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The development of theoretical models for multiple nucleation with diffusion-

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Theoretical and Experimental Advances in Electrodeposition, 2008: 1-23

ISBN: 978-81-308-0224-4 Editor: Luis Humberto Mendoza Huizar

The development of theoretical

1 models for multiple nucleation

with diffusion-controlled three-
dimensional growth
D. Mazaira, C. Borrás, J. Mostany and B.R. Scharifker
Departamento de Química, Universidad Simón Bolívar, Apartado 89000
Caracas 1080A, Venezuela

Abstract
Current transients arising from multiple nucleation
and growth have been of interest since the development
of potentiostatic techniques for the study of the
kinetics of electrochemical processes in the mid 20th
Century. While in many instances rigorous theories
are available, the description of three-dimensional
diffusion-controlled growth electrocrystallization
processes has been particularly controversial; the
major difficulty has been that nucleation occurs on
the electrode surface while phase growth and mass
Correspondence/Reprint request: Dr. B. Scharifker, Departamento de Química, Universidad Simón Bolívar
Apartado 89000, Caracas 1080A, Venezuela. E-mail: benjamin@usb.ve
2 D. Mazaira et al.

transport extend towards the bulk of the solution. Planar diffusion zones were
introduced in the early ’80s; these are projections of the locally spherical
diffusion fields around individual growing centers onto the plane that facilitate
describing the kinetics of the overall process as a two-dimensional phase
transformation via the Avrami theorem. Later generalizations were aimed to
obtain a detailed description of the kinetic processes through elucidation of
nucleation rates and the number densities of active sites on the surface.
Considering then diffusion zones as interacting discs with time-dependent
radii, several formulations have been developed around the so-called standard
model for multiple nucleation with diffusion-controlled three-dimensional
growth. Here we present a critical account of these developments, indicating
their particular features as well as their advantages and pitfalls. We show that
a major difficulty persists for the comprehensive description of the process
within the standard model, namely the unfeasible consideration of a uniform
height for all diffusion zones, which is required for proper consideration of the
process in analogy to a two-dimensional transformation. Through numerical
simulations of the Monte Carlo type we illustrate that a hierarchical model of
overlap, with earlier diffusion zones prevailing over later ones, may lead to
overcoming this major limitation of the standard model.

1. Introduction
1.1 Electrochemical nucleation
The study of electrochemical phase formation processes is a matter of
intense current interest; detailed knowledge of the mechanisms involved is
needed for current and envisaged developments in energy conversion and
storage, electrocatalysis, and in general for the development of nanostructures.
Phase formation processes generally occur by way of nucleation and growth
mechanisms. Under thermodynamic conditions ensuring the viability of a
phase transformation, nuclei are stable structures arising from the clustering of
atoms or molecules constituting centers for the growth of the transformed new
phase. In general phase transformations may arise from changes in pressure,
temperature, compositon or, in electrochemical sytems, by changes of the
electric potential, driven by charge transfer reactions. Hence nuclei for the
formation of a new phase may arise at the interphase between ionically and
electronically conducting phases during the course of electron transfer
reactions [1]. Thus depending on the electrochemical conditions allowing the
formation of a new phase, nuclei will arise on the electrode surface at a certain
rate. Furthermore, clustering processes occur heterogeneously on the electrode
surface, hence they will most likely appear on low energy locations such as,
e.g., surface defects, or active sites on the surface. The new phase propagates
from these centers, growing through incorporation of ions from solution via
charge transfer reactions [1].
The development of theoretical models 3

In broad terms we may classify the growth of nuclei into two distinctive
categories, either limited by the rate at which ions may incorporate to the new
phase, i.e., charge-transfer controlled, or limited by the rate of mass transport
of depositing species from the bulk of the solution to the electrode surface, i.e.,
diffusion controlled [2]. For nuclei developed to sufficiently large sizes during
deposition of most metals from their ions in aqueous solutions or molten salts,
the rates of charge transfer and incorporation of discharged species into the
lattice of the deposited phase are fast in relation to mass transport from
solution to the surface of growing centers, hence diffusion control prevails.
It is often convenient to carry out experimental studies of electrodeposition
processes at constant electrode potential. Under such conditions it is expected
that the rates of charge transfer and in particular the rate constant for the birth
of nuclei on the electrode surface remain constant. The number of nuclei
formed at different times after imposing potentiostatic conditions can be
directly determined from microscopic observation of the electrode surface. It
may be also established from the current response following potential steps,
associating the current to the number and growth rate of the centers.
Given the molar volume of the deposit, the volume of a single growth
center at a given time t may be determined from the electric charge transferred
up to that time from Faraday’s law. The instantaneous growth rate of a single
center is therefore directly given by the electrical current. Then for diffusion
controlled growth and assuming hemispherical symmetry, the current is given
by [3]:

(1)

where F is the molar charge transferred during the electrodeposition process,

A and r0 are the surface area and radius of the hemispherical growth center,
and D and c are the diffusion coefficient and bulk concentration of the
electrodepositing species in solution, respectively. The first term in (1)
describes the steady state radial current to the hemisphere whereas the second
term corresponds to the Cottrell transient current to a plane surface. Owing to
the very small sizes from which they originate, nuclei may be considered as
ultramicroelectrodes for which the steady state condition is swiftly attained [4],
and the first term predominates over the second, thus we may consider that to a
good approximation that [5],

(2)
4 D. Mazaira et al.

For a hemisphere A = 2πr02,

i = 2πzFDcr0 (3)

From Faraday law the current associated to the growth of the deposit is [1]:

(4)

where M/ρ, the ratio of the molar mass and density, is the molar volume of the
deposit. Then equating (3) and (4),

(5)

and after separating variables and integrating,

(6)

the radius of the growing nucleus at time t is then given by:

(7)

Substituting now this result in (3) yields that the current attending the growth
of a single hemispherical nucleus on the electrode surface is given by:

(8)

1.2 Multiple nucleation without overlap

Consideration must be given to the presence of many nuclei on the
electrode surface due to multiple nucleation. With originally N0 active site per
unit surface and provided a constant nuclear birth rate A on the sites at constant
potential, then the number density of active sites available for nucleation
decays with first-order kinetics, and the number density of nuclei increases in
time according to [1]:

N = N0 [1 − exp(−At)] (9)
The development of theoretical models 5

Under conditions of multiple nucleation but considering that the growth of

nuclei occurs independently from each other, then the current may be
expressed as the convolution of the growth rates of individual nuclei at time t
given by (8), after having appeared on the surface at time u according to (9).
Then for multiple nuclei [1],

(10)

yielding for the current density:

(11)

where Φ is the Dawson integral,

(12)

In numerous experiments it has been observed that very rapidly the density of
nuclei attains a limiting value after exhaustion of the available sites on the
surface. This condition is generally known as “instantaneous” nucleation, as
opposed to the opposite condition of “progressive” nucleation, where new
nuclei form continuously [6]. For At ≥ 20, the Dawson function Φ → 1 and
under such circumstances (11) describes the current density associated to
‘instantaneous’ nucleation; for At ≤ 0.2 then Φ → (2/3)At, corresponding to
the limiting case of ‘progressive’ nucleation.

2. Theoretical approaches for multiple nucleation

with overlap of diffusion zones
2.1 The concept of planar diffusion zones
The theoretical decription of the potentiostatic current transient for
multiple nucleation on active sites with growth of nuclei controlled by
diffusion has been controversial for a number of years. Even though nucleation
occurs on the plane of the electrode surface, phase growth and diffusion
gradients due to mass transport extend also in other directions, towards the
bulk of the solution. As depicted in Figure 1, nuclei develop diffusion fields
with hemispherical symmetry around them during growth, and these interfere
as they grow and overlap with each other.
6 D. Mazaira et al.

Figure 1. Scheme showing development and overlap of hemispherical diffusion fields

around nuclei growing under diffusion control on the electrode surface.

Figure 2. Schematic representation of mass transport to planar diffusion zones on the

electrode surface.

Spherical diffusion assists the growth of nuclei on the electrode surface.

