Journal of Electroanalytical Chemistry 505 (2001) 54 61

www.elsevier.nl/locate/jelechem

Characterisation of zinc+cobalt alloy phases obtained by

electrodeposition
E. Gomez a, X. Alcobe b, E. Valles a,*
a
Laboratori de Ciencia i Tecnologia Electroqumica dels Materials (LCTEM), Departament de Qumica Fsica, Uni6ersitat de Barcelona,
Mart i Franques 1, 08028 Barcelona, Spain
b
Ser6eis Cientificotecnics, Uni6ersitat de Barcelona, Lluis Sole i Sabaris 1 -3, 08028 Barcelona, Spain

Received 8 November 2000; received in revised form 12 February 2001; accepted 20 February 2001

Abstract

The anomalous codeposition of Zn+ Co alloys on vitreous carbon, copper and nickel substrates in a chloride bath was studied.
The results indicate that the substrate influences both the initial electrodeposition stages and the alloy formation. For the same
electrodeposition conditions, vitreous carbon and copper substrates favour the formation of deposits richer in zinc than those
obtained over a nickel substrate. In the stripping analysis of deposits obtained during anomalous codeposition, up to three major
oxidation peaks were observed, the two corresponding to the more negative potentials are attributable to the zinc oxidation in the
alloy and the more positive one to the oxidation of the remaining porous cobalt matrix of the alloy. Under our experimental
conditions, two kinds of deposits have been analysed using X-ray diffraction (XRD). XRD analysis showed that deposits with
very low cobalt percentage (less than 3%) and a hexagonal platelet structure had a distorted hcp zinc h-phase. Polyhedral-grained
deposits with between 4 and 10% cobalt were made up of quasi-pure zinc and a Zn + Co g-phase of bcc structure. A correlation
between the stripping curve and the type of deposit has been found. 2001 Elsevier Science B.V. All rights reserved.

Keywords: Zinc cobalt alloys; Electrodeposition; X-ray diffraction; Stripping; Anomalous codeposition

1. Introduction It is well known that the codeposition of zinc with

Zn +Co coatings have attracted interest because
their corrosion resistance is higher than that of pure
zinc coatings, the improvement in corrosion resistance
being similar to that of the Zn+Ni alloy, with the
added advantage that only about 1 wt% Co is necessary
[1 7].
In our laboratory, the Zn+Co alloy deposition on
vitreous carbon from chloride solutions with low total
metal concentration has been studied [8 10]. Zinc-rich
alloy phases were favoured by low potentials (i.e. low
negative current densities), high [Zn(II)]/[Co(II)] ratios
in solution, and stirring. Stripping analysis, morpholog-
ical and compositional analysis and a comparison with
related studies of the same or similar alloys [11] allowed
us to relate tentatively the different stripping peaks to
different types of deposits obtained.
* Corresponding author. Fax: + 34-93-4021231.
E-mail address: e.valles@qf.ub.es (E. Valles).
iron-group metals is anomalous, preferential deposition
of zinc being observed under a wide range of conditions
[12]. Considerable efforts have been made to determine
the cause of this anomaly, the hydroxide suppression
mechanism [13], already proposed for Zn+ Ni deposi-
tion [14], appearing to be most popular. In this model
anomalous deposition occurs due to the formation and
adsorption of a zinc hydroxide film which inhibits
cobalt electrodeposition while favouring that of zinc.
However, with vitreous carbon the formation of zinc
hydroxides and their initial adsorption is uncertain. In
a previous paper we analysed the very initial stages of
deposition, and the results suggested that an initial
deposition of cobalt did not progress as a consequence
of Zn(II) adsorption on the cobalt nuclei [10]. A
modified hydroxide oscillation model has also been
proposed, in which repeating layers of (Zn, ZnO and
Co) would be deposited after an initial cobalt deposi-
tion [15].

