ELSEVIER

Journal of Electroanalytical

Chemistry

397 (1995) 11 1~1 I8

Morphology and structure of nickel nuclei as a function of the conditions of electrodeposition

E. Gbmez, R. Pollina, E. Vall&
Departanzent de Quhica Fhica, Faculfat de Quimica, Unicersitat de Barcelona, Marti i FranquPs 1. 08028 Barcelona. Spain Received 3 January 1995; in revised form 2 May 1995

Abstract on a vitreous carbon electrode from chloride baths was performed at several pH values by the temperature and/or the nickel concentration), bath composition and deposition time (particularly at low overpotentials) on the morphology of nickel nuclei were analysed. Before coalescence and during the early stages of deposition, the morphology of the nuclei was influenced by the bath composition. When solutions with a high concentration of chloride ions were used. a characteristic star-shaped morphology was obtained which was attributed to the adsorption of chloride complexes, This morphology was related to the results obtained from impedance spectroscopy diagrams.
Keywords: Electrodeposition conditions; Impedance spectroscopy; Texture; Morphology; Nickel nuclei

A study of nickel

nuclei

deposited

(1 < pH < 4.5). The effects of growth rate (affected

1. Introduction There have been many studies of nickel electrodeposition from a variety of electrochemical baths, and the morphology related and texture of the final process deposits have been to the dominant in each case [l-19].

It is generally accepted that the growth of deposits during electrodeposition is influenced first by the substrate (epitaxial growth) and, when this influence disappears, by the deposition conditions (bath composition, applied current or potential and pH). When deposition takes place on an amorphous substrate, epitaxial control does not occur and orientation of the deposits depends only on the deposition conditions. Although there have been many observations of nickel electrodeposits using both transmission and scanning electron microscopes, they have provided little information on the development of the nuclei and the factors that affect it. Nickel deposition in a chloride medium is an inhibited complex process [20]. In previous studies the effects of several experimental variables (Ni(I1) and Cl- concentration, pH, overpotential or applied current density and substrate) were analysed as a function of the quality of the resulting deposits. Ranges for these conditions were established such that acceptable deposits were obtained. Owing to the obvious dependence of the final deposit on the deposition conditions, we were interested in
0022.0728/95/$09.50 0 1995 Elsevier Science S.A. All rights reserved SSDl 0022-072X(95)04202-4

analysing the development of the nuclei under the influence of experimental factors. The aim of this study was to establish the way in which the species present in the solution affect the growth of the nuclei and to establish which species were responsible for certain types of growth. The shapes of the first nuclei were analysed for different deposition conditions, with the proviso that the nuclei did not overlap completely. Vitreous carbon electrodes were chosen for this study because of the lower nucleation rate on carbon compared with metallic electrodes. Thus the overlap of the nuclei can be delayed such that the size of the nuclei is increased. Moreover, epitaxial control by the substrate is avoided with vitreous carbon.

2. Experimental

details

NiCl, 6H,O, NiSO, 6H,O and NaCl (analytical grade) were obtained from Merck. The solutions were freshly prepared with water from a Millipore Mini-Q system. Ni(I1) solutions were prepared from chloride or chloride + sulphate salts with Ni(I1) concentrations ranging from 0.5 to 2 M. When necessary the pH was adjusted by suitable HCl or NH,OH additions. The temperature was kept constant at 20C except in investigations of the effect of temperature when a Haake D8 cryostat was used.

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A conventional thermostated three-electrode cell was used. The working electrode was a Metrohm vitreous carbon rod (diameter 2 mm), which was polished to a mirror finish before each run using alumina of different grades (3.75. 1.87 and 0.3 km) and cleaned ultrasonically for 2 min in water. The surface state of the electrode was monitored by optical microscopy using an Olympus PMGC3 metallographic microscope. A rotating-disc electrode (RDE) with an iron rod (2 mm diameter) in a Teflon support was used for the impedance cxpcriments. The iron working electrode was polished to a mirror finish using diamond of different grades (6, 1 and 0.25 pm> and washed ultrasonically for 2 min in water. The counter-electrode was a nickel sheet (Johnson Matthey 99.99%) and the reference electrode was a Ag lAgC1 from Metrohm, mounted in a Luggin capillary containing 1 M NaCl. Voltammctric and potentiostatic experiments were carried out using a Belport 105 potentiostat together with a PAR 175 signal generator and a Philips PM 8133 X-J recorder. The galvanostatic measurements were obtained using a PAR potentiostat model 273 controlled by a Tandon 386 SX20 computer. The impedance spectra were obtained using a Schlumberger 1255 frequency-response analyser linked to an EG & G potentiostat model 273. The impedance was measured between 10 and 5 X 10e4 Hz. The morphology of the deposits was examined using either a Leica Cambridge Stereoscan S360 or a Hitachi S2300 scanning electron microscope. The microstructure of the deposits was examined using a Hitachi H800NA transmission electron microscope (TEM) at an accelerating voltage of 200 kV. The specimens for the TEM studies were cross-sections of deposited electrodes. The deposits were protected by coating the electrode surface with an adherent wax film. Then the electrode was cross-sectioned, polished with diamond paste and ion milled (argon). The samples were examined directly without using a replica.

