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BENJAMIN Depat-tamento de Quimica, Universidad SCHARIFKER



Simdn Bohvar, Apartado

80659, Caracas 1080, Venezuela

and GRAHAM HILLS University of Strathclyde, McCance Building, 16 Richmond Street, Glasgow Gl lXQ, U.K.
(Received 16 November 1982)

Abstract-The theory of thepotentiostatic current transient for three-dimensional multiple nucleation with diffusion controlled growth isdiscussed. Reliable values of nuclear number densities and nucleation rates are obtained from the analysis of the current maximum, and good agreement is obtained with experimental data for nucleation in several electrochemical systems. The termination of the nucleation process by the expansion of diffusion fields is considered, as well as the deviations from randomness observed in the distribution of nuclei on the electrode surface. INTRODUCTION The early stages of electrochemical phase transformations are usually associated with two- or threedimensional nucleation processes, the rate of which, and hence the number of nuclei SO formed, being strongly dependent on the overpotential. It is therefore important to establish the exact relationship between the overpotential and the kinetics of nucleation, either by the direct microscopic observation of the electrode Cl, 21, or by the indirect procedure of relating the current to the area of electroactive surface and thence to the total number of nucleiC3.41. In many cases of electrodeposition reactions, notably in the deposition of metals from molten salts[5, 61 or aqueous sohitions [7,8], the charge-transfer step is found to be fast and the rates of growth of mature nuclei are well described in terms of control by mass-transfer of electrodepositing ions to the growing centres. Earlier descriptions of the growth of nuclei under diffusion control assumed that the transfer of ions to individual nuclei was by one-dimensional, ie linear, diffusion[4]. However, it was later realized that, because of the small size of the nuclei, their growth would better be described in terms of localized spherical diffusion[5]. The current of growth of a single hemispherical nucleus is then zFx(2Dr) 3!2M1!2110 I ,.I = (1) 1:2 P where D is the diffusion coeficient, Lthe bulk concentration and rF the motar charge of the electrodepositing species, M and p are the molecular weight and the density of the deposited material, respectively. That this description of the growth of inditiidual nuclei is essentially correct was subsequently verified by computer simulation[9] and by monitoring the growth current of single nuclei of various metals on microelectrodes[S, 10, 1 I].

In experimental studies of electrochemical nucleation, however, single nuclei are the exception rather than the rule, and consideration of the mutual interplay of nucleation and growth processes that occur during multiple nucleation become important. Thus potentiostatic transients of, say, the three-dimensional nucleation of mercury on a macroscopic electrode of vitreous carbon[ 121 take the form shown in Fig. 1. At the beginning of each transient there is inevitably a charging current that decays during the process of nucleation and growth. The succeeding part reflects the rise In current as the electroactivc area increases. either as each independent nucleus grows in size and/or the number of nuclei also increases. During this stage of the growth of the deposit, the nuclei develop drffusion zones around themselves and as these zones overlap the hemispherical mass-transfer gives way to linear mass-transfer to an effectively planar surface. The current then falls and the transient approaches that corresponding to linear diffusion to the total area of the electrode SUrFdCe, as indicated by the broken line in Fig. 1. In previous treatments of multlple nuclealion[5, 9, 131, the assumption has invariably been made that nuclei grow indrpen&nrl~~ of each other, and that well before the current maximum the total current could be identified with the sum of individual currents. ir

where Ii r is the current at an individual nucleus i ofage r and Nis the total number of nuclei. Furthermore, if the initial nucleation is effectively instantaneous, all the nuclei would be of the same age and grow at the same rate, so that (2) could be simplified to[.5]






Fig. 1. Potentiostatlc current transients for the electrodeposition of mercury onto vitreous carbon 0.01 M Hg, (NOX), in aqueous 1 M KNIUJ and at the overpotentlals Indicated in mV. Electrode = 0.32 cm.