0022-0728/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 0 1 ) 0 0 4 5 0 - 8
 E. Gomez et al. / Journal of Electroanalytical Chemistry 505 (2001) 5461
The aim of the present study was the analysis and
characterisation of different Zn+ Co alloy phases and
to test whether the proposed mechanism for the begin-
ning of the anomalous deposition on vitreous carbon
also holds for metallic substrates in baths of higher
metallic concentration. Vitreous carbon, copper and
nickel substrates and different [Zn(II)]/[Co(II)] ratios
were used. No additives were used since they can
influence the composition and morphology of the
deposits.
2. Experimental
A conventional three electrode cell and a poten-
tiostat/galvanostat EG&G 273 were used. The mor-
phology of the deposits was examined with a Hitachi
55
2300 scanning electron microscope. The deposit compo-
sition was analysed with an electron microprobe,
Cameca SX-50. In some cases an X-ray photoelectron
spectrometer (XPS, PHI 5600 multitechnique system
using standard Al Ka radiation, resolution 0.1 eV) was
used.
X-ray diffraction (XRD) phase analysis was per-
formed on a Philips MRD diffractometer using its low
resolution parallel beam optics. The CuKa radiation
(u= 1.5418 A, ) was selected by means of a diffracted
beam flat graphite crystal. 2q/q diffractograms were
obtained in the 20100 range with a step of 0.05 and
a measuring time of 5 s per step.
The solutions were freshly prepared with analytical
grade ZnCl2 and CoCl26H2O. In all the experiments
[Zn(II)]+ [Co(II)] was maintained at 0.5 mol dm 3 and
the solution pH was adjusted to 4 in order to minimise
hydrogen evolution.
All chemicals were of Merck analytical grade and the
water was first doubly distilled and then treated with a
Millipore Milli-Q system.
Vitreous carbon, copper and nickel were in the form
of rods 2 mm in diameter. Vitreous carbon was from
Metrohm, and Cu and Ni, 99.99% pure, from Johnson
Matthey. Both vitreous carbon and copper were pol-
ished with alumina, and nickel was polished with dia-
Fig. 1. Cyclic voltammograms at 50 mV s 1 in the following solu-
tions: (a) 0.15 mol dm 3 ZnCl2 + 0.35 mol dm 3 CoCl2; (b) 0.05
mol dm 3 ZnCl2 +0.45 mol dm 3 CoCl2. =1000 rpm. (A) Nickel
electrode and (B) vitreous carbon electrode.
mond paste of 6, 1 and 0.25 mm. An Ag  AgCl  NaCl 1
mol dm 3 reference electrode was mounted in a Luggin
capillary. All potentials were referred to this electrode.
The counter electrode was a platinum helix.
Stripping analysis were performed immediately after
potentiostatic or galvanostatic deposition in situ, with-
out removing the electrode from the solution, and
selecting in each case an initial potential at which
deposition did not occur.
3. Electrochemical results
3.1. Voltammetric results
The electrodeposition of Zn+ Co over different sub-
strates was studied first by cyclic voltammetry. In the
negative scan, an increase of the zinc(II) concentration
advanced the start of the main electrodeposition pro-
cess, this advance being higher for a nickel substrate
(Fig. 1A) than for vitreous carbon (Fig. 1B). Several
oxidation peaks appeared in the positive scan, their
relative size depending on the solution composition, the
type of substrate and stirring conditions. For the three
substrates higher zinc(II) concentrations increased the
more negative oxidation peaks (Fig. 1A and B, curves
a), which according to the previous work [8] correspond
to the zinc-rich deposits. At lower zinc(II) concentra-
tions only the more positive peaks appeared in the
positive scan (Fig. 1A and B, curves b). In all cases the
56 E. Gomez et al. / Journal of Electroanalytical Chemistry 505 (2001) 5461

current densities causing a clear decrease of peak AB

and an increase of peaks C and D, although with
copper, as with vitreous carbon, a very high current
density was necessary to minimise peak AB. For the
three substrates, increasing current densities, even un-

Fig. 2. Cyclic voltammograms at 50 mV s 1 in a 0.15 mol dm 3

ZnCl2 + 0.35 mol dm 3 CoCl2 solution. Nickel electrode. Rotation
speed: (a) =1000 and (b) = 0 rpm.

solution was moderately stirred during the electrodepo-

sition to ensure alloy formation, since in quiescent
solutions the depletion of zinc(II) near the electrode
could lead to normal cobalt deposition [9].
The comparison of voltammograms of vitreous car-
bon and copper showed that, as in the usual behaviour,
stirring of the solution hindered the nucleation process.
However, with nickel the opposite behaviour was ob-
served, electrodeposition being clearly enhanced by stir-
ring (Fig. 2).