However, since overlap of diffusion fields occurs in the three-dimensional
solution while nuclei are randomly distributed along the two-dimensional
plane of the electrode, then in order to account for overlap of the diffusion
fields Scharifker and Hills [7] conceived planar diffusion zones on the
electrode surface towards which the same amount of depositing material would
flow through planar diffusion, as that flowing by spherical diffusion to
growing nuclei. In this fashion nuclei develop diffusion zones during their
growth, and as they overlap the locally spherical diffusion around individual
nuclei turns into planar diffusion towards the entire electrode surface, with
mass transport in the direction normal to the electrode surface. Diffusion may
be then regarded as planar throughout to the segments of the electrode surface
area covered by diffusion zones, as represented in Figure 2.
Reducing the spherical diffusion fields to discs along the electrode plane
allows using the well-known Avrami theorem [8-10] to account for their
overlap. The Avrami theorem considers that the growth of a new phase occurs
from seed nuclei or active sites with number density N0. The number of
available sites will vary as a function of time, N0(t), as a result of (i)
conversion of active sites into growing nuclei, and (ii) ingestion of active sites
by growing nuclei originated elsewhere. As diffusion zones grow and cover the
available surface they run into each other and start to overlap, and within the
The development of theoretical models 7

framework of the Avrami theorem growth is assumed to cease within the

overlapped region of the surface. Furthermore, we may also consider the
hypothetical space occupied by a growing nucleus not impeded by others, the
extended volume v1ex, in the domain of the phase transformation. Thus if the
transformation occurs along a line then the extended volume would be in one
dimension, it would be in two dimensions if the transformation occurs at the
interface between two bulk phases, and it would be three-dimensional if the
transformation occurs within a bulk phase. The total extended volume of
transformed phase per unit volume of the transformation domain is given by
[2]:

(13)

where v is the volume of a nucleus and u is the time of its birth. Following the
considerations of Avrami [8,9], we may also consider the non-overlapped
volume v’ as that part of the transformation domain not occupied by
transformed matter. Then, on average, the ratio of the non-overlapped volume
to the extended volume of a randomly selected region is equal to the density of
untransformed matter 1 – V, i.e. v’/v1ex = 1 – V. The same reasoning may be
applied, not to the volumes of single nuclei, but to the non-overlapped and
extended portions of the increments of these nuclei in an element of time. Then
for the average nucleus,

(14)

since the non-overlapped decrease of a nucleus is nothing more than the

increment in transformed volume of that nucleus. For the unit volume this
leads to

(15)

Integrating and rearranging this leads to the well-known Avrami expression,

V = 1 − exp(−V1ex) (16)

The above equation applies to randomly distributed nuclei and this will only
occur in the instantaneous nucleation case where all nuclei are born at the same
time, since during progressive nucleation will be excluded within a region
8 D. Mazaira et al.

around growing nuclei. The random distribution however may be restored

introducing phantom nuclei associated to each of the active sites, that would
have been converted into growing nuclei having not been ingested by the
growth of nuclei born elsewhere. The relevance of phantom nuclei will become
clear later on in this review, but turning our attention back to the model
postulated by Scharifker and Hills [7] mass balance between spherical fields
and planar zones requires that the radial growth rates rd(t,u) of planar diffusion
zones satisfy the following continuity equation [1]:

(17)

from which the radial growth rate rd (t,u) is readily obtained,

rd(t,u) = [kD(t – u)]1/2 (18)

where k = (8πcM/ρ)1/2, leading to the following expressions of the potentiostatic

current transient for nucleation followed by three-dimensional diffusion-
controlled growth [7], where exhaustion of active sites during the process has
not been considered:

(19)

for the case of instantaneous nucleation, and

(20)

for progressive nucleation.

2.2 The standard model

Scharifker and Mostany [11] (henceforth referred to as SM) took on the
concept of planar diffusion zones developed in [7] but with explicit
consideration of the decaying number density of sites available for nucleation,
cf. equation (9). Following arguments developed by Evans [12] leading to
results equivalent to those of Avrami’s [8,9], they obtained a general
expression for the current transient embracing instantaneous and progressive
nucleation as particular cases at opposite extremes of the N0/A ratio, with very
high nucleation rates on a small number density of active sites characterizing
The development of theoretical models 9

instantaneous nucleation, and low nucleation rates on very large number

densities of sites on the surface corresponding to progressive nucleation. The
probability that a representative point randomly selected on the electrode
surface is covered by exactly m diffusion zones is given by the Poisson
equation,

Pm = Em exp(−E) / m! (21)

where E is the expectation number. The probability that the representative

point has not been covered is therefore:

P0 = exp(−E) (22)

P0 then denotes the fraction of electrode area remaining uncovered, and since
E varies with time, then P0 also varies with time. The expression for E, the
number of diffusion zones covering a representative point on the electrode
surface is then [11]:

= N0πkDt [t + (1 − e −At)/A] (23)

The fraction covered by diffusion zones is given by θ = 1 − exp (− E), then

applying the concept of planar diffusion zones [7], SM [11] obtained the
current density,

(24)

The transient current described by (24) exhibits a maximum from which the
number density N0 of active sites on the surface as well as the nucleation
frequency A on them may be determined. From the time derivative of (24) and
evaluating the maximum current density jmax and the corresponding time tmax,
then the following set of equations arise:

ln(1 – jmaxtmax1/2/a) + x − α(1 − e−x/α) = 0

(25)
ln[1 + 2x(1 – e−x/α)] – x + α(1 − e−x/α) = 0
10 D. Mazaira et al.

where a = zFD1/2c/π1/2, x = N0πkDtmax and α = N0πkD/A. For α → 0 nucleation

is instantaneous, whereas as α → ∞ nucleation becomes progressive. x and α
may be found from the experimental jmax and tmax solving this set of equations,
hence A and N0 can be evaluated from the experimental transient by analysis of
the current maximum. Although these transcendental equations can not be
solved algebraically the solution may be found to arbitrary precision using
numerical techniques, a graphical representation of the solution of the set of
equations (25) is given in Figure 3 as the interception of the both curves in the
x as a function of α plane.
Using the quantities jmax and tmax describing the current maximum allows
also representing the transient in non-dimensional form [7,13] as:

(26)

for instantaneous nucleation, and

(27)

for progressive nucleation, as shown in figure 4.

1.9

1.8

1.7
x

1.6

1.5

0.1 0.15 0.2 0.25 0.3 0.35

a

Figure 3. Graphical representation of the set of equations (25) as x vs. α, the solution is
given by the point where the curves intercept.
The development of theoretical models 11

1.0

0.8

0.6

I/Imax
0.4

0.2

0.0
0 2 4 6 8 10
t/tmax

Figure 4. Non-dimensional representation of potentiostatic current transients according

to (26) and (27) for instantaneous (continuous line) and progressive (broken line)
nucleation.

The standard model thus introduced a general equation for the

interpretation of current transients arising during the electrochemical formation
of new phases with three-dimensional growth of nuclei under diffusion control,
and has been widely used to extract the kinetic parameters A and N0 from
experimental data. Some inconsistencies of this model, however, have been
pointed out by Sluyters-Rehbach et alia [14] (henceforth SRWBS), who most
appropriately considered that the Avrami theorem could not be applied to
diffusion zones with different heights, representing non-uniform gradients
across the surface, cf. Fig. 2, as the SM model would imply, and this has
prompted the development of alternative formulations of the standard model,
striving to overcome these difficulties [15].

2.2.1 Developments in the formulation of the standard model

Heerman and Tarallo [16] (HT) took on the inconsistencies pointed out by
SRWBS about the standard model and considering that proper application of
the Avrami theorem to planar diffusion zones requires that their height should
be uniform disregarding their distinct times of birth during progressive
nucleation, arrived to an expression identical to that obtained earlier by Mirkin
and Nilov [17] who did not support their integral equation analysis on the a
priori assumption that the current should conform to that given by the Cottrell
equation in the diffusion zones. According to these authors [16,17], then, the
current density is given by:

(28)
12 D. Mazaira et al.

where Φ has been defined above, cf. (12), and Θ = 1 -(1 – e–At)/At arises from
consideration of the overlap of diffusion zones, cf. (23). The effect portrayed
by Φ/Θ in (28) has been identified as a delay in the development of a uniform
diffusion layer all over the electrode surface during progressive nucleation
[16], as compared with its regular propagation rate also maintained upon
instantaneous nucleation; for instantaneous nucleation thus the diffusion layer
thickness increases as δ(t) = (πDt)1/2, whereas during progressive nucleation
δ(t) = (3/4)(πDt)1/2.
Comparison of (28) with experiments shows that (28) overestimates the
current densities for the case of progressive nucleation. Heerman et al. [18]
deemed this resulted from inaccurate detailed mass balance at individual
diffusion zones when these are born at different times, thus they defined a
single planar diffusion zone for the overall ensemble of growing nuclei instead
of manifold zones associated to each of the growing centers. This introduces a
uniform diffusion layer, related to the mean concentration field brought in by
Bobbert et al. [19]. From the current density and charge associated to the
independent growth of nuclei on the surface, and without considering their
interactions, expressions for the width of the diffusion layer and the extended
coverage of the overall electrode were obtained [18],