from area

However, detailed experimental studies of multiple nucleation combining microscopic observation of the electrode surface with current measurements[ 14,151 indicate that the rate of growth of N crystallites is significantly lower than that predicted by (3), ir it is less than the product of N and the known rate ofgrowth of a single isolated crystallite. These results therefore suggest that the growth of mature nuclei on a polynucleated electrode cannot be considered to occur independently of each other, even well before the current maximum of potentiostatic transients. In addition, the possibility of an effective decrease of the nucleation rate caused by irreversible processes near the boundary of a growing nucleus can and must be consideredC16 For the experiments shown in Fig. 1, a nucleation, Fig. 2a, plot of I us t lJ/2 for instantaneous shows good linearity. However, the currents regress to a positive intercept on the timeaxis and this intercept 1s potential dependent. Further analysis of the early stages of deposition, eg by means of log I L:S log t plots as in Fig. 2b, show that there is a transition from an I-c~~ relationship to that of lPtliz, and therefore that a progressive regime is to be detected in the early stages of the transients. This part of- the transient is described[5] by the equation

to that period in which nuclei were still being produced at a rate comparable with their growth. This picture now seems to be a general feature of nucleation in a number of systems where nuclear growth is masstransfer controlled, and the question then arises as to why the nucleation process terminates with a large proportion of the surface still un-nucleated, ie unaffected by the persistent supersaturation. It is apparent, then, that the final nuclear number density responsible for the instantaneous regime of the current transients does not correspond to the total number density of active sites, but is a consequence of the irreversible processes that occur in the nuclear growth process. That being so, it will be shown that the saturation nuclear number density, N,, contains information on both nucleation and growth rates, in contrast to the trivial limit ofthe final number of nuclei controlled by the exhaustion of active sites. The distribution of mature nuclei on the electrode surface will also be considered, as recent results indicate that their distribution is not random [17, iSI, as would be expected if nuclear growth and nucleation were mutually independent.

I(t) =


(~Dc)!M~~ ____ 1/t 3P

THE (4)



where A is the steady slate nucleation rateconstant per site and N, the number density of active sites. After the period of progressive nucleation, further nucleation is arrested and instantaneous behaviour then follows, with a certain delay, which corresponds

The physical model that accounts for the various features of the current transient for three-dimensional nucleation with diffusion controlled growth has been known for some time[5]. Nevertheless, expressions for both rising and falling parts of the transients, as well as the current maximum, have not been obtained until

Theoretical and experimental studies of multiple nucleation


Fig. 2. (a) Linear dependence between current and t I* for the middle, rising sections of the transients in Fig. 1. (b) Log-log plots of the early parts of potentiostatic transients under conditions similar to those obtained
in Fig. 1 but at lower overpotentials. The slopes of the straight line portions are l/2 and 3/2. recently. The main difficulty in the mathematical analysis is that although nucleation occurs on the plane of the electrode surface the growth of nuclei and the diffusion of depositing species extend into the bulk of the electrolyte, thus generating a 24 dimensional problem[19], intractable in terms of the Avrami theorem[20]. Up till now two approaches have been followed. In one of them[21], overlap between neighbouring centres at a height h from the substrate is considered by means of a thin layer of width dh. The true area of the 2-D projection of this layer on the plane of the substrate is then obtained by application of the Avrami theorem fot 2-D overlap. The true volume of overlapping hemispherical centres is then reconstructed through an integration with respect to h and the current transient follows from application of Faradays law. The other approach[16], which will be followed here, considers the equivalent area of plane surface towards which diffuses, by linear diffusion, the same amount of material that would be transferred, through spherical diffusion, to a hemispherical growing centre. The overlap of diffusion fields of individual nuclei is thus reduced to a 2-D problem, for which the application of Avrami theorem is exact. The current transient is obtained by considering the linear diffusion of electrodepositing species to the true area of projected diffusion fields. Thus we can consider a set of hemispherical nuclei randomly distributed on the electrode surface and growing under diffusion control, as shown in plan view in Fig. 3. A hemispherical diffusion zone radiating from each centre grows at a radial velocity such that its radius, 8, is described as a function of time by the relation:

Fig. 3. Schematic plan view of hemispherical nuclei (D) randomly distributed on the electrode surface. The surrounding circles represent their diffusion zones.

current will be given by (3) but as the radii of diffusion zones grow and overlap, replacement of material in the planes close to the electrode surface is hindered, and the only source of depositing species is that reaching the electrode perpendicularly, as in Fig. 4. The corresponding diffusive flux and growth current can then be expressed in terms of semi-infinite linear diffusion to that fraction of the electrode surface area within the circular perimeter of the growing diffusion zones. The planar area of a single diffusion zone is given by

S(t) = nS2 (t) = nkDt.