3.2. Stripping results

Stripping analysis allows the in situ characterisation

of the deposits. The electrodeposits were obtained po-
tentiostatically or galvanostatically under stirring, so as
to favour the alloy formation. The galvanostatic de-
posits were mostly used because of the ease of reaching
a given electrodeposition charge. Fig. 3 shows the influ-
ence of both the electrode nature (nickel or copper) and
the galvanostatic current density. Galvanostatic tran-
sients show the typical nucleation spike followed by a
potential plateau (Fig. 3A and B). In previous work on
vitreous carbon [8], the stripping peaks were assigned as
follows: peaks AB and C correspond to zinc oxidation
from different Zn+Co alloys phases, peak D to cobalt
matrix oxidation of these phases, and peak E to the
oxidation of pure cobalt. The stripping results with
metallic substrates were similar to those with vitreous
carbon, showing well-defined oxidation peaks A E that
preceded in all cases the massive substrate oxidation
(Fig. 3A and B). The relative predominance of these Fig. 3. Stripping voltammograms at 50 mV s 1 of deposits obtained
peaks depended both on the substrate and on the galvanostatically at =1000 rpm in a 0.15 mol dm 3 ZnCl2 + 0.35
mol dm 3 CoCl2 solution at different current densities. (A) Nickel
current density. In general, low electrodeposition cur- electrode. Current density: (a) 28.7; (b) 63.7; and (c) 86.0
rent densities favoured the appearance of the first peak mA cm. 2 Q = 5 mC. (B) Copper electrode. Current density: (a)
A B (where peak B was a shoulder of peak A), higher 28.7; (b) 63.7; and (c) 318.5 mA cm 2. Q = 5mC.
 E. Gomez et al. / Journal of Electroanalytical Chemistry 505 (2001) 5461
Fig. 4. Galvanostatic deposition transients for 30 s at 22.3
mA cm 2 and =1000 rpm and stripping voltammograms at 50
mV s 1 of the corresponding deposits, in a 0.05 mol dm 3 ZnCl2 +
0.45 mol dm 3 CoCl2 solution. Q = 21 mC. (a) Nickel electrode
and (b) copper electrode.
Fig. 5. Galvanostatic deposition transient on nickel at 22.3
mA cm 2 and = 1000 rpm, and stripping voltammograms at 50
mV s 1 of deposits obtained after: (a) 2 s; (b) 3.33 s; and (c) 5 s, in
a 0.15 mol dm 3 ZnCl2 + 0.35 mol dm 3 CoCl2 solution.
57
der stirring, brought about the appearance of peak E,
corresponding to pure cobalt.
Differences were observed between copper and nickel
substrates. With the same electrodeposition current
density nickel favoured the formation of the alloy that
oxidises mainly under peaks C and D (curve a in Fig.
4), whereas copper favoured the formation of alloys
that oxidise mainly in peak A (curve b).
4. Characterisation of deposits
In order to characterise the deposits formed under
the different condition, deposits at long deposition
times were prepared, after having checked that the
stripping curves, and, therefore, the composition of the
deposits, did not change at longer deposition times
(Fig. 5). In order to identify each oxidation peak,
deposits were prepared under chosen experimental con-
ditions (bath composition, current density and sub-
strate) that produced different, well-defined stripping
curves.
Electrodeposits obtained with solution I (0.15 M
ZnCl2 + 0.35 M CoCl2), a copper electrode, and low
electrodeposition current densities oxidised mainly in
peak A and in a small peak D, and were made up of
hexagonal platelets (Fig. 6A). XRD showed that they
had a very modified hexagonal zinc h-phase, although
they contained only around 1% cobalt (Fig. 6B).
The cell parameter modification affected mainly the c
crystallographic axis, which was clearly lower than that
of pure zinc. The cell parameters of this deposit were
a= 2.681(2) and c =4.839(4) A, , whereas those of pure
zinc are a= 2.665 and c =4.947 A, .
Deposits were obtained from solution I, but at higher
current densities produced stripping curves showing
peaks A, C and D, the charge under peak C being
higher with nickel than with copper. These deposits
were homogeneous and polyhedral grained (Fig. 7A),
with no hexagonal morphology, and with a cobalt
content between 4 and 10%, this being always higher
with nickel. XRD showed, together with the lines of the
substrate, the lines of an undistorted hexagonal zinc
h-phase, and additional lines that can be indexed con-
sidering a Zn+ Co g-phase of bcc structure with the
parameter a=9.03 A, (Fig. 7B). The position of these
three lines did not depend on the composition of the
deposit. XRDs of these samples were recorded both for
the freshly prepared deposit and for the same deposit
after different times from 7 to 14 days, in order to
detect possible zinc segregation. Identical diffrac-
tograms were obtained in all cases.
X-ray photoelectron spectra (XPS) showed a narrow,
well-defined Co2p peak with a binding energy of 778 eV
(Fig. 7C), in good agreement with the presence in the
deposit of metallic cobalt only, since it is well separated
58 E. Gomez et al. / Journal of Electroanalytical Chemistry 505 (2001) 5461

