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 Electrochimica Acta 52 (2006) 892–903

The role of temperature in copper electrocrystallization in

py
ammonia–chloride solutions
Jorge Vazquez-Arenas a , Roel Cruz a,∗ , Luis H. Mendoza-Huizar b

co
a Facultad de Ingenierı́a, Instituto de Metalurgia, Universidad Autónoma de San Luis Potosı́, Av. Sierra Leona 550,
Lomas 2a sección, 78210 San Luis Potosı́, S.L.P., México
b Centro de Investigaciones Quı́micas, Universidad Autónoma del Estado de Hidalgo, Unidad Universitaria,

Km 4.5 Carretera Pachuca-Tulancingo, CP. 42184 Pachuca-Hidalgo, México

Received 2 March 2006; received in revised form 20 June 2006; accepted 21 June 2006
Available online 4 August 2006

al
Abstract
This paper presents the analysis of temperature effect on the copper electrocrystallization process from the stainless steel/Cu(II)–Cu(I)–
on
NH4 Cl–NH3 –H2 O system. Electrochemical techniques and scanning electron microscopy with energy dispersion spectroscopy were employed. An
increment in temperature had a favorable effect in increasing the kinetic and nucleation parameters, favoring the copper reduction on the stainless
steel substrate. From the chronoamperometric study, it was possible to find the transfer coefficient (α), which does not have a significant variation
with temperature, and the exchange current density (i0 ) for different temperatures, where a 50.63 kJ/mol value was estimated for the activation
energy. The potentiostatic study suggested the presence of two processes involved: an electron transfer reaction and a 3D nucleation—growth
rs

process, under combined charge transfer and diffusion limitations. In addition, an important current contribution could be accounted for on the
basis of the existence of a capacitive component in the system. This capacitive behavior was associated to the oxide layer (Cr2 O3 )–chloride
interactions on the stainless steel surface. Current transients analyses at different potentials, based on the models of: Milchev (low overpotential),
pe

Scharifker–Mostany (SM) and Heermann–Tarallo (HT) (high overpotential) allowed to obtain the values of nucleation parameters, such as: the
nucleation rate constant (A), the active nucleation sites number (N0 ), the stationary nucleation rate (Ist = A × N0 ) and the nuclei saturation number
(Ns ). Finally, the deposits obtained were analyzed by SEM, showing an acceptable correlation between the nucleation parameters and morphology
of the deposits obtained. An increment in temperature favored the growth of the cluster before the coalescence occurred.
© 2006 Elsevier Ltd. All rights reserved.

Keywords: Copper; Electrocrystallization; Kinetics; Temperature; Adsorption

r's

1. Introduction perature dependence of the nucleation rate is determined mainly

by the thermodynamic and kinetic barriers for nucleation. Since
o

Electrocrystallization is a complex process affected by factors a temperature decrease produces two effects: a decrease of the
such as: substrate, additives, electroactive species, bath compo- thermodynamic barrier, due to an increase in the thermodynamic
th

sition, mass transport, temperature, etc. Although, the effect of
temperature is well known, only few studies have been reported
about this factor effect [1–5]. Such studies indicate that nucle-
ation and growth rate increase with the temperature, which could
Au
driving force for crystallization, leading to a higher nucleation
rate and an increase of the kinetic barrier leading to a lower
nucleation rate [6].
However, a contrary behavior has been observed [1–5],

intrinsically suggests a diminution of energy requirement for the
electrodeposition process. The Gibbs’s energies as well as the
activation energies are potential-dependent, but the temperature-
dependence of these quantities is at all not obvious. The tem-
∗ Corresponding author. Tel.: +52 444 825 43 26; fax: +52 444 825 43 26.
E-mail address: rcuz@uaslp.mx (R. Cruz).
which is probably because the value of the surface energy
(σ) leads to a slight increase with increasing temperature
(dσ/dT ∼ (0.06–0.16) × 10−3 J/m2 K) regardless of the method
of estimating the kinetic barrier [7–11]. Moreover, if one take
in account a possible curvature (or nucleus size) dependence
of the surface tension (the specific surface energy, estimated
from nucleation rate data, refers to nuclei of critical size) [6].
Curvature corrections can be expected to lead to a reduction in

0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.06.022
 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903 893

the effective value of the surface energy. As the critical nucleus

size increases with temperature, the effect of curvature correc-
tions decreases, leading to higher effective values of the surface
energy [12]. Thus, the increase in the surface energy produces
an increment in the value of the rate constant for nucleation
favoring the electrodeposition process [12].
Another effect of temperature in the electrodeposition pro-
cess is the increase of the coefficient diffusion value as the
temperature increases [13], which generates a major flux to the

py
chemical species to electrode surface.
At present work, the temperature effect in the electrode-
position process of copper has been analyzed for the system
stainless steel (SS)/Cu(II)–NH4 Cl–NH3 –H2 O. For this study,

co
electrochemical techniques and scanning electron microscopy
with energy dispersion spectroscopy were utilized. This study
is part of an investigative work aimed at the understanding Fig. 1. Typical cyclic voltammogram obtained in the SS/0.2 M Cu(II), 4 M Cl−
and NH4 + + NH3 (pH 7.5) system. The temperatures studied are indicated in
of electrochemical systems based on Cu(II)–NH4 Cl–NH3 –H2 O
figure. Scan rate: 100 mV s−1 .
electrolytes [14,15].
ing bath was used to fix and to control temperature within

