electroless NiP (11.812.8 wt.% P) in de-aerated 1 N NaOH solution at 1.2 V. Van Der Kouwe [19] also reported C dl values of 30 and 42 AF/cm2 for high phosphorus electroless nickel coatings having a thickness of greater than 20 Am in 3%

Fig. 6. Surface morphology of electroless NiP coatings (a) Nihigh P coating; (b) Nimedium P coating; and (c) Nilow P coating.

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Table 2 Corrosion resistance of non-graded and graded electroless NiP coatings in 3.5% sodium chloride solution System studied EL NiLow P coating (L) EL NiMedium P coating (M) EL NiHigh P coating (H) EL NiP graded coating (LMH)a EL NiP graded coating (HML)a
a

E corr (mV vs. SCE) 536 434 411 403 481

i corr (AA/cm2) 4.22 1.17 0.60 0.41 1.70

R ct (kV cm2) 6.90 24.86 37.45 38.22 14.77

C dl (AF) 289 55.60 49.10 36.70 103

LMHLowMediumHigh P; HMLHighMediumLow P.

Fig. 7. Cross-sectional micrograph of the graded electroless NiP (LMH) coating.

Nihigh PNEL Nimedium PNEl Nilow P. The results obtained in the present study also confirm this fact (Figs. 8 and 9 and Table 2). The difference in corrosion resistance between NiP coatings with varying phosphorus content is addressed by several researchers [13,2024]. According to Mimani and Mayanna [20], the corrosion behaviour of electroless NiP coatings is governed by three principal factors, namely, the degree of amorphous state, extent of internal stress and the percentage of phosphorus content. The combined effect of all of these factors or dominance of any one of these factors is responsible for the observed corrosion behaviour. Raicheff and Zaprianova [21] have suggested that the higher corrosion resistance of amorphous electroless NiP coatings is due to their homogeneous structure and the absence of grain boundaries, dislocations, kink sites and other surface defects. Lu and Zangari [13] have also suggested that the difference in corrosion resistance between electroless Nilow P and Nihigh P coatings is in part due to the difference in structurea crystalline, inhomogeneous structure for the low P materi-

als, and an amorphous, homogeneous one for the high P materials. Bai et al. [22] have suggested that the P content of the electroless NiP coating has a positive effect on reducing the corrosion rate and on positively shifting the corrosion potential in brine media. Diegle et al. [12], Lu and Zangari [13], Lee and Liang [23] and Aoki and Takano [24] have also pointed out that electroless NiP coatings with higher P content show nobler E corr and lower i corr and potentially better corrosion resistance. Besides structure and homogeneity, electronic effects are also considered to be responsible [13]. It has been pointed out that the P in the amorphous NiP coating acts as an acceptor and gains 0.4 0.8 electrons from Ni with increasing P content between 13 and 25 at.% [25]. The corresponding partially covalent character of the NiP bonding arrangement influence the equilibrium involved in NiO formation and Ni dissolution. The formation of an adsorbed film of hypophosphite generated by the oxidation of phosphorus present in the coating surface, which in turn blocks the water molecules from interacting with nickel, thus inhibiting nickel oxidation is considered to be one of the most convincing model [12] proposed to explain the difference in corrosion behaviour of electroless NiP coatings. According to this model, preferential dissolution of nickel occurs even at the open circuit

Fig. 8. Potentiodynamic polarization curves obtained for non-graded as well as graded electroless NiP coatings, in 3.5% sodium chloride solution (Potentials in mV vs. SCE).

Fig. 9. Nyquist plots obtained for non-graded as well as graded electroless NiP coatings, in 3.5% sodium chloride solution, at their respective open circuit potentials.

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Fig. 10. Equivalent electrical circuit model proposed to explain the corrosion behaviour of non-graded as well as graded electroless NiP coatings.