(a)

j t mA Cm

I : / ,\
-0.5

(7

E/V

-1

-2o--

b)

j/mAcm-2

Fig. 1, (a) Cyclic voltammogram of 0.5 M NiCI, solution (pH 3; c = 50 mV 5-l at lower limits of -1080 mV (-----I and - 1480 mV (b) potential step transients for nickel deposition from -SO0 ( ---_); mV to (a) -910 mV, (b) -930 mV, and (c) -985 mV in 0.5 M NiCI, solution (pH 3).

3. Results Our previous studies of nickel deposition on vitreous carbon in chloride media [20,21] showed voltammetric curves with a complex reduction peak (Fig. l(a)) which was related to an inhibition process. Potentiostatic experiments at the optimum conditions established previously (0.5 M NiCl, and pH 3) showed that at low overpotentials the j-t transients had a normal dependence on potential with a monotonic increase in current with time (Fig. I(b), curve (a)), leading to a compact bright deposit. Morphological studies revealed that the deposition began with dense polyhedrical nuclei of hemispherical symmetry, leading to a compact cauliflower-like deposit [20]. When the overpotential was increased, the current de-

creased after a certain time (Fig. l(b), curve (b)). At higher overpotentials the j-t curve showed a clear first peak followed by a sharp fall and posterior growth (Fig. l(b), curve (c)). Samples deposited in this way had flat black inhibited deposits. It was established that Hads was present throughout the potential range but it did not have a deleterious effect on the growth of deposits. However, when high overpotentials were applied, the local pH varied and nickel hydroxides precipitated owing to the sharp increase in hydrogen production. The hydroxide precipitation was related to the steep decrease in current observed in the j-t transient. However there was a range of conditions where this inhibition was delayed. As the morphology of the final deposit depends strongly on the experimental conditions, an analysis of the morphology and shape of the nuclei before coalescence was made varying both electrochemical and solution composition parameters. 3.1. Influence of overpotential or current density in the potena monotonic

A number of experiments were performed tial range where the j-t transients showed

increase in current, always at potentials at which hydrogen evolution did not occur on the vitreous carbon electrode. A series of experiments were performed in which the deposition charge or the deposition time was kept constant. As expected, at a fixed charge, high overpotentials induced a large number of nuclei whereas for low overpotentials fewer nuclei of larger size were obtained. In the fixed charge experiments (Q = 5 mC>, the nuclei obtained in the potential range between - 750 and - 9.50 mV have a radial structure and a polyhedral shape (Fig. 2). Similar nuclei were obtained using galvanostatic deposition at low current densities (j < 5 mAcm_*), for which the E-t transient shows the typical nucleation spike followed by a stationary potential value. As the deposition time is increased, the nuclei become more structured as a consequence of either the different growth rates of the crystallite facets or the adsorption of H Ods on the deposited nickel. The adsorbed H slowly evolved to H? at these potentials [22-241. When potentials more negative than - 1000 mV are used and the j-t transient corresponds to a clearly inhibited process, changes in the deposition process are observed. The first nuclei obtained quickly coalesce to a thick passivated film (cracked film in Fig. 3) whose structure is difficult to observe. However, a second nucleation stage can bc seen in this film. This stage, which is less extended owing to the high coverage of the surface by nickel hydroxides, corresponds to hemispherical nuclei at short deposition times which can be seen as rounded nuclei on the cracked film in Fig. 3. The presence of precipitates on the electrode reduces the number of nucleation sites so that very few nuclei grow to a considerable size in a short deposition time owing to the high overpotential. When high growth rates arc observed, growth does not take place in preferential directions and spherical nuclei are obtained. However, at longer deposition times in these conditions the final deposits are cracked films [21] composed of star-

