Surface and Coatings Technology 179 (2004) 314323

Kinetic and morphological investigation of CoFe alloy electrodeposition in the presence of organic additives
F. Lallemand*, L. Ricq, M. Wery, P. Bercot, J. Pagetti
` Laboratoire de Chimie des Materiaux et Interfaces, Pole Corrosion, Traitements de Surface et Systemes Electrochimiques, 16 route de Gray, Besancon Cedex 25030, France Received 10 March 2003; received in revised form 3 June 2003

Abstract The use of organic additives is widespread in the manufacturing of thin films using electrodeposition. Common additives like saccharin (SAC) are used as leveling and brightening agents. In the present work, a comparative study of the influence of organic additives containing a similar saccharin molecular structure on CoFe alloy electrodeposition has been performed in order to obtain information about the kinetics of the cathodic process and the morphology of the deposits. The study was based on an electrochemical investigation using steady-state polarization measurements, coupled with scanning electron microscopy and X-ray dispersive analysis of the CoFe deposits. The composition, the current efficiency and the partial current densities of the CoFe alloy were determined in order to study the influence of SAC, phthalimide (PHTA) and another additive containing sulfur element: o-toluene sulfonamide (oTOL) on the CoFe deposition from sulfate and chloride electrolytes at pH 3. Experimental results indicate that saccharin influence strongly the electrode kinetic contrary to oTOL and PHTA. The morphology of the CoFe deposits depends on used organic additive. It was also noted that the presence of saccharin results in smoother, more compact and more leveled deposits as compared to PHTA or oTOL. 2003 Elsevier B.V. All rights reserved.
Keywords: Electrodeposition; CoFe; Organic additives; Polarization; Efficiency; Morphology

1. Introduction Soft magnetic films are essential for producing thinfilm recording heads to meet the future trends in highdensity magnetic recording. For this purpose, it has been necessary to develop recording heads using material with optimized magnetic and corrosion properties. Three major groups of magnetic films can be distinguished: nickeliron w13x, cobaltiron w48x and ternary alloys composed of cobaltiron and a third element like nickel w912x, copper w13,14x or chromium w15,16x. Practically all commercial electroplating baths contain one or more addition agents, which lead to leveled and bright deposits. Several electroactive species can be added into the plating electrolyte in order to improve coating characteristics. Several studies have investigated the influence of organic additives in the electrolytes w7,8,11,12,17
*Corresponding author. Tel.: q33-381-66-20-30; fax: q33-38166-20-33. E-mail address: fabrice.lallemand@univ-fcomte.fr (F. Lallemand).

20x. Some additives are known to enhance the morphology and physical properties of metal electrodeposits w7,2022x. Saccharin, thiourea and other compounds are commonly used as levelling and brightening agents in electroplating w7,2022x. Moreover, saccharin is considered as a stress reducer of iron-group metals by several authors w7,11,19,23x. Despite the widespread use of plating additives, the relationship between additive molecular structure and final performance for a deposited metal are still not completely known. This work is a continuation of previous works w7,8,16x, which reported the effects of the organic additives saccharin (SAC), phthtalimide (PHTA) and another additive containing the sulfur element: o-toluene sulfonamide (oTOL) on the electrodeposition of the CoFe alloy. Saccharin is commonly used in manufacturing. This is the reason why, in this study, saccharin is considered as a reference. It was supposed that the sulfonamide group plays an important role on the electrodeposition by including the sulfur element in the