<δ(t)> = (πDt)1/2Ψ (29)

and

θex(t) = Ν0πkDtΦΨ (30)

where Φ, cf. (12), reflects the current delay resulting from slow nucleation, and

Ψ = Φ−1/2[1 – (3Φ/2At)]1/2 (31)

the slower expansion of the overall diffusion layer as compared to that

corresponding to the Cottrell equation normally applicable to regular planar
electrodes. In these terms the overall extended current density without having
considered interactions among nuclei is,

(32)

and from this the current follows from consideration of the real area using the
Avrami theorem, θ = 1- exp[−θex(t)], cf. (16),
The development of theoretical models 13

(33)

More recently Matthijs et al. [20] (MLMH) considered the phantom nuclei
needed to recover the random distribution required for proper application of
the Avrami theorem to progressive nucleation, as discussed above, and
conjectured that the current density should be given by

(34)

where j*(t) and θ*(t) are the extended current and coverage associated to the
fictitious independent growth of real nuclei, discounting contributions by
phantoms. For progressive nucleation, these are given by [20],

(35)

where a = (πDkAN0/2)1/2, and

(36)

Further below we show that the MLMH conjecture [20] fits well experimental
and simulated data approaching progressive nucleation, however it only
applies to this limiting case and hence it is not possible to obtain A and N0
separately from analysis of (36).

2.2.2 A hierarchical model of overlap

All detailed treatments of the standard model discussed hitherto use the
Avrami theorem [8,9] or equivalent derivations such as that given by Evans
[12] to account for the overlap of planar diffusion zones. Since proper
consideration in these terms only holds within the dimensional domain of the
phase transformation, e.g., for the overlap of circular regions within the plane,
it is therefore required that all diffusion zones have the same width. This is
readily realized when all nuclei are born at the same time, i.e., when nucleation
is instantaneous. Yet uniform width of diffusion zones will hardly be the case
if nuclei started growing at different times, and it stems clear then from the
succeeding formulations of the standard model, that the requirement of
14 D. Mazaira et al.

uniform width for all diffusion zones poses a major difficulty for the treatment
of the current transient within the framework of the Avrami theorem when
nucleation is not instantaneous. Circumventing this difficulty requires either
compelling uniform width for all diffusion zones to retain use of the Avrami
theorem, or discarding the use of the Avrami theorem to account for the
overlap of diffusion zones of variable width. From the discussion above it is
apparent that this latter path is now necessary; thus we will now turn to
describe a hierarchical model accounting for overlap of diffusion zones born at
various times, and consequently with differing widths of their respective
diffusion layers.
Consider a set of diffusion zones expanding on the surface of the electrode
with radial rate rd(t,u) = [kD(t - u)]1/2, cf. (18), and width

δ(t,u) = [πD(t – u)]1/2 (37)

Consider as well that once a diffusion zone has been established, the growth of
a nucleus and a diffusion zone within it has no bearing on mass transport, and
hence current flow is unaffected by nuclei appearing, or newer diffusion zones
growing, within the already established one. Therefore whereas in the usual
unranked situation described by the Avrami theorem growth ceases as circles
collide with each other during radial growth, within the hierarchical model
older diffusion zones with larger radii and taller widths prevail over younger
and consequently shorter ones. Hierarchy upon impingement then implies that
at short times during progressive nucleation there will be a spread of diffusion
zones widths, though at longer times the older diffusion zones will run over
younger ones and eventually, as t → ∞, only the older zones will survive and
the width will attain uniformity all over the surface, approaching the
corresponding Cottrell value.
Since analytical solutions for the hierarchical overlap of diffusion zones
are as yet not available, then this model has been explored by way of Monte
Carlo type simulations on a small square segment of surface (10–4 cm–2) with
periodical boundary conditions to reduce border effects [21]. Simulations were
run with various ratios N0/A of number densities of active sites to nucleation
rates in order to cover the range from instantaneous to progressive nucleation.
The current was given for each nucleus k from the Cottrell contribution