Fig. 3. Scanning electron micrograph of a nickel deposit obtained 0.5 M NiCI, solution (pH 3): 40 s at - 1010 mV; Q = 24 mC.

from

shaped crystallites owing to the formation of nickel hydroxyl species which inhibit the growth in some directions. In galvanostatic deposition, at j > 5 mA cm- the E-t , curves display a narrow spike followed by stabilization corresponding to growth of the initial nickel deposited and then the evolution of the potential to more negative values and a new stationary value at which hydrogen evolution and nickel deposition take place simultaneously. When the deposition follows this type of E-t curve, the morphology of the deposits is similar to that obtained using potentiostatic techniques at potentials more negative than - 1000 mV. On the basis of these results, the influence of the remaining parameters on the formation of nickel crystallites was studied potentiostatically mainly at low overpotentials at which monotonic j-t transients are obtained. 3.2. Temperature effects

Fig. 2. Scanning electron micrograph of a nickel deposit obtained 0.9 M NiClz solution (pH = 3): I5 min at -770 mV; Q = 5 mC.

from

Nickel deposition was studied at different temperatures to determine the sequence in which the morphology of the nuclei was modified. The temperature range selected was 5-45C. Although the increase in temperature advances the onset of deposition, it does not extend the relative potential range in which the inhibition processes are not clearly manifested. As the temperature increases the process may take place more easily and at a higher deposition rate, but this temperature increases is insufficient to raise the solubility of the alkaline nickel salts formed at the interface between the deposit and the Ni solution during the process. The increase in local pH leads to the precipitation of these hydroxyl species. At these temperatures the deposition process begins at lower potentials but inhibition also occurs sooner. Polyhedral nuclei are obtained at all temperatures, with more structured nuclei at low growth rates. The scanning electron micrographs were used to estimate the growth rate L:~of nuclei; uZ was evaluated from the change in the size

I14 Table 1 Effect of temperature T/C 10.4 20.0 29.2 39.5

E. GBmez et al. /Journul

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Chemistry 397 (1995) III-118

T on the growth rate u, of the nickel nuclei 10 cg /cm s- 0.36 I .6 3.0 8.3

of the nuclei with increasing deposition time (Table I). At a fixed potential, it was found that the growth rate increased on increasing the temperature but the shape of the nuclei did not show any structural modifications. 3.3. Effect of Ni(ll) concentration Since more spherical nuclei were expected with increasing growth rate, experiments were performed at a higher concentration (2 M NiC12). Surprisingly, the nuclei deposited from 2 M NiCl, solution are not spherical but star-shaped under all conditions (Fig. 4). Two series of experiments were performed, one analysing the effect of varying the applied potential while keeping the charge constant (Q = 5 mC>, and the other studying the potentiostatic deposition at several deposition times. In these experiments the nuclei became denser as the overpotential increased, and the edges became sharper as the deposition time increased. This kind of morphology can be related to the possible adsorption of species present in solution during growth of the initial cluster. In order to determine the extent to which the presence of chloride ion was responsible for the growth of the nuclei in characteristic directions, the extra chloride ion was replaced by a sulphate ion, maintaining the total Ni(I1) concentration at 2 M. Solutions of 0.5 M NiCl, + 1.5 M NiSO, at pH 3 were used. Potentiostatic j-t transients for this solution have a similar shape and current values to those obtained for the
Fig. 5. Scanning electron micrograph of a nickel deposit obtained from 0.5 M NiCI, + I.S M NiSO, solution (pH 3): 100 s at -830 mV; Q= 5 mC.

chloride solution, but are shifted towards more negative potentials. The difference in characteristic potentials for chloride and sulphate media has been explained on the basis of the different activity coefficients in sulphate and chloride solutions [25,26]. Morphological studies show that, even at very low overpotentials and/or high deposition times, the nuclei never display an edged morphology. Instead, they are always dense polyhedra (Fig. 5). However, when the deposition is performed from a solution containing 0.5 M NiCl, and NaCl salt to give a chloride concentration of 4 M, the nuclei have the characteristic star-shape (Fig. 6). This result demonstrates that the excess chloride in the medium induces changes in the nickel growth. Deposits obtained after coalescence are also different. When deposited from chloride + sulphate solution, they have characteristic cauliflower morphology (Fig. 71 similar

Fig, 4. Scanning electron micrograph of a nickel deposit obtained from 2 M NiCI, solution (pH 3): 100 s at -720 mV; Q = 5 mC.