0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0257-8972(03)00812-0

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deposit. In this purpose, two other organic compounds are tested. Phthalimide is used, because its formula differs from saccharin by only one functional group. The sulfonamide group present in the saccharin molecule is replaced by a carbonyl group in the phthalimide (Fig. 1-b). Contrary to phthalimide, o-toluene sulfonamide is considered because of the sulfonamide group present in its molecular structure. The oTOL structure is similar to SAC. This work is composed of two parts. The first objective is to investigate the kinetics of cobaltiron cathodic process from sulfate and chloride electrolytes at pH 3, in the presence of organic additives. As a basis for comparison, results for CoFe deposition using no organic additives are presented. The effects of organic additives were studied during the CoFe electrodeposition by determining the composition, the current efficiency and the partial current densities of iron and cobalt. In the second part, CoFe deposits are examined via direct current experiments with the same composition in order to study the effect of organic additives on the structure and morphology of the binary Co91.5Fe8.5 alloy. 2. Experimental 2.1. Electrolyte compositions The cobaltiron electrolyte was prepared from analytical grade cobalt sulfate (CoSO47H2O), ferrous sulfate (FeSO47H2O), sodium chloride (NaCl), boric acid (H3BO3). Sulfuric acid (H2SO4 ) was used to adjust the electrolyte pH. Saccharin, phthalimide and o-toluene sulfonamide were from Aldrich. The structure and the symbols of organic compounds used as additives are shown in Fig. 1. All the solutions were prepared using ultra-pure Millipore water (Millipore MilliQ system). 2.2. Electrochemical studies Electrochemical studies consist of two parts with different experimental set-up. 2.2.1. Voltametry The experimental set-up for voltammetric measurements was performed with a three-electrode cell consisting of a platinum counter electrode, a mercury sulfate electrode (SSE) immersed in a separated compartment filled with a K2SO4 solution and a working electrode. The electrolytes consisted of 0.2 M of CoSO4, 0.02 M of FeSO4, 0.4 M of H3BO3, 0.5 M of NaCl and organic additives which were added in the electrolyte with a 2.5 10y3 mol Ly1 concentration. The electrolyte used for studies is deaerated using N2 bubbling for 60 min prior to use and maintained over the solutions during all the experiments in order to inhibit the ferrous ion oxidation. The pH was adjusted by the addition of an aqueous

H2SO4 solution until a value of 3.00"0.05 was reached. The working electrode was a copper plate with a 4.5 cm2 working surface. Before electrodeposition, copper working electrodes were immersed for 5 min in an alkaline solution, then 30 s in an acid solution and rinsed with MilliQ water. The temperature was constant (30"0.5 8C). The agitation was realized by a magnetic stirrer. The anolyte was not separated from the catholyte. The distance between the different electrodes was similar during all experiences. All electrochemical measurements were carried out using a computer-controlled potentiostat (PGP 301; Tacussel, France). After each electrodeposition at a fixed potential, the film was stripped in a known volume of HCl and HNO3 (2:1 of concentrated solutions) to analyze the film composition using Perkin-Elmer spectrometer atomic absorption spectrophotometry (AAS). Nitric acid, hydrochloric acid and copper ions did not cause interference with AAS measurements of cobalt and iron species. The results of metal concentrations from AAS allowed for the calculation of the weight fractions for binary alloys. Calibration standards for atomic absorption indicated an accuracy of "3% for analysis of the solution concentration. Like for voltammetry curves, film compositions of CoFe alloys were determinated by AAS, each experimental value given in this article is the average of five experiments. The curves are representative of the material behavior. 2.2.2. Co91.5Fe8.5 electrodeposition Galvanostatic electrolysis was performed in the absence and in the presence of organic additives, employing a plexiglass cell equipped with an electrolyte recycling system and temperature controllers. The deposits were plated with an approximate thickness of 2.0 mm onto silicon wafers with a sputtered Permalloy (80 nm) interlayer with a working surface of 3 cm2. In addition, a sputtered chromium (20 nm) adhesion layer has been deposited between Si and NiFe. The interelectrode distance was 3 cm. In all cases, the current density was held constant at 0.3 A dmy2, during the deposition time of 30 min. The composition of the plating bath used to produce the Co91.5Fe8.5 alloy is summarized in Table 2. As previously, the pH was adjusted by the addition of an aqueous H2SO4 solution until a value of 3.00"0.05 was reached. The bulk pH was measured before and after every deposition. In the event of a pH change, the value was corrected by adding hydrochloride acid. 2.3. Deposit examination Morphological examination of the CoFe deposits involved visual inspection and SEM observations. The

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Fig. 1. Chemical structures of saccharin (SAC), (b) phthalimide (PHTA) and (c) oTOL.

roughness was evaluated by profilometry with a whitelight phase shifting method. This method was described in a previous work w8x. The brightness was evaluated with a three-angle reflectometer (REFO 3-D). The preferential orientation of the crystals was performed by X-ray diffraction (XRD), using Co Ka radiation. The different phase and texture were determined with the JCPDS card of cobalt. 3. Results and discussion 3.1. Influence of the additives on the cathodic process The effects of organic additives on the electrode kinetic of the cobaltiron codeposition were investigated using linear sweep voltammetric techniques. The chronoamperometry curves were used in order to study the current density variation, according to the potential applied at the working electrode (y1000 to y1600 mV vs. SSE). For each applied potential, the total average current density Jtot was evaluated. For example, in the case of the CoFe co-deposition without organic addi-

tives, the chronoamperometry curves were represented in Figs. 2 and 3. We can observe that the transient state was limited and that the current density rapidly reaches a constant value. 3.2. Current efficiency The influence of organic additives on the cobaltiron codeposition can be estimated by measuring changes in the efficiency, which was given by: 100=mexp ymtheo (mexp: experimental mass). The efficiencies for CoFe electrodeposition varied from 0 to 95%, as shown in Fig. 4. The CoFe deposit was stripped and so the AAS results were allowed for the cobalt and iron weight percentage in the binary alloy. According to Faradays law, theoretical mass: mtheo of CoFe electrodeposits can be calculated. The efficiency increased as the applied cathodic potential increased. We can observe that for all electrolytes except in the case of SAC, for potentials more negative than y1350 mVySSE, the value stays constant at approximately 93"5%. The calculated efficiency under the same experimental conditions for