from the cobalt oxides, located at around 780 eV. A

Zn2p peak appears at around 1022 eV, but unfortu-
nately the peaks of metallic zinc (1022 eV) and of zinc
oxides (1022 1022 5 eV) overlap, so that XPS cannot
throw light on the oxidation state of Zn. However,
since XPS showed that oxygen was detected at the
beginning of sputtering only, the presence of metallic
oxides in the bulk of the deposits can be disregarded.
At lower zinc concentrations in the bath (solutions II
(0.10 M ZnCl2 + 0.40 M CoCl2), and III (0.05 M
ZnCl2 +0.45 M CoCl2)), deposits which oxidised
mainly in peaks C and D were obtained on both copper
and nickel electrodes. Deposits obtained with low elec-
trodeposition current densities were polyhedral grained
and with a Zn h-phase and Zn+ Co g-phase bcc, as
those deposited from solution I at higher current densi-
ties. However, with current densities more negative
than 15 mA cm 2, peak E appeared in the stripping
curve together with peaks C and D. Deposits obtained
under these conditions were inhomogeneous, showing
two distinct zones, a predominant zinc-rich polyhedral-

Fig. 7. (A) SEM micrograph of a deposit obtained galvanostatically

on nickel at 62.7 mA cm 2 for 650 s in a 0.15 mol dm 3 ZnCl2 +
0.35 mol dm 3 CoCl2 solution. =1000 rpm. Cobalt percentage:
7%. (B) X-ray diffractogram corresponding to the deposit of Fig. 7A.

grained zone, and a second zone with a cobalt content

greater than 70% (Fig. 8).

5. Initial stages of alloy deposition

Since alloys deposited on nickel showed some differ-

Fig. 6. (A) SEM micrograph of a deposit obtained galvanostatically
on copper at 22.3 mA cm 2 for 1800 s in a 0.15 mol dm 3
ZnCl2 + 0.35 mol dm 3 CoCl2 solution. = 1000 rpm. Cobalt per-
centage: 1.3%. (B) X-ray diffractogram corresponding to the deposit
of Fig. 6A.
ences with respect to those deposited on vitreous car-
bon or copper, possible differences in the initial
deposition stages were investigated. With vitreous car-
bon, more positive potentials and long deposition times
were necessary in order to detect the formation of the
initial deposit. Upon stepping the potential to 1030
mV the current density increased slowly, nearly reach-
ing a plateau of about 40 mA cm 2 (Fig. 9). The
stripping curve of the deposit obtained during 170 s
under these conditions (curve a) showed only one peak
at around 200 mV, probably corresponding to pure
cobalt. When the deposition time was increased to 375
s (curve b) a large peak of cobalt oxidation, now at
100 mV, appeared together with a small peak centred
at 500 mV, related to the start of the alloy
deposition.
 E. Gomez et al. / Journal of Electroanalytical Chemistry 505 (2001) 5461 59

Fig. 7C. Co2p XPS spectrum of the deposit of Fig. 7A at different sputtering times.