If immediately following t = 0, N centres were instantaneously nucleated per unit area, then,at a later time t, O,, = NnkDt, (7)

s(t) = (kDr),


where k is a numerical constant determined by the conditions of the experiment. At short times, the

of the area covered bv where 8.. is the fraction diffusion%nes without taking overlap into account. if the N centres are randomly distributed on the elec-





If, on the other hand, N(r) = AN,l and I),, =


is progressive,


c ANnkDtdt I0

= AN,rckDt/2.


It follows

that s[l -exp(~AN,~kDt/2)]. (15)

and k is again evaluated by taking the limit AiV,t + 0 and comparing it with (4). For progressive nucleation, k is then defined by the relation k = ; (&rcM/~)~. Fig. 4. Schematic representatmn of the growth of diffusion zones and their eventual overlap. The arrows indicate the directIons of the diffusional field durmg the growth of the


trode surface, the actual fraction be related to H,, by the Avrami

of area covered, theorem, ie

8, can (8)

0 = I -exp(-OU,,), so that from (7) B = I -exp(-NN?rkDt)


and the radial flux density through the boundaries of the diffusion zones will be given by the equivalent planar diffusive flux to an electrode of fractional area 0. Conservation of mass requires that the amount of material entering the diffusion zones is equal to the amount being incorporated into the growing nuclei and the current density to the whole electrode surface is therefore I= zFDct) 7L1,2t1!2 =s [l ~~exp(~NnkDt)].

Thus (10) and (15) describe the current transient for instantaneous and progressive nucleation. In each case, the current passes through a maximum and then approaches the limiting diffusion current to a planar etectrode. The current, I,, and the time t,, corresponding to the maximum can be evaluated[16] by equating the first derivative of the I-t relation to zero. The resulting expressions for these quantities for both instantaneous and progressive nucleation are given in Table 1. The product Ikr,,, does not contain the quantities k, k, AN, or N and is therefore a convenient diagnostic criterion of the particular form of nucleation occurring. Alternatively, the transients can be presented in non-dimensional form by plotting I/li vs t/t, and compared with theory through (20) and (24) for instantaneous and progressive nucleation, respectively, which also appear in Table 1. The theoretical non-dimensional plots arising from these equations are shown in Fig. 5.




At very short

times, 1 -exp(


1 and C= NrkDt. Nkr2 (11)

- NJrkDt)


in the limit

Nt + 0, (10) becomes (12)

I Nr-0 = .FD32C/2

and this current must be identical to that flowing to N isolated hemispherical nuclei, ie as described by (3). Equating these two expressions defines k as k = @lrcM/p). (13)

A family of potentiostatic transients for the electrochemical nucleation of lead onto a single crystal zinc oxide electrode[22] from a 50 x 10m3M solution of Pb(NO& in aqueous 1 M KNO, is shown in Fig. 6. A reduced variable plot of the data is shown in Fig. 7, from which it is evident that the nucleation of lead on ZnO follows closely the response predicted for instantaneous nucleation, ie following the onset of the potential step that nucleation is fast and on a relatively small number of active sites that are exhausted at an early stage of the process,

Table 1. Expressions

resulting from the analysis of the current maxima for instantaneous nucleation nucleation Progressive nucleation

and progressive


tin I,

NnkD zFDc (kN)12


(17) (18)

f, = y3k3D)ll I,

(22) (23) 1)

= 0.6382

= 0.4615 rFD3!4c(kAN,)!4
= 0.2598 (zF#D

= 0.1629

I2 -= I:,



1= (20) Pm

= F

( 1 - exp [ - 2.3367 (t&J2


Theoretical and experimental studies of multiple nucleation


Fig. 5. Non-dimensional

lz/l& vs t/r,plots

for (a] instantaneous nucleation and fb) progressive nucleation.