2. Methodology
The experiments were carried out in 0.2 M Cu(II), 4 M
on
NH3 + NH4 + and 4 M Cl− electrolyte. All solutions were pre-
pared using ultrapure water (18.2 ␮ cm NanopureDiamond
TM
(Barnstead ) and CuCl2 ·2H2 O (Fisher), NH4 Cl (Fisher) and
NH4 OH (Fisher) analytic grade reagents. In each case, the
rs
al
±1 K.
A conventional three-electrode cell (100 mL) was used for
the electrochemical experiments. A 304 stainless steel (∼19%
Cr, ∼08% Ni and ∼2% Mn) rod was embedded in resin to
generate a rotating disk working electrode with a 0.125 cm2
area. A graphite rod (Alfa AESAR, 99.999%) was utilized as
counter electrode and a saturated calomel electrode (SCE) was

pH was controlled by addition of 4 M NaOH (Fisher) and the reference electrode; all reported potentials are referred to this
10 M H2 SO4 (J.T. Baker) solutions, and by a pH meter scale. Prior to each experiment, working electrode surface was
TM TM
Termo Orion 420A. A 10 L Polyscience heater circulat- polished to mirror finish using 0.05 ␮m Buehler alumina pow-
pe
o r's
th
Au

Fig. 2. Typical cyclic voltammograms obtained in the SS/0.2 M Cu(II), 4 M Cl− and NH4 + + NH3 (pH 7.5) system, at different temperatures: (a) 298, (b) 313 and
(c) 323 K and at different scan potential rates indicated in figure.
894 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903
der, pre-washed for 5 min with pure water in an ultrasonic bath.
Inert (nitrogen) atmosphere was maintained during all experi-
ments. The working electrode potential was controlled by an
TM
AUTOLAB model PGSTAT 30 potenstiotat–galvanostat cou-
TM
pled to a personal computer using GPES software.
3. Results and discussion
3.1. Voltammetric study
Fig. 1 show the voltammetric direct scans from the 0.2 M
Cu(II), 4 M NH3 + NH4 + and 4 M Cl− solution at 298, 313, 323
and 343 K, at pH 7.5 on the SS substrate. At 298 K, it was
possible to observe three cathodic peaks: Ic, IIc and IIIc, at
−0.380, −0.550 and −0.650 V, respectively (see Fig. 1). In a
recent work, Vazquez-Arenas et al. have shown that, for this
system, the reduction process for predominant chemical species
(Cu(NH3 )3 Cl+ complex) involves the following steps [14,15]:
(a) Cu(NH3 )3 Cl+ /Cu(NH3 )2 Cl, occurring in the region labeled
as Ic. The low current obtained in this step has been
on
attributed to a slow reduction process due to the barrier
formed by the oxide layer (Cr2 O3 )–chloride interactions in
the SS surface.
(b) Cu(NH3 )2 Cl/Cu(0), occurring in the region labeled as IIc.
rs
This step is characterized by an important increase in the
cathodic current.
(c) A faster reduction Cu(NH3 )3 Cl+ /Cu(0) labeled as peak IIIc,
which take place due to the higher overpotential.
pe
o r's
th
Au
Fig. 3. Experimental cathodic peak current (−Ip ) as a function of scan rate (v1/2 ), obtained at temperatures indicated in figure.
Note that the current peak Ic increases as temperature,
which could be due to enhancement of kinetic and diffusive
processes, such as it is indicated by a better defined peak.
However, this current increment could also suggest a diminu-
tion of the Cr2 O3 –chloride interaction, which persist even at
323 K.
Fig. 2 shows a set of voltammograms obtained for different
potential scan rates and temperatures. Observe that for all cases,
a fast increase in cathodic current was obtained after the slow
py
current step (−E > 0.5 V). This result indicates that a favorable
kinetic condition for the copper electrodeposition (IIIc peak)
on the substrate surface has been reached. Furthermore, it can
be observed that the cathodic current associated with peak IIIc
co
increases with the temperature. Similar results were obtained
by Ramos et al. [16], where the electrocrystallization stage of
(Cu(NH3 )2 + /Cu(0)) was explained in terms of diffusional con-
trol.
The peak IIIc formation is certainly due to species deple-
tion in the electrode/solution interface. Observe that a gradual
al
shifting of peak (Ep ) toward more negative values occurs as the
scan rate (v) increases. In order to determine the control type
limiting this process, the current value associated with the peak
(−Ip ) was plotted as a function of v1/2 (Fig. 3). Note that a
reversible behavior is obtained approximately at scan rate lower
than 50 mV s−1 (Fig. 3a), 80 (Fig. 3b) and 50 mV s−1 (Fig. 3c)
for 298, 313 and 323 K, respectively. On the other hand, an irre-
versible behavior was observed at higher scan rates. This feature
is characteristic when a process passes through a region known
as quasi-reversible [17]. The linearity showed by the −Ip ver-
sus v1/2 at the different temperatures, suggests an irreversible
 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903 895

py
co
al
Fig. 4. A set of experimental current transients recorded in the SS/0.2 M Cu(II), 4 M Cl− and NH4 + + NH3 (pH 7.5) system, at different potential step (V) indicated
on
in figure. System temperature: (a) 298, (b) 313 and (c) 323 K.

reduction process occurring under diffusion control [17–19], ficient and C is the bulk concentration of the electroactive
according with the following equation: species.
rs

The absolute value between the cathodic potential peak (Ep )

Ip = 2.99 × 105 n(αnα )1/2 AD1/2 Cv1/2 (1) and the cathodic potential half-peak (Ep/2 ) was obtained from
the voltammograms shown in Fig. 2. The calculated values were
pe

where n is the number of the transferred electrons in the reduc- quite close to the expected for an irreversible system [18,19].
tion process, nα the number of electrons transferred up to, These results newly suggest that the process is changing, from
and including, the rate determining step, D the diffusion coef- reversible to irreversible system.
o r's
th
Au