Fig. 6. Scanning electron micrograph of a nickel deposit obtained from 0.5 M NiCI, + 3 M NaCl solution (pH 3): 400 s at - 860 mV; Q = 5 mC.

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115

Fig. 7. Scanning electron micrograph of a nickel deposit obtained from 0.S M NiClz + I.5 M NiSO, solution (pH 3): 70 s at - 880 mV; Q = S mC.

Fig. 9. Transmission electron micrograph of nickel crystallites from 2 M NiCI, solution (pH 3): 300 s at -730 mV.

obtained

3.4. Effect of pH Several solutions were prepared with pH values in the range 1.0-4.5 and all other conditions kept constant. The overpotential used for each potentiostatic deposition was selected so that the shape of j-t transients and the charge were kept constant during the experiments. A direct comparison of morphological results obtained at different pH values is possible in this pH range [20]. As expected, polyhedral nuclei were deposited from 0.5 M NiCI, solution and 0.5 M NiCl, + 1.5 M NiSO, solutions throughout the potential range analysed and all the pH values studied. When 2 M NiCI, solutions were used, the nuclei were star-shaped for all pH values within the range (Fig. 10); however, at lower pH values the nuclei were more rounded with smoother edges. 3.5. impedance measurements

to that obtained from the 0.5 M NiCl, solution, whereas deposits from 2 M NiCl, or 0.5 M NiCl, + 3 M NaCl solutions have a sharp-edged morphology (Fig. 8). The nickel crystallites, imaged by TEM without special preparation, are star-shaped where their hemispherical envelope is penetrated by acicular crystals (Fig. 9). Selected-area diffraction studies of the crystallites showed spotty diffraction rings which revealed their polycrystalline nature and the very small size of the crystalline domains. Studies of the crystallites using convergent beam electron diffraction with a spot size of 2 nm showed different orientations when different points on the crystallite were chosen, although no preferential orientation was found. Despite the different final morphology, these results are in good agreement with those obtained for nickel deposited from 0.5 M NiCl, [27].

Two sets of impedance measurements were obtained using solutions with a fixed Ni(I1) concentration and a

Fig. 8. Scanning electron micrograph of a nickel deposit obtained from 2 M NiCI, solution (pH 3): 2 min at -814 mV.

Fig. 10. Scanning electron micrograph of a nickel deposit obtained from 2 M NiCI, solution (pH 4.3: 160 s at - 685 mV; Q = 5 mC.

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Chemistry 397 (199.5) II l-1 18

250 : (4 zoo-

150-

IOO-

5O-

-E/mV

O10 -54 SC

oooL
600 700 800

11
d)

250 : 03

C)

i
900 1000

-E/mV Fig. Il. Steady-state polarization curves for nickel deposition onto an iron electrode (area 0.03 I4 cm from solutions of various compositions ) (pH 3): (a) 0.5 M NiC12 + 1.5 M NiSO,; (b) 2 M NiCI,; (c) 0.5 M NiCl,; (d) 0.5 M NiCI, + 3 M NaCl. Rotation rate, 3000 rev min- .

250

w
i

variable chloride content, one at 0.5 M Ni(I1) (from either 0.5 M NiCl, or 0.5 M NiCl, + 3 M NaCl solutions) and the other at 2 M Ni(I1) (from 2 M NiCI, or 0.5 M NiCl, + 1.5 M NiSO, solutions). Since similar behaviour has been found for nickel electrodeposition from a chloride medium onto different substrates (vitreous carbon, nickel, iron and platinum electrodes) [27], the impedance measurements were made on an iron electrode to ensure the formation of more adherent deposits. The polarization curves obtained are shown in Fig. 11. They show that the presence of excess chloride in the solution activates the electrodeposition process, i.e. at a given potential the deposition is easier from solutions with a high chloride content. The corresponding impedance plots for a fixed current of 0.1 mA are shown in Fig. 12. The impedance plot for a 0.5 M NiCl, + 1.5 M NiSO, solution (Fig. 12(A)) shows a capacitive loop (100 Hz) and an inductive feature (below 1 Hz). When the experiment was repeated using a solution with the same Ni(KI) concentration but containing only the chloride salt (2 M NiCl,), two clear inductive loops were detected (Fig. 12(B)). Thus it is evident that the excess chloride ion has an influence on the electrodeposition process.