Fig. 6. Potentiostatic transients for thedepositionofPbon ZnO from 50 x 10e3 MsolutionofPb(NO,), aqueous 1 M KNO,, at the potentials indicated, in mV us XP. Electrode area = 0.033 cm*.


The treatment of the potentiostatic transient discussed above requires that the product I$, be independent of the nucleation and growth rates. Thus at a given bulk concentration of electrodepositing species K&r,,,should not vary with the overpotential for sufficiently high step potentials, for which the surface concentraton of lead ionsis effectively zero, That this is so is shown in Table 2, where the values of that product remain constant, within experimental error, over a

wide range of overpotentials. From the mean value, (64.1+ 3.1) x 10m6 A% cmW4, and the known concentration of PbzC ions in solution, the diffusion coefficient is obtained, by means of (19), as D = (0.42 & 0.02) x 10-5cm2s-. This value is in good agreement with that obtained from an I us t-l piot of the decaying portion of high overpotential transients by means of the Cottrell equation, ie D =0.46 x 10-5cm~s-i. Once it is established that the nu-






Fig. 7. Non-dimensional I/I~ CTt/t,plot ofthe data in Fig. 6 for 490 (o), SO0 (o), 510 (A),and 520 mV (A). The continuous lines correspond to (20) and (24) for instantaneous and progressive nucleation, respectively. Table 2. Analysis of the current maxima for deposition of Pb on 200 IOJI, (Acm-*) -9.2? 10.3 11.7 12.9 14.5 16.1 17.9 20.0 21.2

485 490 495 500 505 510 515 520 525

(cm 0.75 0.6 1 0.50 0.40 0.31 0.22 0.20 0.16 0.14 64.4 64.7 68.4 66.6 65.2 57.0 64.1 640 62.9

62 67 72 77 82 87 92 97

84.4 105 135 164 207 256 316 395 443

cleation is instantaneous, the nuclear number densitics at different overpotentials can be calculated from the current maxima by means of (IS), and the values thus obtained also appear in Table 2. Three-dimensional nucleation with diffusion controlled growth, a common phenomenon in the electrodeposition of metals, also obtains in some processes ofanodic film formation, especially when the deposit is a good electronic conductor. Copper sulphide is one of these1231 and thus potentiostatic transients for its electrodeposition[24] from a 10 Y 10m3M solution of NaZS in aqueous 1 M NaHCO, take the form shown in Fig. 8. The most significant feature of them is the current maxima followed by decaying portions which in all cases converge to the limiting current corresponding to linear mass-transfer of sulphidc ions to the copper substrate. A large decaying current is also observed at the beginning of each transient, due to double layer charging and possibly to adsorption-desorption processes[25], whtch obscure the nuclear growth current at short times. Nevertheless, in Fig. 9, non-dimensional plots of some of the transients

in Fig. 8 indicated that nucleation of Cu,S on Cu is progressive. A more detailed description of the phase formation processes attending the electrocrystallization of copper sulphide on copper will be presented etsewhere[24]. As a final evidence of the convenience of nondimensional plots of 12/1i vs c/t,,, for the diagnostic evaluation of potentiostatic transients for 3-D nucleatlon with diffusion controlled growth, Fig. 10 shows data obtained from several electrochemical systems. It is verified that, in all cases, one or other of the two extreme forms of nucleation considered here predominate.

SATURATION NUCLEAR NUMBER DENSITIES AND THE SPATIAL DISTRIBUTION OF NUCLEI It has been observed that an exclusion zone for further nucleation always develops around an already nucleated centre. The experimental study of this effect,

Theoretical and experimental studies of multiple nucleation


Fig. 8. Potentiostatic current transients for the electrodeposition of Cu,S on Cu from a 0.01 M solution of Na,S in aqueous 1 M NaHUJ3 and at the overpotentials indicated, in mV. Electrode area E 0.26 cm.