Fig. 2. Chronoamperometry curves of the electrolyte without organic additives.

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Fig. 3. Chronoamperometry curves of the electrolyte without organic additives.

different additives was slightly higher in the presence of PHTA, oTOL and without additives, compared to the results with SAC. 3.3. Film composition According to Fig. 5, which represents the cobalt weight percentage as the function of applied potential, we can observe that the cobalt percentage increases from 70 to 85% for CoFe produced without additive and with oTOL and PHTA, when the applied potential varies from y1200 to y1250 mVySSE. For potential more negative than y1250 mVySSE, the cobalt percentage stays constant at 85"2 wt.%. In the presence of SAC, we can observe that the Co weight percentage is higher

for potentials in the range of y1250 to y1350 mV vs. SSE. This effect of inhibition of the iron element was already observed w7,8x. Concerning the efficiency and the CoFe composition, we can affirm that the SAC molecule was more influential on the CoFe deposition than the oTOL and the PHTA molecules. To study these effects, the partial current densities of both the metals were investigated. 3.4. Polarization curves Voltammetry was used to characterize the organic additives, influence on the kinetic of the CoFe electrodeposition process. The cobalt weight percentage determination allows the calculation of the cobalt and the

Fig. 4. Current efficiency vs applied potential for CoFe deposits produced by electrolyte containing no additives (s), oTOL (=), PHTA (m) and SAC (j).

Fig. 5. Cobalt content vs. applied potential for CoFe deposits produced by electrolyte containing no additives (s), oTOL (=), PHTA (m) and SAC (j), without organic additives.

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Fig. 6. Partial current densities of CoFe (j), Cobalt (q), Iron (m), Jside(=), produced without organic additives.

Fig. 8. Partial current densities of iron for CoFe deposits produced by electrolyte containing no additives (s), oTOL (=), PHTA (m) and SAC (j).

iron partial current densities. Indeed, after every experiment, the partial current densities are determinated for each species. The total current density is equal to the sum of the partial current densities: JtotsJCoqJFeqJside It was assumed that the remaining current density Jside, besides that for metal species deposition, was mainly due to hydrogen evolution. This partial current density during the metal deposition was found to reach a plateau for each electrolyte studied as shown in Fig. 6, which represents partial current density Jside for a CoFe alloy, deposited without additive. As expected, the curves show a steady rise in the current densities as the applied cathodic potential increases. In a first part, the cathodic linear sweep polarization curves for cobalt electrodeposition in the

presence of additives are shown in Fig. 7. It can be seen that the reduction potential of cobalt in the binary alloy was approximately y1200 mVySSE in all cases. But the cathodic polarization depends on the nature of the additive. The highest polarization is observed for SAC, on the contrary there is no polarization for oTOL, PHTA and without additive. Consequently, the slower electrolytic deposition kinetic of cobalt is observed in the presence of SAC. Then, analysis of the iron and the cobaltiron partial current densities reveal the same effect as for cobalt in Figs. 8 and 9, respectively. Indeed, the reduction potential of iron species is shifted towards negative values when the SAC molecule is present in the electrolyte. This effect is not detected with the presence of oTOL and PHTA. The cobaltiron kinetic also depends on the organic additive nature. From the point of view of these different results, we could

Fig. 7. Partial current densities of cobalt for CoFe deposits produced by electrolyte containing no additives (s), oTOL (=), PHTA (m) and SAC (j).

Fig. 9. Partial Current densities of cobaltiron for CoFe deposits produced by electrolyte containing no additives (s), oTOL (=), PHTA (m) and SAC (j).