When nickel was used as substrate, less negative
potentials than on vitreous carbon were necessary to
allow the deposition process, i.e. with an electrodeposi-
tion potential of 735 mV the current density
recorded in the j t transient, although low (Fig. 10,
curve a), and although the deposition potential used
was 300 mV more positive, was always higher than that
detected on vitreous carbon at the start of the process.
These deposits oxidised at about 350 mV, as corre-
sponds to a fresh cobalt deposit (Fig. 10, curve b), more
negative potentials being required to attain alloy
deposition.
dise at potentials more negative than those obtained on
nickel substrates.
The second goal of this work was to determine
whether a given stripping peak corresponded to a given
phase, independently of the substrate, used. For the
three substrates, the deposits that oxidised under peak
AB (zinc oxidation) and under a small peak D (cobalt
matrix oxidation) had less than 3% cobalt, had a hexag-
onal platelet structure, and XRD analysis allowed a
clear assignment to a hcp zinc h-phase with cell
parameters clearly different from those of pure zinc and
continuously varying c/a (ratio of c-axis and a-axis)
with cobalt content. Under these conditions of low
cobalt content metallic zinc can incorporate the cobalt

6. Discussion

It has been shown that the stripping technique is an

useful tool to characterise in situ the Zn+ Co electrode-
posits formed in chloride medium on metallic susbtrates
(copper and nickel), as had been shown to be the case
for vitreous carbon. The number of stripping peaks and
their positions were unaffected by the nature of the
substrate. Moreover, the stripping peaks of deposits
obtained with a total metallic concentration of 0.5 M
were similar to those of deposits previously obtained
from more dilute concentrations [8], whose stripping
peaks had been tentatively assigned by combining the
electrochemical and compositional results with the data
of the thermal phase diagram. The study was restricted
to conditions under which anomalous codeposition
takes place. Although the general trends of deposition
are similar, the substrate influences the alloy formation
Fig. 8. SEM micrograph of a deposit obtained galvanostatically on
and the corresponding stripping curve. In general, for copper at 22.3 mA cm 2 for 1800 s in a 0.05 mol dm 3 ZnCl2 +
the same electrodeposition conditions, vitreous carbon 0.45 mol dm 3 CoCl2 solution. =1000 rpm. Cobalt percentage:
and copper favour the formation of deposits that oxi- 70%.
60 E. Gomez et al. / Journal of Electroanalytical Chemistry 505 (2001) 5461

ing the same variation of parameter a as reported for

this phase in the phase diagram. It seems that, in
electrodeposition, the crystalline lattice of zinc cannot
incorporate all the cobalt, and consequently a heteroge-
neous deposit of zinc and a Zn+ Co alloy forms.
Although the thermal diagram of Zn+ Co indicates
that the solubility of cobalt in zinc is around 78% [16],
under electrodeposition conditions the zinc can incor-
porate only up to 3% cobalt, a different phase forming
at higher cobalt contents The (Zn+ Co g-phase) phase
is obtained directly during the electrodeposition, since
the stripping peak C, corresponding to the oxidation of
zinc of this g-phase, appears even for low deposition
times. Therefore, peak A-B corresponds to the zinc
oxidation of the h-phase and the peak C corresponds to
the oxidation of zinc from the Zn+ Co g-phase. The
possibility of zinc segregation was discarded, since the
XRD results of fresh and aged deposits were identical.
Previously, Yan et al [15] found that the electrode-
posits of similar cobalt contents (6.6%) obtained from
an acidic sulphate bath are also heterogeneous, and
contained Zn, ZnO and a-Co. Under our conditions the
existence of a non-distorted Zn phase is clearly de-
tected, but the lines corresponding to a-Co do not
appear. Moreover, the presence of both zinc and cobalt
Fig. 9. Potentiostatic transient and stripping voltammograms at 50
oxides is discounted from XPS results.
mV s 1 of deposits on vitreous carbon obtained potentiostatically at
1030 mV in a 0.05 mol dm 3 ZnCl2 + 0.45 mol dm 3 CoCl2
solution. =1000 rpm. Deposition time: (a) 170 and (b) 375 s.