Fig. 9. Non-dimensional 12/I$,vs t/r,plot ofthe datainFig. 8 for67 (V)and 70 mV (0). Thecontinuous correspond to instantaneous (upper curve) and progressive (lower curve) nucleation.

within electrochemical systems, was initiated by Markov, Boynov and Toschev[28], who concluded that it was due to a local deformation of the electric field around the growing nuclei. The study was then extended to more dilute solutions[29] from which similar conclusions were drawn. Whilst the deformation of the electric field may be a factor, it will be considerably reduced by the presence of a supporting electrolyte. Even so the concentration depletion around centres growing under mass-transfer control

will remain and will reduce the probability of nucleation in the vicinity of each nucleus, as in the analogous case of surface diffusion in deposition from vapours[30, 3 11. Nucleation will therefore be confined to those active centres that have not been included within an exclusion zone. On this basis, Markov and Kashchiev[32] proposed a formalism for the derivation of the dependence of the number of nuclei on time and more recently Markov[33] obtained a solution of the problem in terms of the rate of nucleation,





Fig. 10. A comparison of the theoretical non-dimensional plots for instantaneous and progressive nucleation with experimental data of the deposition of Hg on C (Fig. I) (o), Ph on C[lOJ (0). Ag on C[27] (A), and Cu,O on Cu[26] (V).

AN, 9 and a power law for the rate of growth of the exclusion zone, which was experimentally determined in the absence of supporting electrolyte. A closed form solution for the saturation nuclear number density can be obtained from the treatment leading to the description of the current transient for progressive nucleation, as new nuclei will only develop on that fraction of the electrode surface uncovered by diffusion zones. Because of the random nature of the nucleation process, the probability that any randomly selected nucleation site had not been crossed by the perimeter of a diffusion zone is, at any time, (1 - 3). From (8) and (14), that probability can be expressed as

N, = (ANJ2kD):


The nuclear number densities integratmg the instantaneous time t, ie

at time t can be found by probabilities, (23, up to

= AN, The saturation nuclear number setting L + cc, such that N,= lim I-e N(t) = AN,


nkDr2 2




NE, is found by

gives the nuclear number density observed at long times, ie after the entire surface had been covered by nucleation exclusion zones. The effective rate of variation of the nuclear number density and its integral, together with the current transient, are shown in Fig. 11 in non-dimensional form. At a time corresponding to the current maximum, the effective rate of variation of the number density of nuclei is only 10% of its original value at t = 0, and the nuclear number density has reached 95 /,, of its saturation value, it follows that at that point the nucleation process has been virtually arrested by the nucleation exclusion zones around each growing nucleus. The inhibition of the process of nucleation within the exclusion zones introduces a correlation in the spatial distribution of nuclei, since it becomes increasingly improbable to observe a nucleus developing near an already mature nucleus, even though an active site for nucleation may exist within its exclusion zone. Thus the nearest neighbour distribution of nuclei, once the saturation nuclear number density is reached, should differ from the distribution expected for the direct exhaustion of randomly distributed active sites on the surface. If mature nuclei were randomly distributed on the surface, the distribution function of the distances between nearest neighbours would be[ 17, 341 p(r) dr = 2xN,r exp (xN,r) dr, (2%

di. (27)

It may be noted that 1, exp( - a2r) dt = (1/2a) r (l/2) = (1/2a)rr;2, for a = (AN,_lckD/2) > 0, where r is the Gamma function. Therefore the expression

where N, is the number density of nuclei on the surface and p(r)dr denotes the probability that the nearest neighbour to a nucleus occurs between r and r + dr. In order to compare experimentally determined nearest neighbour distributions with the theoretical functions


and experimental studies of multiple nucleation




Fig. 11. Non-dim&sional representation of the rate of variation of the nuclear number density, the nuclear number density, [N(t/t,)]/N,, and the current transient, i*/I&, as a [dN/dWt,)jlAN,. function of normalized time, t/t,.

on the basis of (29), it is necessary to determine the probability p (r)A r of observing the nearest neighbour within a finite interval (r, r + Ar). Thus
r2 P(r)Ar 2xN,rexp(-aN,r*) J rl Ar== r2-rl = dr,


so that


= exp(-IcN&)-exp(--nN,r:).