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conclude that oTOL and the PHTA organic additives do not influence the kinetics of CoFe deposition. In the literature, there are various opinions about the possibility to obtain cathodic Tafel plots in the presence of organic additives. In our experiments, in the investigated concentration range, a well-defined Tafel region in the presence of additives was not evident. This is in accordance with results of Varvara and Muresan w24x, who attributed this fact to a decreasing of the activity of cathodic surface in the presence of organic additives, due to its blocking effect of the surface active sites. This phenomenon can be attributed to the diffusion of cobalt and iron ions through an adsorbed complex, which is responsible for the absence of a Tafel region. Another possibility could be the strong inhibition exerted by additives on the nucleation process. The nucleation becomes the rate-determining step and leads to a flat region at low overpotentials in the polarization curves, which disables the Tafel treatment. However, by comparing the kinetic results for the CoFe codeposition, we have observed that saccharin can influence the codeposition process. The influence of this organic compound has been studied and can be viewed as a surface coverage in which SAC reduces the surface coverage of an electroactive species by decreasing the active area for the reduction process. Indeed, Osaka and co-workers w25x showed that SAC was only physically and reversibly adsorbed on the electrode. In the case of SAC, it is possible that the maximum surface coverage of the metal hydroxy ions is shifted toward more negative overpotentials. The complexation process can be added to this adsorption. In fact, it was well known that SAC could form a complex with iron or cobalt w26x. The presence of this organic molecule would slow down the diffusion of cations towards the cathode causing the complexation. This article deals with a study of two other additives for the electrodeposition of the binary CoFe alloy. According to the different experimental results, we can affirm that the oTOL and the PHTA molecules do not have the same behavior in the plating bath as the SAC molecule, because they do not influence the cobalt and iron reduction kinetic. 3.5. Effect of additives on the binary Co91.5Fe8.5 alloy CoFe alloys with an approximate thickness of 2.0 mm were deposited onto Permalloy-seeded glass to evaluate the coating morphology. To compare the different deposits with different additives, the concentration of iron salt was adjusted in the plating bath (Table 2) in order to obtain CoFe deposits with the same composition: Co91.5Fe8.5 3.6. CoFe deposit surface morphology According to Oniciu and Muresan w27x, a refinement of the deposit in regard to crystal size is found in all

cases of leveling and brightening. The dimensions of grains are determined by the number of grain-producing dislocations and as well by the number of nuclei appearing during the electrodeposition of metal. All factors promoting formation of dislocations or nucleation as high overpotential and foreign molecules contribute to the grain size. Indeed, high overpotential led to a high degree of supersaturation of the surface by adatoms and foreign molecules adsorbed at the surface create disorder in the incorporation of adatoms into lattice or inhibit surface diffusion of adatoms towards growing centres. But, grain refinement is a necessary, but not sufficient, condition for the production of bright and evenly leveled deposits. As it can be seen from Fig. 10a and b, the tested additives changed significantly the morphology of the CoFe deposits as compared with those obtained from solutions with oTOL or without additive (Fig. 10c). CoFe deposited with saccharin is usually homogeneous and no aggregate can be distinguished among used magnification (Fig. 10a). Moreover, by visual observation, we can notice that the addition of saccharin produced bright samples. As a consequence, we can confirm the role of saccharin as a brightening agent. In the case of phthalimide, deposits were dark and mat and we can note an inhomogeneous morphology with crystal aggregates of size between 0.5 and 0.7 mm (Fig. 10b). When oTOL is used in the bath, the CoFe alloy seems to the CoFe alloy deposited without additive (Fig. 10c). We can distinguish an acicular deposit by SEM photographs and a dark and a mat deposit by visual observation. Consequently, only saccharin can be considered as a levelling and brightening agent. The roughness of the CoFe deposits has been investigated for the ability of leveling by organic additives w8x. The working surface was 245=220 mm2. The results concerning the CoFe deposits plating with organic additives are summarized in Table 1. The Ra value represents the arithmetic mean of the profile on the entire working surface. SAC decreases a lot of roughness of the CoFe deposit, contrary to oTOL and PHTA. SAC can be considered as a leveling agent. According to Oniciu and Muresan w27x, a strong influence of the additives on the polarization curves was used as selection criteria for efficient levelling agents, but a large slope of the polarization curves is not always associated with a good levelling properties of the additive. In our case, for Co91.5Fe8.5 electrodeposition, we can affirm that SAC influences strongly the polarization curves and it can be considered as a good levelling agent contrary to phthalimide and oTOL. 3.7. CoFe deposit structure From the X-ray diffractometry analysis the structure of the binary CoFe deposits with different composition

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F. Lallemand et al. / Surface and Coatings Technology 179 (2004) 314323 Table 1 Roughness of Co91.5Fe8.5 alloy electrodeposited with and without additives Deposits CoFe CoFe CoFe CoFe without additives with SAC with PHTA with oTOL Ra (nm) 262 2 64 98