atoms in its crystalline lattice, although the inclusion of

cobalt causes a significant distortion of the hexagonal
structure, as can be inferred from the variation of the
cell parameters with respect to those of pure zinc.
Although the formation of this Zn-rich phase is fa-
voured by higher zinc(II) concentrations in the bath
and by low electrodeposition current densities, with a
nickel substrate very low current densities are required.
Deposits that oxidise mainly under peaks A and C
(corresponding to oxidation of zinc) and peak D (oxi-
dation of cobalt matrix) are favoured on a nickel
substrate and with cobalt contents ranging between 4
and 10%, are very different from those discussed above.
Although they appear homogeneous under SEM, XRD
shows that they are constituted by two phases, zinc and
a bcc Zn+Co g-phase. The assignation of the addi-
tional lines in the diffractograms to a g-phase of bcc
structure has been possible thanks to the phase diagram
information, where a bcc structure of the g-brass type
with a parameter a between 8.91 and 8.99 A, is de-
scribed [16]. Moreover, the patterns of the g-brass
phase of the JCPDS (PDFc 25-1228, 71-397) [17]
match well with the observed positions and intensities
Fig. 10. Potentiostatic transient and stripping voltammograms at 50
of the additional peaks if the corresponding a parame- mV s 1 of deposits on nickel obtained potentiostaticaly at 735 mV
ter of 9.03 A, is used. This value of the parameter a from a 0.05 mol dm 3 ZnCl2 +0.45 mol dm 3 CoCl2 solution.
leads to a composition of around 89.7% in zinc assum- = 1000 rpm. Deposition time: (a) 70 and (b) 150 s.
 E. Gomez et al. / Journal of Electroanalytical Chemistry 505 (2001) 5461
Therefore, deposits of 4 10% cobalt obtained from
these electrodeposition conditions are formed by the
h-phase of zinc and g-phase of Zn + Co alloy. Similar
results were obtained by Hayashi et al. [18] that de-
tected, from a sulphate bath, the presence of the g-
phase in deposits when the cobalt percentage is greater
than around 7%. Koura et al. [19,20] found that from
molten-salt electrolytes the Zn+ Co deposits consist in
Zn and an intermetallic compound (Co5Zn2) at low
cobalt percentage in the deposits.
On the other hand, in previous work [10] from results
obtained at low total metallic concentration, it was
proposed that the very initial stage of the Zn+ Co
anomalous codeposition on vitreous carbon consisted
of an initial cobalt deposition that could be blocked
later by the adsorption of zinc(II) species. The results
presented here confirmed this proposal on vitreous
carbon and show that cobalt deposition also occurs
initially on nickel electrodes, less negative potentials
being necessary, as is normal, to attain the deposition
process. Moreover, a study of the stripping curves of
the deposits obtained on nickel and vitreous carbon
shows that initial cobalt deposition is favoured on
nickel, so much so that it can be easily detected by
stripping from the first deposition times. A catalytic
effect for cobalt deposition on the nickel electrode
compared with other substrates was also reported pre-
viously [21].
Alloy formation over the initial cobalt deposit takes
place on both nickel and vitreous carbon, although the
nature of the substrate influences alloy formation, vit-
reous carbon and copper favouring the formation of
deposits richer in zinc than those obtained with nickel.
7. Conclusions
In the oxidation of Zn+ Co deposits obtained under
conditions of anomalous codeposition, four stripping
peaks (A D) were detected. A relation between these
stripping peaks and the phases present in the deposit
was found. Deposits with %CoB 3% corresponding to
the hcp h-phase with a c/a ratio variable as a function
of cobalt percentage, oxidise under peak A B (zinc
oxidation) and a small peak D (porous cobalt matrix
oxidation). Deposits formed by pure zinc and the bcc
Zn + Co g-phase oxidise in peaks A (zinc oxidation
from h-phase), C (zinc oxidation from g-phase) and D
(porous cobalt matrix oxidation). Therefore, the ap-
pearance of peak C shows the presence of the g-phase
in the deposit.
At low deposition potentials or current densities, the
formation of deposits of the h-phase were favoured. An
influence of the substrate was observed. Nickel favours
61
the formation of the g-phase and both copper and
vitreous carbon maintain the deposition of the h-phase
under a wide range of conditions.
Results confirm that, independently of the substrate,
the deposition process begins by cobalt deposition.
Over some initial cobalt deposited, more favoured on
the nickel electrode, deposition becomes anomalous
and formation of zinc-rich alloys takes place. The later
cobalt deposition could be hindered by the adsorption
of zinc(II) species over the initial cobalt.
Acknowledgements
The authors thank the Serveis Cientfico-Tecnics
(Universitat de Barcelona) for equipment provision.
This research was supported financially by contract
MAT 2000-0986 of the Comision Interministerial de
Ciencia y Tecnologa (CICYT) and by the Comissionat
of the Generalitat de Catalunya under Research Project
SGR98-027.
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