(38)

of their respective planar diffusion zones, with sizes established after each time
step during simulations according to the hierarchical criterion described above.
The overall current was then obtained as the summation of all contributions.
The development of theoretical models 15

40

30

10 r / cm
4
20

10

0
0 4 8 12 16 20
t (s)

Figure 5. Radii of individual diffusion zones as a function of time, during a simulation

with A = 0.05 s-1 and N0 = 1x106 cm-2.

Simulation parameters were chosen to correspond to the electrodeposition of

mercury from 0.5 mM Hg22+ aqueous solution in the presence of excess
supporting electrolyte, at room temperature. Because of the parabolic growth
rate rd(t,u) = [kD(t – u)]1/2, younger diffusion zones grow at a given time faster
than older ones, as shown in Figure 5. Therefore younger diffusion zones born
inside already established ones may conceivably overflow these. It has been
established that such phantom nuclei may account for up to 4% error in the
estimation of coverages using Avrami theorem [22], an effect not arising in the
present digital simulation of the hierarchical model.
Thus during simulation of nucleation and growth with hierarchical overlap
of diffusion zones, the age and radius of each individual diffusion zone was
tracked at all times, giving priority to older zones in extending their coverage
following each time step. Figure 6 shows the coverage of individual diffusion
zones during hierarchical overlap, resulting from simulation of the process
with A = 0.025 s-1, N0 = 1x106 cm-2. The coverage corresponding to the oldest
nucleus in the set increases continuously, whereas the coverage of younger
zones increase linearly with time only at short times, then falling at longer
times while being ingested by older zones, vanishing in the limit of t → ∞,
when only the oldest of the diffusion zones survives.
Given the coverage of the various diffusion zones shown in Fig. 6, then the
currents attending their growth are given by (38), and these are shown in
Figure 7.
16 D. Mazaira et al.

The resulting overall current transient is obtained summing the individual

current contributions at every time step, as shown in figures 8 and 9 for several
values of the ratio A/N0, with N0 kept constant at N0 = 1x106 cm-2 throughout,
while A varying from 0.025 s-1 to 0.75 s-1 (figure 8), and from 1 s-1 to 100 s-1
(figure 9).

0.4

0.3

θ(t)

0.2

0.1

0.0
0 4 8 12 16 20
t/s

Figure 6. Coverage of individual diffusion zones during hierarchical overlap,

A = 0.025 s-1, N0 = 1x106 cm-2.

16

12
10 I / A
9

0
0 4 8 12 16 20
t/s

Figure 7. Current contributions attending the growth of individual nuclei according to

(38), during hierarchical overlap shown in Fig. 6, with A = 0.025 s-1, N0 = 1x106 cm-2.
The development of theoretical models 17

0.15

0.75
0.12
0.5
0.25
0.1

10 I / A
0.09 0.075

6
0.025

0.06

0.03

0.00
0 4 8 12 16 20
t/s

Figure 8. Simulations of potentiostatic current transients with hierarchical overlap of

diffusion zones, A between 0.025 s-1 and 0.75 s-1, N0 = 1x106 cm-2.

0.18

0.12
10 I / A
6

100
50
0.06
20
10
5
2
1

0.00
0.0 0.5 1.0 1.5 2.0 2.5 3.0
t/s

Figure 9. Simulations of potentiostatic current transients with hierarchical overlap of

diffusion zones, A between 1 s-1 and 100 s-1, N0 = 1x106 cm-2.