10%, we can notice a solid solution of aCo and gFe containing a fair proportion of each of the parent metals. In our case, CoFe alloys, which are electrodeposited with various additives, have the same composition Co91.5Fe8.5. Consequently, the aFe phase was not observed in all deposits. The preferential orientation of crystals in deposits is the result of a great number of variables, including a well-known tendency to continue the structure of the base metal (epitaxy). After the influence of the substrate becomes less important, the observed orientation in electrodeposits is more likely to be determined by electrolyte composition and plating conditions. In the presence of additives, the crystals may adopt a preferential orientation, which is a result of various rates of growth of various crystal faces. The difference is enhanced by preferential adsorption of foreign molecules such as additives. It is found that for all deposits, the 111 texture of fcc-aCo predominates in a large part of the diagram of Figs. 1113. In all cases, we can observe the peak of Si. Consequently, the predominance of this texture can be attributed to the same mechanism. The diagram of CoFe deposits elaborated without additive is not represented, because it is similar to the CoFe deposits found with oTOL (Fig. 11). Based on observations, CoFe alloys electrodeposited with oTOL and without additives have two similar crystalline regions: fcc-aCo and hcp- Co contrary to the CoFe films produced with PHTA and SAC. The phase hcp-Co is localized with the texture 100. Different peaks can be noticed as 200, 220, 311 and 222 of fcc-aCo. The phase hcp-Co cannot be observed for CoFe alloy deposited in the presence of SAC and PHTA. The intensity of 200, 220, 311, 222 diffraction peaks decreased in the case of PHTA. The CoFe alloy, deposited with PHTA is strongly textured 111.
Fig. 10. SEM micrographs of CoFe alloy electrodeposited in the presence of (a) SAC, (b) PHTA and (c) oTOL or without additive. Table 2 Composition of the plating electrolyte to produce Co91.5Fe8.5 alloy (mol ly1) Plating electrolyte Without additive SAC PHTA OAS H3BO3 0.4 0.4 0.4 0.4 NaCl 0.5 0.5 0.5 0.5 CoSO4 0.2 0.2 0.2 0.2 FeSO4 0.007 0.021 0.018 0.008

has been identified in a previous experiment w16x. Different CoFe alloys were produced without organic additives and various compositions in order to observe the iron content (between 18 and 6.5%) influence. It was shown that a new phase aFe could be observed when the percentage of iron is higher than 10%. Below

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Fig. 11. X-ray diffraction analysis of CoFe elaborated with oTOL.

4. Conclusions Thin films of the iron-group metals have been developed because of potential applications in microelectromechanical systems (MEMS). In this article, the kinetic and morphology of the CoFe alloy electrodeposition was studied by plating onto a copper substrate from

mixed sulfate and chloride electrolytes. The choice of organic additives has been investigated from an electrochemical behavior point of view yielding the following results: 1. In the presence of SAC, the polarization curves of cobalt and iron were shifted towards more negative values contrary to that found in the presence of oTOL

Fig. 12. X-ray diffraction analysis of CoFe elaborated with SAC.

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Fig. 13. X-ray diffraction analysis of CoFe elaborated with PHTA.

and PHTA. The PHTA and the oTOL molecules do not cause significant changes in the composition and efficiency of the codeposition. On the other hand, we have seen a different behavior in the presence of SAC vs. applied potential. The lowest efficiency can be observed with SAC contrary to with oTOL and PHTA. However, limited information was obtained about the cathodic process due to the lack of the well-defined tafel region. 2. The presence of the additives has a slight influence on the preferred orientations of the CoFe deposits. Only the CoFe films deposited with SAC can be considered as bright. 3. In our particular case, and based on empirical observations, it was noted that the presence of saccharin results in smoother, more compact and more leveled deposits as compared to phthalimide or o-toluene sulfonamide. Consequently, even though the molecular structure of oTOL is nearly of the saccharin structure, the behavior of this organic compound on the CoFe deposits were completely different. Consequently, it is very difficult to establish a relationship between the nature and the structure of addition agents and the nature of the metal being plated. We can only conclude that even if the molecule contains the sulfonamide group, it cannot be considered as an organic additive used in industrial CoFe plating baths. Acknowledgments The authors would like to acknowledge, the L.E.T.I. (Laboratory of Electronic, Technology and Instrumen-

tation) of CEA-Grenoble, the Microscopy Center and the Optic Laboratory P.M. Duffieux of Besancon for its assistance. The authors also thank the technical person S. Linget (LCMI) for her assistance throughout the AAS analysis. References
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