Fig. 5. Comparison between experimental transient normalized through the coordinates of its respective local maximum (tm , Im ), obtained during the copper
nucleation on SS at (a) −0.72 (298 K), (b) −0.71 (313 K) and (c) −0.717 V (323 K), with the theoretical non-dimensional curves corresponding to 3D instantaneous
and progressive nucleation.
896 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903

3.2. Potentiostatic study This process is known to take place in two steps:
Cu2+ + e− → Cu+ (slow) (6)
The charge transfer and nucleation kinetic of copper elec-
trocrystallization process on SS electrode, were studied from Cu+ + e− → Cu0 (fast) (7)
a system 0.2 M Cu(II), 4 M NH3 + NH4 + and 4 M Cl− at dif-
ferent temperatures by the potentiostatic technique. Fig. 4a–c The slow step (Eq. (6)) may lead to the accumulation of Cu+ at
shows a set of current transients obtained from different over- the electrode surface if the nucleation and growth of copper clus-
potentials and at differente temperatures. All transients shown ters is not sufficiently fast [25,26]. Accordingly with Milchev et
in the figure exhibited a falling current in the initial period of al., an electron transfer reaction takes place prior to and simulta-

time. After this falling current, the transients showed a typical
current maximum (Im ), related with the coalescence of diffusion
fields with spherical symmetry. Once the current maximum was
reached, a decay of the current was obtained, which approaches
py
neously with the process of the nucleus formation. The current
density associated to these processes, before the nuclei overlap-
ping, but when the crystal formation has already started, is given
by:

co
to a planar diffusion. The shape of these transients exhibited the 3
IM = aR exp(−bR t) + q[(1 + 2nt)1/2 − 1] (8)
features of typical three dimensional nucleation process with
hemispherical diffusion control (3D-dc) of the growing crystal- where
lites [20–22]. The nucleation model proposed by Scharifker and  
sπF4 (DC)3 3αFη
Hills allows classifying the nucleation and growth mechanism q= Ist exp − (9)
as instantaneous (Eq. (2)) or progressive (Eq. (3)), by compari- i0 VM RT
vi0 VM Q

al
son between the dimensionless curves of the experimental and
n= (10)
theoretical transients [20]. F 2 DC
   2 with s = 32/3 and v = 1/4 and
I2 t
1.9542
on
= 1 − exp −1.2564 (2)    
Im2 t/tm tm 2αFη −2(1 − α)Fη
Q = exp − exp (11)
   2 RT RT
I2 1.2254 t
= 1 − exp −2.3367 (3) i0 is the exchange current density at the “copper–solution” inter-
Im2 t/tm tm
rs

face, α the charge transfer coefficient, η the overpotential, Ist the

Fig. 5 shows a comparison of the theoretical dimension- stationary nucleation rate and Vm is the volume molar. All other
less transients generated by Eqs. (4) and (5), with experimental parameters have their conventional meanings. Since the values
pe

dimensionless current transients obtained at different tempera-
tures. It is clear that at 313 K (Fig. 5b), most of the experimental
data fall within the range of validity of the theory proposed by
Scharifker et al. [20,21]. Last result suggests that the experimen-
tal transients could be fitted using the following equation:
1
I3D−dc(SM) (t) = zFDC
(πDt)1/2
r's
obtained for the number of reduced species were higher than an
effective monolayer, first term in Eq. (8) has been related with the
electron transfer reaction, i.e. Iet = aR exp(−bR t), discarding an
ion transfer reaction [25,26]. The second term describes the cur-
rent of progressive nucleation and growth of the copper crystals
on the substrate, under combined “charge transfer” and “diffu-
sion limitations” [27]. Therefore, the region of current falling

observed at short times may be related with the discharge of the

×[1 − exp(−αS N0 (πDt)1/2 t 1/2 Θ)] (4) copper complexes, in two monoelectronic steps.
In order to evaluate the existence of a similar behavior for the
with system here analyzed, Milchev’s model was applied to poten-
o

1 − exp(−At) tiostatic curves obtained at low overpotentials and short times,

Θ=1− (5)
At ensuring that any overlapping and coalescence of the clusters do
th

not occur during the growth. In this analysis, the model proposed
where z is the number of exchanged electrons, F the Faraday
by Milchev et al., could not account for the transient behavior at
constant, N0 the number of active nucleation sites, A the nucle-
shorter times than 0.4 s. The capacitive effect generated by the
ation rate and αS = 2[2Vm DC]1/2 .
Au

oxide layer (Cr2 O3 )–chloride interactions, suggested by voltam-

Observe that the values (I/Im ) at 298 and 323 K (Fig. 5a and
metry, involves the contribution of two capacitances in series,
c) are always lower than those obtained from the experimental
namely the oxide film thicknesses barrier, and the double layer
data. This difference might be associated to the contribution, to
capacitance, which could be influenced by chloride adsorption
the total current, of another processes not considered by the non-
and/or its reaction with oxide layer. A detailed study of this two
dimensional analysis [22–24]. Also, note that the falling current
capacitance contributions has been reported elsewhere [24,29].
cannot be accounted for the Scharifker’s model.
Hence, taking into account the above described, the initial falling
cathodic currents observed in the experimental current transients
3.2.1. Analysis of current transients at low overpotentials (IT ) obtained during copper deposition on SS electrode, may be
Recently, Milchev et al. [25] reported that, for the case of described by the following equation:
copper in sulfate solution, falling currents observed in transients,
as shown in Fig. 4, must be related to the copper ions discharge. IT = IC + IM (12)
 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903 897

py
co
al
on
Fig. 6. Experimental current transients at different overpotentials, with the theorical transients () generated by non-linear fitting of Eq. (12) to the experimental
data. The temperatures are given by figures.
rs

where IC = k1 exp(−k2 × t) is the current due to the capacitive (outer sphere reaction), in agreement with the reported in the
effect of Cr2 O3 –Cl− interaction, being k1 = k2 QC , where QC is literature [30,31].
the charge density due to the overall capacitance effect. An average value of 0.0456, 0.0487 and 0.0509 was obtained
pe