potential, leading to the enrichment of phosphorus on the surface layer. The enriched phosphorus surface reacts with water to form a layer of adsorbed hypophosphite anions (H2PO2 ). This layer in turn will block the supply of water to the electrode surface, thereby preventing the hydration of nickel [12], which is considered to be the first step to form either soluble Ni2+ species or a passive nickel film. Van Der Kouwe [19], using glow discharge optical emission spectrometry, confirmed the presence of a phosphorus rich surface layer in a high phosphorus (8 wt.% P) electroless nickel deposit even before it is subjected to any corrosive environment. Accordingly, such a condition of phosphorus enrichment at the surface provides a competitive advantage for the hydrolysis of phosphorus and would not favour the hydrolysis of nickel. Hence the better corrosion resistance obtained for electroless Nihigh P coatings is due to the enrichment of phosphorus on the electrode surface, a condition, which is not favoured in electroless Nilow and medium P coatings. Since electroless Nilow P coating is crystalline and electroless Nimedium P coatings is not totally amorphous, the passive films that form on surface of these coatings are not as glassy or protective as that of the one form on electroless highP coatings. The phase boundaries present in low and medium P coatings also produce passive film discontinuities, which are preferred sites for corrosion attack to begin. Hence when electroless Nihigh P coating forms the outer layer of the graded (LMH) NiP coating, the corrosion resistance increases. In contrast, when electroless Nilow P coating forms the outer layer of the graded (HML) NiP coating, the corrosion resistance is lower than its counterpart. However, the corrosion resistance offered by the latter type of graded coating is better than that of electroless Nilow P coating. This is due to the barrier properties of the underlying Ni medium P and Nihigh P layers. Heat treatment at 400 8C for 1 h tends to induce crystallization of the electroless NiP coatings and decrease their corrosion resistance [15]. Hence it is of interest to know the effect of heat treatment (400 8C for 1 h) on the gradation and corrosion resistant behaviour of electroless NiP graded coatings. Heat-treatment of electroless NiP

deposits will induce diffusion of both Ni as well as P and several authors have discussed about this aspect [2631]. Keong et al. [26] confirms the occurrence of thermally activated diffusion process between electroless NiP deposit and the mild steel substrate underneath it, during annealing at 400 8C for 1 h. They have observed an increase in iron content with a corresponding decrease in Ni content of the electroless NiP deposit, as well as an increase in the nickel content of the diffusion layer at the metal-coating interface. Li et al. [27] confirms the possibility of diffusion of P from the bulk to the surface during oxidation of the electroless NiP coating. The formation of NiCu diffusion layer, following diffusion of Ni from the electroless NiP coating and Cu from the substrate, supports the occurrence of thermal motion of atoms which renders the absence of cracks in the electroless NiP coating at higher annealing temperatures of the order of 400 8C [28]. Jang et al. [29] proposed that the diffusion species in solder-reaction assisted crystallization could be either Ni or P, which is further confirmed by Hung et al. [30]. Papachristos et al. [31] have confirmed the loss in gradient nature of the coating following heat-treatment of electrodeposited NiW P graded deposits at 400600 8C. Hence it is presumed that during heat-treatment at 400 8C for 1 h, diffusion of Ni as well as P will occur in the electroless NiP graded coatings. This will result in the modification of the graded layers in such a way that the gradation will be lost. Moreover, heattreatment at 400 8C for 1 h also leads to crystallization of the electroless NiP deposits (Figs. 3(b), 4(b) and 5(b)), making available more number of grain boundaries which are highly prone to corrosion attack. As a result, the corrosion resistance of the heat-treated electroless NiP graded coatings will be drastically reduced. Hence the concept of graded electroless NiP coatings is valid only in as-plated condition and the gradation will be lost if the coating is heattreated at 400 8C for 1 hour. The corrosion resistance claimed for graded electroless NiP coatings is also valid only in as-plated condition since heat-treatment at 400 8C for 1 h will drastically reduce the corrosion resistance.

4. Conclusion From the study it can be concluded that it is possible to prepare electroless NiP graded coatings by sequential immersion in three different hypophosphite-reduced electroless plating baths. One important aspect of depositing electroless NiP graded coatings is the application of a nickel strike between each layer, so that the deposition proceeds without any hindrance when the substrate is sequentially immersed in electroless plating baths. The graded electroless NiP coatings are uniform and the compatibility between the three layers is good. Comparison of the corrosion resistance of all the coatings studied is of the following order: EL graded NiP (LMH)NEL Nihigh PNEL Nimedium PNEL graded NiP (HML)NEL Nilow

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P. When electroless Nihigh P coating forms the outer layer of the graded (LMH) NiP coating, the corrosion resistance increases. In contrast, when electroless Nilow P coating forms the outer layer of the graded (HML) NiP coating, the corrosion resistance is lower than its counterpart. However, the corrosion resistance offered by the latter type of graded coating is better than that of electroless Nilow P coating, due to the barrier properties of the underlying Nimedium P and Nihigh P layers. Heat-treatment of electroless NiP graded coatings is likely to modify the graded layers so that the gradation is lost. Hence the concept of graded electroless NiP coatings is valid only in as-plated condition. The corrosion resistance claimed for electroless NiP graded coatings is also valid only in as-plated condition since heattreatment at 400 8C for 1 h will drastically reduce the corrosion resistance.

Acknowledgements Financial support given to this work by the Council of Scientific and Industrial Research (CSIR), New Delhi, India was gratefully acknowledged. The authors are thankful to Prof. S.P. Mehrotra, Director, National Metallurgical Laboratory, Jamshedpur and Dr. S. Srikanth, Deputy Director, National Metallurgical Laboratory, Madras Centre, for their constant support and encouragement to carry out this research work.

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