2.2.3 A comparison of transients arising from hierarchical and non-

hierarchical models
The chief differences among the various formulations of the standard
model describing nucleation with diffusion-controlled three-dimensional
growth rest in the consideration of overlap of diffusion zones. Deriving from
first principles, moreover, the hierarchical model of overlap does not rely on
18 D. Mazaira et al.

mean field approximations [19,23]. Comparison of the transients obtained

from simulations of hierarchical overlap with models considering the Avrami
non-hierarchical overlap has been made following two approaches. First the
transients obtained from simulations of hierarchical overlap of diffusion zones
with given A and N0 values were graphically compared with those predicted by
the various formulations of the standard model in terms of non-hierarchical
Avrami overlap. Then, in a second approach for a more quantitative
assessment of differences among the various models, transients generated from
simulation of hierarchical overlap of diffusion zones were analysed using the
different theoretical expressions of models corresponding to Avrami non-
hierarchical overlap, and the kinetic parameters A and N0 obtained from such
analyses were contrasted to the values of A and N0 actually used to generate the
simulated transients. Figure 10 shows examples of the results obtained with the
first approach. For cases approaching the limit of instantaneous nucleation at
N0/A → 0, cf. Fig. 10 (c) and (d), the various models –except for the MLMH
conjecture– coincide with each other, as well as with the simulated results.
Under instantaneous nucleation conditions, thus, ranking of nuclei vanishes as
all nuclei are born at the same time. In the opposite extreme of progressive
nucleation, with N0/A >> 1, cf. Fig. 10 (a) and (b), the currents simulated under
the hierarchical model of overlap approach those predicted by the MLMH
conjecture [20], nevertheless invariably attaining higher maximum currents,
and approaching faster the Cottrell diffusion limit. The SM formulation of the
standard model does not consider the spread of birth times of the diffusion
zones and the corresponding currents remain invariably below the Cottrell
limit at all times. The HT expression takes into account the successive
appearance of nuclei and normalizes the width of all the diffusion zones,
significantly overestimating the limiting diffusion current with respect to the
transients generated considering hierarchical overlap of diffusion zones with
non-uniform widths. As already mentioned, the MLMH formalism, devised to
describe nucleation only in the strict progressive limit, severely diverges from
all models and simulations as the instantaneous limit is approached.
Having compared simulations of hierarchical overlap with the various
expressions for unranked overlap, evaluated at the A, N0 values used to obtain
the numerical counterpart, we will now turn to illustrate the kinetic parameters
A and N0 obtained from the analysis of the hierarchical simulation result with
these formulations, assuming no prior knowledge of their values. This may
provide insight on similarities and differences of each with respect to the
hierarchical postulate. When analytical methods were available, as in the SM
case, A and N0 where obtained from {im,tm} values at the current maximum; for
other models, the simulated data were non-linearly fitted to theoretical
expressions, with A and N0 as the sole fitting parameters.
The development of theoretical models 19
1.5 1.5
SM(at)
HT(at) SM(at)
HML(at) HT(at)
Sim(at) HML(at)
1.0
Cotrell(at) 1.0 Sim(at)

1/2
1/2
MLMH(at) Cotrell(at)

j(t)(πD) /zFDc(a)
j(t)(πD) /zFDc(a)
MLMH(at)

1/2
1/2
0.5 0.5

0.0 0.0
0 1 2 3 0 2 4 6 8 10

at at

a) A = 0.025 s−1 b) A = 0.25 s−1

2
2.0

SM(at) SM(at)
HT(at) HT(at)
1.5 HML(at) HML(at)
MLMH(at) MLMH(at)

1/2
Sim(at) Sim(at)
1/2

j(t)(πD) /zFDc(a)
j(t)(πD) /zFDc(a)

Cotrell(at) Cotrell(at)
1.0 1

1/2
1/2

0.5

0.0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0 3 6 9 12
at at

c) A = 2 s−1 d) A =20 s−1

Figure 10. Comparison of transients simulated with hierarchical overlap of diffusion

zones (b), with different formulations of the unranked, standard model with overlap
accounted for by the Avrami theorem: SM (ƒ), HML (c), MLMH (f), and HT&MN
(y). N0 =1x106 cm−2, A = 0.025s−1 (a), 0.25 s-1 (b), 2.0 s-1 (c), and 20 s-1 (d). The Cottrell
limiting diffusion current to a uniformly accessible planar electrode is also shown (⎯).