Fig. 6 shows the comparison of the experimental current
transients obtained at low overpotentials with the theoretically
generated by non-linear fitting of experimental data by Eq. (12).
It can be observed, that the model expressed by Eq. (12) ade-
quately accounts for the behavior of all experimental transients.
In Table 1, the best-fit kinetic and nucleation parameters at
different temperatures are shown. In this table, the reference
r's
for the i0 , at temperatures of 298, 313 and 323 K, respectively.
The value obtained at 298 K is similar to that reported in litera-
ture in a case of a copper reduction from sulfate solutions [25].
The (ln i0 ) was plotted as a function of (1/T), Fig. 7, exhibiting
a linear relationship, according with the Arrhenius’s equation
[19]. From the slope value and Eq. (13) it was possible to calcu-
late the activation energy (H = ) of the system as 50.63 KJ/mol.

electrode potential (SCE) values for 313 and 323 K were cor-
rected according with the methodology reported in literature
[28]. It is important to mention, that the charge transfer coeffi-
cients obtained from the fitting parameters of Table 1 and Eq. (9),
o
Last result compares favorably with the obtained in the case of
electrodeposition of copper from cupric pyrophosphate solu-
tions [32].

do not vary significantly with temperature, and they are around

0.5. This fact is indicative that the reduction reaction involv- ∂ ln i0 H =
=− (13)
ing Cu(NH3 )3 Cl+ /Cu(NH3 )2 Cl is an electron transfer reaction ∂(1/T ) R
th

Table 1
Potential dependence from kinetic and nucleation best-fit parameters at different temperatures, obtained through the fitting process of the experimental transients
Au

using Eq. (12)

−E (V) vs. SCE 298 K −E (V) vs. SCE 313 K −E (V) vs. SCE 323 K

aR (A) bR (s−1 ) Ist (cm2 s−1 ) aR (A) bR (s−1 ) Ist (cm2 s−1 ) aR (A) bR (s−1 ) Ist (cm2 s−1 )

0.367 0.0017 0.173 3835.095

0.4 0.0006 0.136 1390.488 0.41 0.0008 0.143 2315.287 0.417 0.0025 0.226 4447.202
0.45 0.0010 0.155 2492.439 0.46 0.0013 0.165 2850.112 0.447 0.0033 0.257 5124.677
0.5 0.0013 0.175 2076.329 0.51 0.0019 0.199 3411.408 0.467 0.0037 0.294 5618.889
0.55 0.0018 0.189 2412.502 0.55 0.0029 0.232 4032.103 0.487 0.0031 0.237 6590.043
0.6 0.0022 0.207 2921.393 0.56 0.0029 0.212 4081.080 0.497 0.0043 0.534 8110.426
0.62 0.0023 0.243 3573.664 0.58 0.0045 0.729 8182.813 0.517 0.0052 0.717 9064.838
0.6 0.0028 0.191 8453.429
898 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903

Note in Table 1, that for similar overpotentials, the Ist value

increases as a function of temperature and the overpotential
applied. Similar results have been obtained for copper reduc-
tion from sulfate solutions [25].
Under the methodology proposed by Scharifker for the satu-
ration nucleus densities (Ns ) assess [33], Ns values were cal-
culated from the parameters reported in Table 1, using the
following equation:
 

py
Ist 1/2
Ns = (14)
2k D
where

Fig. 7. Arrhenius equation linear plot (ln i0 vs. 1/T) for reaction
Cu(NH3 )3 Cl+ /Cu(0).
co
k = [8πCVM ]1/2 (15)
Results obtained for Ns are summarized in Table 2. These
results reveal that the Ns value increases with the applied overpo-
tential and with temperature at same overpotential value, remark-
ing an important role of these parameters in the generation of a
high saturation nucleus density. The charge contribution of the

al
Table 2
Potential dependence of the Ns , calculated from physical constants showed in Table 1 and Eq. (14)
on
−E (V) vs. SCE Ns (×10−3 cm−2 ) −E (V) vs. SCE Ns (×10−3 cm−2 ) −E (V) vs. SCE Ns (×10−3 cm−2 )

0.367 36.327
0.4 21.874 0.41 28.225 0.417 39.119
0.45 29.285 0.46 31.316 0.447 41.993
rs

0.5 26.729 0.51 34.261 0.467 43.971

0.55 28.812 0.55 37.248 0.487 47.620
0.6 31.705 0.56 37.474 0.497 52.828
0.62 35.067 0.58 53.063 0.517 55.850
pe

0.6 53.933
o r's
th
Au

Fig. 8. Comparison between an experimental current transient (−) recorded at (a) −0.66 (298 K), (b) −0.65 (313 K) and −0.657 V (323 K), with the theorical
transient () generated by non-linear fitting of Eq. (16) to the experimental data.
 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903 899

Table 3
Potential dependence for the physical constants involved during copper reduction, at different temperatures
−E (V) 298 K −E (V) 313 K
vs. SCE vs. SCE
aR (A) bR (s−1 ) A (s−1 ) N0 (×10−6 D (×107 aR (A) bR (s−1 ) A (s−1 ) N0 (×10−6 D (×107
cm−2 ) cm2 s−1 ) cm−2 ) cm2 s−1 )