Figure 12 shows a comparison of theoretical histograms according to (31) with two experimentally measured nearest neighbour distributions[ 171 for the

nucleation of silver on glassy carbon from a 6 M solution of AgNOJ. It is seen from the figure that the nucleation predicted at the smallest distances by (31) is not observed in the experimental histograms due to inhibition of nucleation by the exclusion zones around each growing nucleus. In order to study further the effect of the diffusion fields around each nucleus on the spatial distribution of nuclei, we carried out a digital simulation of the process. A square was defined as the simulation area, into which nuclei were allowed to develop at randomly selected locations, using a random number generator to define the pairs of co-ordinates corresponding to their positions. The time step of the simulation was chosen in such a way as to introduce one nucleus per

Ptri a r 0.L a 0.L









Fig. 12. Nearest neighbour distribution of nuclei. Continuous histograms: (a) deposition of silver at 0.13 V,
N, = 477; (b) deposition of silver at 0.14 V, N, = 771[17]. (31). Broken histograms: distributions according to







time step. Thus the steady state nucleation rate, AN,, was equal to l/t,, where t,is the length of the time step. Around each growing nucleus a nucleation exclusion zone was allowed to develop, with a radius given by (5), ie by 6, = (kDr)/, where k is the numerical constant defined by (16) and 5 is the age of the nucleus. The radius of each exclusion zone was updated at the end of the time steps. lf, during a particular time step, the randomly selected pair of coordinates was located inside the exclusion zone of an already growing nucleus, the pair was discarded and a new time step was begun. In this way nucleation inside an exclusion zone was avoided and, as a consequence, the effective rate of establishment of new nuclei was continuously decreasing as the simulation progressed. Eventually, the entire area of the simulation would be covered by exclusion zones and the number of nuclei would thereafter remain constant. The simulation was therefore continued until the probability of the total area being covered by exclusion zones was better than 0.99, ie until no new nuclei were established after 100 consecutive time steps. At this point the nearest neighbour distribution was determined by calculating the distance separating each nucleus from any other to establish which was its nearest neighbour, and the distribution was then displayed as a histogram for comparison with experiment. Figure 13 shows the results of simulations related to two experimentally measured nearest neighbour distributions[17]. Here the nucleation rate, AN,. was taken as 7.7 x 103 s-l cm- for nucleation at u = 0.13 V and 20 x lo% cm- at q = 0.14 V. These. values can be deduced from the work of Milchev et al.[17] either from their N-t curves or from the N, values through (28) above. The value of the diffusion coefficient of Ag + in solution used in the simulations was D = 1 x 10-5cmzs- and that of k, 1.66, was calculated from the concentration of silver ions in solution and the known values of M and p for silver. A comparison of Figs 12 and 13 shows that the simulated histograms reproduce better the experimen-

tal results than the theoretical histograms deduced from (31), especially at the smaller distances. Also, the probability maximum is displaced to somewhat larger distances as compared to the predictions of (31), reflecting the inhibitory effect of the exclusion zones. It is also interesting to note that, although the number density of active sites for nucleation in the simulations is, in principle, infinite, the saturation values of the nuclear number densities obtained from them are close to the experimentally oljservcd values, confirming that exclusion zones are of major importance in the arrest of the process of nucleation under these conditions of mass-transfer controlled growth of nuclei. In spite of the success of the simulations in reproducing qualitatively the nearest neighbour distribution of nuclei, there are still important quantitative differences between them. One possible reason of discrepancy may be the absence of supporting electrolyte in the experiments reported by Milchev et nl.[17]. It may be thought that its presence is irrelevant at the high concentration of electrodepositing species (6 M) used, but it is a well known fact that masstransfer is enhanced in the absence of a supporting electrolyte, due to the migration of ions in the electric field. Also, the large concentration gradients generated in concentrated solutions promote the onset of natural convection, thus increasing even further the rate of mass-transfer. These two eftects increase the rate of growth of the exclusion zones, shifting the experimental nearest neighbour distributions to longer distances. It is therefore convenient, in order to minimize the effects of migration and convection, to determine the nearest neighbour distributions from dilute solutions of electrodepositing species and in the presence of an excess supporting electrolyte. This work is now in progress and its results will be. presented elsewhe35]. One further aspect, relating the simulations to the theory represented by (+(28), deserves comment. The nuclear number density as a function of time can be obtained from (26) which, after integration. becomes[ 361