__

250

(4

Fig. 12. Complex plane impedance polarization curves

plots at points A, B, C and D on the

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Differences in the impedance plots were also observed for solutions containing 0.5 M Ni(I1) and variable chloride concentrations. For 0.5 M NiCl, solutions, a single inductive loop followed by a capacitive loop was obtained (Fig. 12(C)); the latter is related to inhibition of the process by adsorbed hydrogen. However, when 0.5 M NiCl, + 3 M NaCl solution was used, the impedance plot showed a second loop at very low frequencies (below 4 mHz) (Fig. 12(D)). This second loop in Figs. 12(B) and 12(D) is related to anion desorption when excess chloride is present in solution. When the impedance diagrams were recorded at currents above 0.1 mA, the second inductive loop gradually became smaller and eventually disappeared.

4. Discussion A fundamental electrochemical and morphological study of the initial formation of nickel crystallites on vitreous carbon has shown that experimental conditions such as overpotential, current density, temperature and bath composition influence the growth process from the early stages until coalescence. The nuclei deposited from solutions containing either 0.5 M NiCl, or sulphate show a radial structure for short deposition times. It is known [22-241 that these nuclei develop polyhedral structures as a consequence of the different growth rates of the crystallite facets, and that this is also influenced by the different adsorption capacity of the hydrogen produced during nickel deposition. In these conditions the presence of either adsorbed hydrogen or complexes in solution does not seem to affect the growth of nickel deposits, so that coherent and compact deposits are obtained at potentials less negative than _ 1000 mV. When the crystal growth is faster (application of sufficient overpotential or current density), the anisotropic distribution of the surface Gibbs energy is minimized [24] and, in addition, Hads evolved to hydrogen more easily, allowing the crystallites to become denser and polyhedral forms to become spherical. However, local precipitation of nickel hydroxides at high overpotentials or high current densities has a dramatic effect on nickel growth. In contrast, nuclei formed at short deposition times from solutions with high chloride content develop into star-shaped crystallites with sharp edges. Such a characteristic growth mode is due to the species present in the bath. In this case, the possibility of direct adsorption of chloride anions is rejected in this potential range. Many different nickel complexes can appear in nickel solutions at different pH values [28]; Ni(I1) can be present in solution in the form of hexaquo-nickel complexes when the solution pH is very low. At a pH near 3 water molecules of the coordination sphere may deprotonate quickly leading to the formation of aquo-hydroxy nickel

complexes. Moreover, deprotonation is known to labilize the H,O in the coordination sphere, thus facilitating the incorporation of other ligands such as OH- or Cl-. Therefore chloro-hydroxy nickel complexes may exist at high chloride ion concentrations. The participation of sulphate in the nickel coordination sphere is less likely, and only aquo or aquo-hydroxy nickel complexes are formed in sulphate media. The different morphology observed in nickel crystallites obtained in baths with high chloride contents may be related to the predominant existence of chloro-hydroxy nickel complexes in solution. These complexes adsorb on nickel crystallites and either hinder or favour growth of the deposit in certain directions. These complexes are formed extensively in solutions with high chloride concentrations or when the ratio of chloride to nickel in the solution is high. The suggestion that adsorption of chloro-complexes is responsible for this characteristic growth is in good agreement with the morphology observed for nickel crystallites deposited from 0.01 M NiCl, + 1 M NaCl solution [29]. Nickel crystallites with a star-shaped morphology were also obtained from this solution. However, under conditions where hexaquo-nickel complexes are the main form of nickel (pH < 1) and the existence of hydroxychloro complexes is not favoured, the nuclei obtained are more polyhedral and rounded. The results of impedance spectroscopy can also be interpreted in terms of the role played by these chloro-hydroxy nickel complexes. The impedance diagrams for solutions investigated have a common inductive feature. This first inductive loop has been related to the monovalent intermediate NiOH,,, proposed in the mechanism for nickel deposition [30]. In addition to this feature, a second inductive loop appears at low frequencies for solutions with a high chloride concentration; it is related to a desorption process [30,3 11. When there is sufficient chloride in solution to allow the formation of chloro-hydroxy complexes, they adsorb on the electrode and their desorption causes the appearance of the second inductive loop in the impedance diagram. The adsorption of these complexes can be prevented by using higher current densities whereupon the second inductive loop disappears from the impedance diagrams. Thus the results obtained from the impedance measurements also imply that a mechanism for nickel deposition from a bath with a high chloride content must take into account the presence of chloro-nickel complexes as adsorbed inhibiting agents. In view of the reproducibility of all these features as well as the large differences in the morphologies of crystallites obtained from the various baths, the results indicate the existence of different adsorption processes in the deposition mechanism. The prevalence of these mechanisms depends on the bath composition. When conditions are favourable for the formation of the chloro-hydroxo complexes, these species produce struc-