0.58
0.60 0.61 0.004 0.715 1.225 11.61 2.828
0.62 0.63 0.004 1.070 1.947 17.18 2.907

py
0.64 0.002 0.198 0.926 2.202 2.428 0.65 0.006 1.321 2.641 21.67 2.833
0.66 0.003 0.238 1.511 3.235 2.339 0.67 0.007 1.032 2.898 25.87 2.794
0.68 0.003 0.226 1.785 3.759 2.665 0.69 0.001 0.496 2.862 50.83 2.688
0.70 0.004 0.358 2.305 4.552 2.460 0.71 0.002 1.178 8.873 57.30 2.703
0.72 0.005 0.488 2.754 8.661 2.383 0.73 0.004 1.569 11.675 65.88 2.534

co
0.74 0.005 1.187 3.510 33.95 2.356 0.75 0.005 2.292 14.158 88.79 2.506
0.76 0.005 1.279 3.472 55.20 2.126 0.77 0.004 2.368 12.675 150.3 2.446
0.78 0.006 1.652 4.849 79.15 2.042
0.80 0.008 2.269 5.029 88.01 2.334

−E (V) vs. SCE 323 K

aR (A) bR (s−1 ) A (s−1 ) N0 (×10−6 cm−2 ) D (×107 cm2 s−1 )

al
0.597 0.004 0.407 1.495 4.613 3.647
0.617 0.004 0.705 3.341 8.606 3.322
0.637 0.005 1.044 4.510 12.95 3.477
0.657 0.007 1.536 8.194 20.55 3.333
on
0.677 0.008 3.177 9.373 49.33 3.144
0.697 0.010 4.753 10.098 82.93 3.052
0.717 0.009 0.890 27.477 6.194 4.116

Data were obtained from best-fit parameters found through the fitting process of the experimental transients using Eq. (16).
rs

capacitive effect generated by the oxide layer (Cr2 O3 )–chloride increment in temperature. It is interesting to observe that the
pe

interactions shows an increase as a function of the tempera-
ture (2.08 × 10−4 , 3.87 × 10−4 and 5.11 × 10−4 C, for 298, 313
and 323 K respectively). Even when charge increasing is almost
negligible, it could be indicative of a higher interaction between
Cr2 O3 and Cl− as temperature increases. However, deeper ana-
lyzes about this kind of interaction are still to be done.
r's
diffusion coefficient is greater at 323 K, suggesting that the dif-
fusion of the chemical species in solution is favored with the
temperature, similar to reported by others authors [1–3,5]. Like-
wise, this result agrees with the predicted by Hirschfelder et
al. [34] and Einstein–Stoke’s equations [13]. Thus, as diffusion
coefficient increases, more chemical species of copper reach the
SS electrode, favoring the nucleation process. Also, it is clear

3.2.2. Analysis of current transients at higher
overpotentials
From last section it is possible to observe that the falling cur-
rent in transients shown in Fig. 4 can be well described by Eq.
o
that the same behavior is obtained in the case of the number of
active nucleation sites. Additionally, at the higher temperature
system, which probably involves a lower adsorption of the chlo-
ride ion, it facilitates the formation of the growing centers of

(12), while after this initial falling current, the data approaches copper phase on SS.
to the Scharifker’s et al. model behavior (Fig. 5b). Therefore, Heerman and Tarallo [35] have proposed a correction to the
th

we propose that the transients shown in Fig. 4 in higher overpo- model suggested by Scharifker et al. [21]. Thus the corrected
tentials could be described by following equation: equation it is expressed as follows:

IT = IC + Iet + I3D−dc(SM) 1 Φ
Au

(16) I3D−dc(HT) (t) = zFDC 1/2 Θ

(πDt)
Fig. 8 shows the comparison of the experimental current tran-
sients with the theoretically generated by non-linear fitting of ×(1 − exp[−αS N0 (πDt)1/2 t 1/2 Θ]) (17)
experimental data to Eq. (16). It can be observed, that the model
where
expressed by Eq. (16) adequately accounts for the behavior of
all experimental transients. Table 3 shows the best-fit nucle-  (At)1/2
exp(−At)
ation parameters at different temperatures, obtained through the Φ=1− exp(λ2 ) dλ (18)
(At)1/2 0
fitting process of the experimental transients using Eq. (16).
Note that in all cases the nucleation rate and the number of Thus, considering the model proposed by Hermann and Tarallo
active nucleation sites increases with the overpotential applied. and the contribution of the electron transfer and the capacitive
At similar overpotential, the nucleation rate increases with the effect, the transients (at higher overpotentials) showed in Fig. 4
900 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903

Table 4
Potential dependence for the physical constants involved during copper reduction, at different temperatures
−E (V) 298 K −E (V) 313 K
vs. SCE vs. SCE
aR (A) bR (s−1 ) A (s−1 ) N0 (×10−6 D (×107 aR (A) bR (s−1 ) A (s−1 ) N0 (×10−6 D (×107
cm−2 ) cm2 s−1 ) cm−2 ) cm2 s−1 )