Figures 11 and 12 again reflect the confluence of the SM, HT, HML and
hierarchical models for the instantaneous limit, where differences between
widths of diffusion zones vanish due to the narrow distribution of nuclei ages.
At the progressive limit, in contrast, new information becomes apparent from
the present analysis. With respect to hierarchical overlap, the SM model
underestimates the nucleation frequencies A while significantly overestimating
the number densities of active sites N0, whereas the HT and HML models do
quite the opposite. None of these models contemplates hierarchical overlap,
therefore it is not expected that they should predict appropriately the A and N0
values involved in the generation of digital data. As stated, the various models
20 D. Mazaira et al.

differ in the way they homogenise the widths of diffusion fields and treat their
overlap using the Avrami theorem, hence the observed differences in figures
11 and 12. Nonetheless, when the product AN0, namely the stationary
nucleation rate (cm−2 s−1) is considered, then the differences between the SM,

100

10

-1
Amod / s
1

Sim
0.1
SM
HT
HML
0.01

0.01 0.1 1 10 100

-1
Asim / s

Figure 11. Values of Amod (s−1) obtained from analysis of the hierarchical digital
simulations with the SM (○), HT (U) and HML (V) formalisms, for different values of
Asim and N0 = 1x106 cm−2. Continuous line corresponds to Amod=Asim.

Sim
7 SM
10
HT
HML
-2
N0 /cm

6
10

5
10
0.01 0.1 1 10 100
-1
Asim / s

Figure 12. Values of N0 (cm−2) obtained from analysis of the hierarchical digital
simulations with the SM (○), HT (U) and HML (V) formalisms, for different values of
Asim and N0 = 1x106 cm−2. Continuous line corresponds to N0 = 1x106 cm−2.
The development of theoretical models 21

HT, HML models vanish, as shown in Figure 13, and moreover the AN0
product obtained is close to that of the parameters A and N0 used to generate
the data with simulations of hierarchical overlap. This indicates that the
product AN0, determined from the various models accounting differently for
overlap of diffusion zones, is quite robust, but, conversely, that establishing
precisely and unequivocally the values of the independent variables A and N0
requires determining which of these models affords the most fitting description
of reality.
As a final remark, we cannot discard that some of the differences observed
may have risen from the different mathematical methods employed to obtain A
and N0 from the corresponding models. A and N0 were found from the SM
model solving a system of non-linear equations using the coordinates of the
current maximum, which is a significant point in a current transient regarding
the nucleation and growth process. In the case of the HML and HT models, the
kinetic parameters were obtained by non-linear fitting of the whole data sets to
the theoretical equations using the Levenberg-Marquardt algoritm, with A and
N0 as fitting parameters. Values obtained from the MLMH model have not
been included in our analysis here because the approximate solution developed
by these authors has been based on cubic polynomials that hold for at ≤ 0.85, a
time span too short for comparison with other models.

8
10 Sim
SM
HT
7 HML
10
-1
AN0/ cm s
-2

6
10

5
10

4
10

0.01 0.1 1 10 100

-1
Asim / s

Figure 13. Values of the stationary nucleation rate AN0 (cm−2 s−1) obtained from
analysis of the hierarchical digital simulations with the (○) SM, (U) HT and (V) HML,
for different values of Asim and N0 = 1x106 cm−2. Continuous line corresponds to the
AN0 product used in simulations (N0 = 1x106 cm−2).
22 D. Mazaira et al.

Conclusions and outlook

We have examined some of the major difficulties arising in the rigorous
treatment of the kinetics of nucleation and diffusion-controlled growth of three-
dimensional electrodeposits, as well as the several formulations available about
the so-called standard model for multiple nucleation with diffusion-controlled
three-dimensional growth. We have shown that consideration of uniform height
for all diffusion zones, an unrealistic feature common to all treatments relying on
application of the Avrami or related theorems to account for their overlap, poses
a major difficulty. We then presented a novel method for the description of
multiple nucleation with three-dimensional diffusion-controlled growth, based
upon hierarchical overlap of planar diffusion zones associated to the growing
nuclei, with older zones prevailing over younger ones. Through digital
simulations we have shown the main features of such model, and the results
arising from hierarchical overlap were compared both qualitatively and
quantitatively with other models based upon applications of the Avrami theorem.
Hierarchical overlap of diffusion zones avoids mean field approximations,
considering also realistically the effects of dispersion in the age of nuclei on their
growth rates, which is particularly important in the limit of progressive
nucleation. A further step in the formulation of such model is obtaining a closed
form expression for the current transient, from which A and N0 could be
unequivocally evaluated from single-step, potentiostatic experiments. Work is
currently in progress in our laboratory following this direction.

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