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tural modifications in the nickel crystallites. However, whatever the characteristic morphology, the structural analysis did not reveal the preferential growth orientations expected on vitreous carbon [ 11,141. In conclusion, the deposition parameters (temperature, overpotential, current density) affect the morphology of the deposits on an amorphous substrate, even in the early stages. However, bath composition has the strongest influence, with the presence of species that may adsorb on the deposit being particularly important. These species may be present either in the freshly prepared bath (chloro-hydroxy complexes) or may be formed during the electrodeposition process (NiOH,,,, Hads, Ni(OH), etc.).

l81 J. Amblard, M. Froment and N. Spyrellis, Surf. Technol., S (1977)

205. [91 J. Amblard, 1. Epelboin, M. Froment and G. Maurin, J. Appl. Electrochem., 9 (1979) 233. J. Appl. Electrochem., 12 (1982) [IO1 8. Nayak and K. Karunakaran, 323. [III J. Amblard, M. Froment, G. Maurin, D. Mercier and E. TrevisanPikacz, J. Electroanal. Chem., 134 (1982) 345. [121 M.Y. Abyaneh. Electrochim. Acta, 27 (1982) 1329. [I31 0. Teschke and D. Menez Soares, J. Electrochem. Sot., I30 (1983) 306. [141 J. Amblard, M. Froment, G. Maurin, N. Spyrellis and E. TrevisanSouteyrand, Electrochim. Acta. 28 (1983) 909. [ISI M.L. Lain and D. Pletcher, Electrochim. Acta, 32 (1987) 99. 24 (1988) [I61 R. Ragauskas and V. Leuksminas. Sov. Electrochem., 675. [I71 A.A. Sambi and V.B. Sing, J. Electrochem. Sot., I36 (1989) 2950. 1181C. Kollia, N. Spyrellis, J. Amblard, M. Froment and G. Maurin, 1. Appl. Electrochem., 20 (I 990) 1025. [191 A.A. Vikarchuk, Sov. Electrochem., 28 (1992) 805. 23 001 E. Vallts, R. Pollina and E. Gomez, J. Appl. Electrochem., (1993) 508, and references cited therein. [211 E. G6mez, C. Muller, R. Pollina, M. Sarret and E. VallCs. J. Electroanal Chem., 333 (1992) 47. Ed A.K.N. Reddy, J. Electroanal. Chem., 6 (1963) 141. [231 N.A. Pangarov, J. Electroanal. Chem., 9 (1965) 70, and references cited therein. [241 E.I. Girargizov, Oriented Crystallization on Amorphous Substrates, Plenum Press, New York, 199 I. WI J. Yeager, J.P. Gels, E. Yeager and F. Hovorka, J. Electrochem. Sot., 106 (1959) 328. [261 I. Epelboin, M. Joussellin and R. Wiart, J. Electroanal. Chem., 1 I9 (1981) 61. [271 E. G6mez, R. Pollina and E. Vallts. J. Electroanal. Chem., 386 (1995) 4s. [281 R.M. Smith and A.E. Martell, Critical Stability Constants, Vol. 4, Plenum Press, New York, 1976. [291 E. Gomez, C. Muller, W.G. Proud and E. Valles, J. Appl. Electrochem., 22 (1992) 872. [301 R. Wiart, Electrochim. Acta, 35 (1990) 1587, and references cited therein, [311 E. Chassaing, M. Joussellin and R. Wiart, J. Electroanal. Chem.. IS7 (1983) 75.

Acknowledgements The authors are indebted to the Servei de Microscbpia i Espectroscbpia of the Universitat de Barcelona for help with the SEM and TEM studies. They gratefully acknowledge financial assistance from the Comision de Investigacion Cientifica y Tecnica (Project MAT 94-1338).

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