0.58
0.60 0.61 0.004 0.715 1.225 13.14 2.500
0.62 0.63 0.004 1.070 1.947 19.98 2.500

py
0.64 0.002 0.198 0.926 2.325 2.304 0.65 0.006 1.321 2.641 24.56 2.500
0.66 0.003 0.238 1.511 3.426 2.209 0.67 0.007 1.032 2.896 30.10 2.401
0.68 0.003 0.226 1.785 3.762 2.401 0.69 0.001 0.496 2.862 56.92 2.401
0.70 0.004 0.296 2.305 4.860 2.304 0.71 0.002 1.178 8.873 64.50 2.401
0.72 0.005 0.488 2.754 8.959 2.304 0.73 0.004 1.569 11.675 72.44 2.304

co
0.74 0.005 1.187 3.511 34.73 2.304 0.75 0.005 2.292 14.158 96.57 2.304
0.76 0.005 1.279 3.472 53.13 2.209 0.77 0.004 2.368 12.675 159.6 2.304
0.78 0.006 1.652 4.849 73.17 2.209
0.80 0.007 2.324 5.029 87.45 2.401

−E (V) vs. SCE 323 K

aR (A) bR (s−1 ) A (s−1 ) N0 (×10−6 cm−2 ) D (×10 cm2 s−1 )

al
0.597 0.004 0.407 1.495 5.989 2.809
0.617 0.004 0.705 3.341 10.57 2.704
0.637 0.005 1.044 4.510 16.65 2.704
0.657 0.007 1.536 8.194 25.33 2.704
on
0.677 0.008 3.177 9.373 59.64 2.601
0.697 0.010 4.753 10. 098 97.32 2.601
0.717 0.010 0.935 27.291 8.542 3.025

Data were obtained from best-fit parameters found through the fitting process of the experimental transients using Eq. (16 ).
rs

can be accounted for the following total current equation: each temperature. This plot is similar to that obtained by using
pe

the HT model (Figure not shown). In the framework of atomistic

IT = IC + Iet + I3D−dc(HT) (16 ) theory of nucleation [36–40], it is possible to estimate the critical
size of the nuclei [40,41] with:
Similar fits to those showed in Fig. 8 were obtained employing
Eq. (16 ). The model described by Eq. (16 ) gives similar results   
to that obtained by the Scharifker et al. model, see Table 4, and kT d ln A
nc = −α (19)
only slight differences were registered in the N0 value indicating ze0 dE
a strong dependence of the kinetic and nucleation parameters
r's

with temperature. where k is the Boltzmann constant, T the absolute temperature

Fig. 9 shows a plot of ln A versus Eappl , obtained from Eq. and e0 is the elementary electric charge. By substituting the
(16) (see Table 3). Note that a linear relationship was found for values of d ln A/dE at 298, 313 and 323 K from Scharifker’s
model, in Eq. (19) and by considering the value of α found in
o

this study, it was obtained nc = 0 for every temperature. Same

results were obtained from the HT’s model. Within the atom-
th

istic theory of nucleation, the largest cluster for which one atom
attachment probability is less than one-half is defined as crit-
ical. Thus, the attachment of a new atom converts this cluster
Au

into a stable one, for which the probability of attachment of

Fig. 9. ln A vs. −Eappl. , obtained from data reported in Table 3, at temperatures
indicated in figure.
the next atom is already higher than one-half and henceforth is
able to grow spontaneously. Thus, in these cases every active
site onto the substrate surface acts as a critical nucleus [42,43],
suggesting that within the investigated potential interval, the
thermodynamic barrier for the nucleus formation are negligible
in comparison with the kinetics contribution [43]. Moreover,
accordingly with the Arrenihus equation the reaction rates are
function of temperature, suggesting an increase of the nucleation
rate with the temperature. Similar results have been reported for
cobalt and rhodium electrocrystallization [42,43].
 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903 901

Table 5
Potential dependence of the Ns , calculated from physical constants showed in Table 3 and Eq. (14)
−E (V) vs. SCE 298 K −E (V) vs. SCE 313 K −E (V) vs. SCE 323 K

N0 (×10−6 cm−2 ) Ns /N0 Ns (×10−6 cm−2 ) Ns /N0 Ns (×10−6 cm−2 ) Ns /N0

0.58 – – – – 0.597 1.541 0.334

0.60 – – 0.61 2.214 0.191 0.617 3.148 0.366
0.62 – – 0.63 3.390 0.198 0.637 4.486 0.346
0.64 0.838 0.381 0.65 4.441 0.205 0.657 7.617 0.371

py
0.66 1.298 0.401 0.67 5.082 0.196 0.677 12.620 0.256
0.68 1.520 0.404 0.69 7.080 0.139 0.697 16.990 0.205
0.70 1.901 0.418 0.71 13.240 0.231 0.717 7.658 1.236
0.72 2.867 0.331 0.73 16.280 0.247 – – –
0.74 6.408 0.189 0.75 20.810 0.234 – – –

co
0.76 8.126 0.147 0.77 25.620 0.170 – – –
0.78 11.500 0.145 – – – – – –
0.80 12.350 0.140 – – – – – –

Through the physical constants reported in Table 3 and 4, the within an exclusion zone, enhanced by the concentration deple-
saturation number of nuclei (Ns ) was obtained. This estimation tion around centers growing under mass-transfer control in the

al
was made using Eq. (20) [20]: vicinity of each nucleus [20].
 1/2
AN0
on
Ns = (20)
2k D 3.3. Scanning electron microscopy