Fig. 13. Nearest neighbour distribution of nuclei. Continuous histograms: experimental results as in previous figure. Broken histograms: results of simulations which produced N, values of (a) N, = 482 and (b) N, = 800 (for details see text).


and experimental


of multiple



Fig. 14. Nuclear

number density as a function of time. Continuous line according to (32). (o), (V): results from simulations carried out under the same conditions as in Fig. 13.


= N,erf-

@ 1z at) 2

Il. 12. 13. 14. 15. 16. 17.

is erf the error function and a = (AN, nkDj2) I2 . A non-dimensional plot of (32) is shown in Fig. 14, together with simulated results for the evolution of the nuclear number density with time under different conditions. The excellent agreement between the simulated results and the theoretical curve


thus verifies that the simulation theory are self-consistent.





of us (B.S.) thanks the Conse~o National de Investigaciones Cientificas y Tecnol6gicas (CONICIT) of Venezuela for a reasearch grant during which part of this work was carried out.

18. 19. 20. 2 I.

1. R. Kaischew

2. 3. 4. 5. 6. 7. 8. 9.

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32. 33. 34. 35. 36.

G. J. Hills, A. Kaveb Pour and B. R. Scharifker, Electrochim. Acta 28, 891 (1982). G. A. Gunawardena, G. J. Hills and I. Montenegro, Faraday Symp. Chem. Sot. l&90 (1978). D. Kashchiev and A. Milchev, Thin Solid Films 28, 201 (1975). S. Toschev, A. Milchev and E. Vassileva, Electrochim. Acto 21. 1055 119761. A. Milchev. B. i. S&rifker and C. J. Hills,J. electroanol. Chem. 132, 277 ( 1982). G. A. Gunawardena, G. J. Hills, I. Montenegro and B. R. Scharifker, J. electroan& Chem. 138, 225 (1982). A. Milchev, E. Vassileva and V. Kertov. J. electroanal. C-hem. 107, 323 (1980). A. Milchev, Electrochim. Acta 28, 947 (1982). S. Fletcher and D. B. Matheus, J. appl. Electroc~m. 11, 1 (1981). M. Avrami, J. them. Phys. 7,1103 (1939); 8,212 (1940); 9, 177 (1941). E. Bosco and S. K. Rangarajan, b. electroanal. Gem. 1~. 213 (1982). L. M. Peter and 8. Scbarifker, unpublished results. M. Sato, Electrorhim. Acto 11, 361 (1966). R. Rugeles, J. MOZOtdand B. Scharifker, to be published. E. Bosco and S. K. Rangarajan, J. them. Sot., Faraday Trans. I77, 1673 (1981). S. Fletcher, R. G. Barradas and J. D. Porter, J. electrochem. Sot. 125, 1960 (1978). G. A. Gunawardena, G. J. Hills and I. Montenegro. J. electroanol. Chem. 138. 241 (19821. 1. Markov, A. Boynov and S.Toschev, Electrochim. Acta IS. 377 119711 I. Markovand S. Toschev, Electrodep. andSurJ:Treotmenr 3, 385 (1975). I. Markov, Thin Solid Films 8, 281 (1971). M. J. Stowell, Phil. Mag. 21, 125 (1970). I. Markov and D. Kashchiev, J. Cryst. Growth 13, 131 (1972); 16, 170 (1972). I. Markov, Thm Solrd Films 35, 11 (1976). S. Chandrasekhar, Reu. mod. Phys. 15, 1 (1943). A. Milchev, personal communication (1982). I. Markov and E. Stoycheva, Thin Solid Films 35, 21
~I~ I -I