The results obtained for Ns in this study, employing the data Fig. 10 shows the SEM micrographs of copper deposits
shown in Tables 3 and 4, are summarized in Tables 5 and 6 obtained at different temperatures, when approximately −1.0 V
rs

for the SM and HT models, respectively. Observe that the Ns was applied during 10 min to the SS/Cu(II)–NH4 Cl–NH3 –H2 O
values increase with the applied potential. It is important to men- system. In this figure it can be observed that granular deposits
tion that, due to the exclusion zones of the deposit, caused by were obtained for each temperature. The deposits with granular
pe

the hemispherical difusional gradients of 3D nucleus, the Ns
will be always lower than the N0 values in the same applied
potential, and both grow in accordance with a more negative
potential.
Analyzing the Ns /N0 ratio, it can be seen that this value is
small (lower than 0.3 in most of the cases). This result suggests
that the copper electrodeposition is not favored in all initially
r's
morphology could be obtained due to the interaction between
the oxide layer (Cr2 O3 ) and Cl− , because of an inhibitory effect
of adsorbed chloride on the initially available active sites, as a
consequence it would produce free zones of growth. An anal-
ysis of the grain density distribution was not possible due to
high grains agglomeration. Instead of, some characteristics of
the deposit could be used to conclude that the above approach

available sites. The reason for this behavior could be the con- is acceptable. Grain size averages obtained were 1.04, 0.96 and
version of sites into growing nuclei, and because nucleation is 0.87 ␮m for 298, 313 and 323 K, respectively. If one perform the
confined to those active centers that have not been included profile analysis of the micrographs shown in Fig. 10, it is pos-
o

Table 6
th

Potential dependence of the Ns , calculated from physical constants showed in Table 4 and Eq. (14)
−E (V) vs. SCE 298 K −E (V) vs. SCE 313 K −E (V) vs. SCE 323 K

Ns (×10−6 cm−2 ) Ns /N0 Ns (×10−6 cm−2 ) Ns /N0 Ns (×10−6 cm−2 ) Ns /N0

Au

0.58 – – – – 0.597 1.756 0.293

0.60 – – 0.61 2.355 0.179 0.617 3.488 0.330
0.62 – – 0.63 3.661 0.183 0.637 5.087 0.305
0.64 0.861 0.370 0.65 4.727 0.192 0.657 8.457 0.334
0.66 1.336 0.390 0.67 5.480 0.182 0.677 13.880 0.233
0.68 1.521 0.404 0.69 7.492 0.132 0.697 18.400 0.189
0.70 1.965 0.404 0.71 14.040 0.218 0.717 8.962 1.049
0.72 2.916 0.325 0.73 17.070 0.236 – – –
0.74 6.482 0.187 0.75 21.700 0.225 – – –
0.76 7.972 0.150 0.77 26.400 0.165 – – –
0.78 11.060 0.151 – – – – – –
0.80 12.310 0.141 – – – – – –
902 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903
on
rs
pe
r's
o
th
Fig. 10. SEM images recorded for SS/0.2 M Cu(II), 4 M Cl− and NH4 + + NH3
(pH 7.5) system, at: (a) −1.0 (298 K), (b) −1.01 (313 K) and (c) −1.017 V
(323 K) during 10 min.
Au
sible to get further conclusions. Thus, by employing this skill
we plot the average profiles of the deposits showed in Fig. 10
(see Fig. 11), by the software ImageDig. V.2TM . In this skill the
white zone is considered as closer to viewer while the black zone
has the opposite mean. From Fig. 11, it is clear that at 298 K,
the grains are width and small, while at 323 K the grains are
thick and sharp, an intermediate situation is obtained at 313 K.
Moreover the cluster’s size increases in height and decreases
in width with the temperature increment. Thus, a raise in tem-
perature favors the growth of the cluster before the coalescence
py
Fig. 11. Average profiles of the deposits showed in Fig. 10.
co
occurs. Note that the deposit obtained at 323 K, exhibits sharp-
ness. Thick and sharp deposits are certainly due to a kinetical
and diffusionally favored system.
4. Conclusions
al
Temperature effect on electrocrystallization process of cop-
per from the SS/Cu(II)–NH4 Cl–NH3 –H2 O system was ana-
lyzed. From the chronoamperometric study, it was possible to
evaluate the transfer coefficient (α), and the exchange current
density (i0 ) at different temperatures. The potentiostatic study
suggested that at least three processes are involved: an elec-
tron transfer reaction, a 3D nucleation and growth process and
a capacitive behavior because of the interaction between oxide
layer (Cr2 O3 )–Cl− , i.e. the combined contribution of the double
layer and the oxide layer barrier on the stainless steel. Analysis
of the transients allowed the obtaining of the nucleation param-
eters values, such as: the nucleation rate constant, the number of
active nucleation sites, the stationary nucleation rate and the sat-
uration number of nuclei, which are favored by the temperature
increment. SEM images of the deposits obtained at different tem-
peratures suggest that Cl− adsorption plays an important role,
blocking the surface active sites, which inhibits the electrocrys-
tallization process in some zones of stainless steel electrode.
The copper electrocrystallization in zones no inhibited by Cl−
adsorption favors the formation of granular deposits and revealed
that the number of grains and the deposit thickness increases
with temperature. The nucleation kinetic enhancement could be
related with a decrease in adsorption at higher temperature, on
the basis from that revealed with the SEM micrographs. The
increase in temperature favors the growth of the cluster before
the coalescence occurs.
The nature of oxide layer–Cl− interactions could evolve by
the temperature, from adsorption to chloride-oxide reaction.
Indeed, further experimentation is needed to reveal the temper-
ature effect on this interaction.
Acknowledgements
This research has been financially supported by CONACyT
– Mexico (project No. 39585-Y). J. Vazquez-Arenas thanks
CONACyT for his postgraduate scholarship. L.H. Mendoza-
Huizar wishes to thank SNI (Mexico) for the stipends received.
 J. Vazquez-Arenas et al. / Electrochimica Acta 52 (2006) 892–903
We also acknowledge to Professor Ignacio Gonzalez for fruitful
discussions.
References
[1] J. Yu, L. Wang, L. Su, X. Ai, H. Yang, J. Electrochem. Soc. 150 (2003)
C19.
[2] T. Montiel, O. Solorza, H. Sánchez, J. Electrochem. Soc. 147 (2000) 1031.
[3] G.R. Pattanaik, D.K. Pandya, S.C. Kashyap, J. Electrochem. Soc. 149
(2002) C363.
[4] S. Peulon, D. Lincot, J. Electrochem. Soc. 145 (1998) 864.
[5] G. Trejo, A.F. Gil, I. González, J. Appl. Electrochem. 26 (1996) 1287.
[6] J.W.P. Schmelzer, Nucleation Theory and Applications, WILEY-VCH Ver-
lag GmbH & Co. KGaA, Weinheim, 2005.
[7] V.M. Fokin, E.D. Zanotto, J. Non-Cryst. Solids 265 (2000) 105.
[8] D. Turnbull, Physics of Non-Crystalline Solids, North-Holland, Amster-
dam, 1964.
[9] I. Gutzow, D. Kashchiev, I. Avramov, J. Non-Cryst. Solids 73 (1985) 477.
[10] A.I. Rusanov, Phasengleichgewichte und Grenzflächenerscheinungen,
Akademie-Verlag, Berlin, 1978.
[11] V.P. Skripov, M.Z. Faizullin, in: J.W.P. Schmelzer (Ed.), Nucleation Theory
and Applications, Wiley-VCH, Berlin, 2005, pp. 4–38.
[12] M.Y. Abyaneh. The electrocrystallization of Niquel. Ph.D. Thesis, Univer-
sity of Southampton, Department of Chemistry, London, 1980.
[13] J.R. Welty, C.E. Wicks, Robert E. Wilson, Fundamentos de Transferencia
de momento calor y masa, Editorial Limusa. Noriega editores, México,
1991, p. 550.
[14] J. Vazquez-Arenas, Study of the involved processes in the electrowinning
of copper from NH4 Cl-NH3 -H2 O solutions. M. Sc. Thesis, Universidad
Autónoma de San Luis Potosı́, Instituto de Metalurgia, San Luis Potosı́,
Mexico, 2006.
rs
[15] J. Vazquez, R. Cruz, ECS Trans. 2 (3) (2006) 355.
[16] A. Ramos, M. Miranda-Hernández, I. González, J. Electrochem. Soc. 148
(2001) C315.
[17] D. Pletcher, R. Greef, R. Peat, L.M. Peter, J. Robinson, Instrumental Meth-
pe
ods in Electrochemistry, Horwood Publishing, Chichester, 2001.
o r's
th
Au
903
[18] A.J. Bard, L.R. Faulkner, Electrochemical Methods. Fundamentals and
Applications, John Wiley & Sons, New York, 2001.
[19] C.H. Hamann, A. Hamnett, Electrochemistry, Wiley-Wch, New York,
1998.
[20] B. Scharifker, G. Hills, Electrochim. Acta 28 (1983) 879.
[21] B.R. Scharifker, J. Mostany, J. Electroanal. Chem. 177 (1984) 13.
[22] M. Palomar-Pardavé, M. Miranda-Hernández, N. Batina, I. González,
Recent Res. Dev. Electrochem. 1 (1998) 15.
[23] L.H. Mendoza-Huizar, J. Robles, M. Palomar-Pardavé, J. Electroanal.
Chem. 545 (2003) 39.
py
[24] M.H. Hölzle, U. Retter, D.M. Kolb, J. Electroanal. Chem. 371 (1994) 101.
[25] A. Milchev, T. Zapryanova, Electrochim. Acta 51 (2006) 2926.
[26] A. Milchev, T. Zapryanova, Electrochim. Acta 51 (2006) 4916.
[27] A. Milchev, Electrocrystallization: Fundamentals of Nucleation and
Growth, Kluwer Academic Publishers, Boston/Dordrecht/London, 2002.
co
[28] D.J.G. Ives, G.J. Janz, Reference Electrodes Theory and Practice, Aca-
demic Press, New York, 1961.
[29] T. Pauporté, J. Finne, J. Appl. Electrochem. 36 (2006) 33.
[30] W. Schmickler, Electrochim. Acta 41 (1996) 2329.
[31] L.M. Torres, A. Gil, L. Galicia, I. González, J. Chem. Educ. 73 (1996) 808.
[32] H. Konno, M. Nagayama, Electrochim. Acta 22 (1977) 353.
[33] B.R. Scharifker, Acta Sci. Venez. 35 (1984) 211.
[34] J.O. Hirschfelder, R.B. Bird, E.L. Spotz, Chem. Rev. 44 (1949) 205–
al
231.
[35] L. Heerman, A. Tarallo, J. Electroanal. Chem. 470 (1999) 70.
[36] A. Milchev, S. Stoyanov, R. Kaischev, Thin Solid Films 22 (1974)
on 255.
[37] A. Milchev, S. Stoyanov, R. Kaischev, Thin Solid Films 22 (1974)
267.
[38] A. Milchev, S. Stoyanov, J. Electroanal. Chem. 72 (1976) 33.
[39] A. Milchev, E. Vassileva, J. Electroanal. Chem. 107 (1980) 323.
[40] A. Milchev, Contemp. Phys. 32 (1991) 321.
[41] D. Kaschiev, J. Chem. Phys. 76 (1982) 5098.
[42] L.H. Mendoza-Huizar, J. Robles, M. Palomar-Pardavé, J. Electroanal.
Chem. 521 (2002) 95.
[43] M. Arbib, B. Zhang, V. Lazarov, D. Stoychev, A. Milchev, C. Buess-
Herman, J. Electroanal. Chem. 510 (2001) 67.