Elrcrrochmca Am. Vol. 41, Nos. 718. pp. 104-1049.

1996
CopyrIght I, 1996 Published by Elsevier Science Ltd.
Pergamon Printedin Great Britam. Allrights reserved
COl3-4686/96 $75.00 + 0.00

0013-4686(95)00436-X

ELECTRODEPOSITION OF Zn-Ni ALLOYS IN SULFATE

ELECTROLYTES

F. J. FABRI MIRANDA,~ 0. E. BARCIA,~$ S. L. DIAZ,§ 0. R. MATTOSQ:and R. WIART//*

t Centro de Pesquisa da Usiminas, Ipatinga, Mg, Brazil
$ Departamento de Fisico-Quimica-IQ/UFRJ, Rio de Janeiro, Brazil
0 Lab. de CorrosBo, PEMM/COPPE/UFRJ, Rio de Janeiro, Brazil
// UPR 15 CNRS ‘Physique des Liquides et Electrochimie’,
Universite P. et M. Curie, Paris, France

(Received 8 May 1995)

Abstract-The electrodeposition of Zn-Ni in sulfate solutions has been investigated by means of polar-
ization curves, morphological analysis and electrochemical impedance using a rotating disc electrode.
The polarization curves showed two parts, the first one related to the Zn-Ni normal codeposition and
the second one to the Zn-Ni anomalous codeposition. The mass transport influenced only the Zn-Ni
normal codeposition and had no influence on the anomalous codeposition. The temperature showed a
great influence on the Zn-Ni alloy deposition and affected both parts of polarization curves. The electro-
lyte composition had no influence on the Zn-Ni anomalous codeposition, but it affected the transition
current density between normal codeposition and anomalous codeposition.
The impedance diagrams were obtained in sulfate electrolytes and showed four loops at low frequency
domain at the beginning of anomalous codeposition: three capacitive loops and one inductive. For the
high polarizations, one of the capacitive loops disappears. These results were discussed comparatively to
those previously obtained for chloride electrolyte, in view of establishing a kinetic model for the sulfate
electrolyte.

Key words: alloy electrodeposition kinetics, alloy electrocrystallization mechanism, electrochemical

impedance spectroscopy.

1 INTRODUCTION pH increase which would induce zinc hydroxide pre-

Usually the mechanical and chemical properties of
metals are improved by alloying. In recent years,
great interest has been shown in the electrodepo-
sition of alloys, as a technique having great indus-
trial possibilities, mainly in the automotive industry.
Many kinds of alloys are deposited commercially
to supply the automotive industry, among them, the
Zn-Ni alloys. The corrosion resistance of electro-
plated Zn-Ni alloys is higher than that of pure zinc
coatings[ l-43.
The electrodeposition of Zn-Ni alloys is classified
by Brenner[S] as an anomalous codeposition, where
zinc, which is the less noble metal is preferentially
deposited. Meanwhile, the Zn-Ni alloy codeposition
is not always anomalous since in certain conditions
(low current density) it is possible to obtain normal
codeposition, where nickel deposits preferentially to
zinc. Therefore, there is a transition current density
that has to be reached in order to start anomalous
codeposition[4]. Although this phenomenon has
been known since 1907[6], the codeposition mech-
anisms of zinc and nickel are not well understoodC7,
81. There are some propositions to explain the
anomalous codeposition of the Zn-Ni alloys. The
first attributes the anomalous codeposition to a local
l Author lo whom correspondence should be addressed.
cipitation and would inhibit the nickel deposition[9-
111. Another proposition is based on the
underpotential deposition of zinc on nickel-rich zinc
alloys or on nickel nucleic 12, 13-J.
On the other hand, kinetic studies of Zn-Ni co-
deposition are not easily found in the literature,
mainly with the use of electrochemical impedance.
Only recently, Chassaing and Wiart[14] proposed a
kinetic model for Zn-Ni codeposition in chloride
electrolytes.
In this paper, the Zn-Ni codeposition process was
studied in sulfate electrolytes by polarization curves,
surface morphological analysis and electrochemical
impedance. The results are compared with those
obtained by Chassaing and Wiart[lrl] in a chloride
electrolyte.
2. EXPERIMENTAL
The electrolytes used in this study were prepared
using p.a. Merck products and double distilled water
(see Table 1). The electrolytes were prepared without
addition of supporting electrolyte. For all electro-
lytes, the pH value was measured and adjusted to
pH = 1.5 using sulfuric acid. The effect of the ratio
Ni*+/Zn *+ of ion mass in the electrolyte was investi-
gated in the range of 0 to 2.

1041
1042 F. J. FABRIMIRANDAet al.

Table 1. Electrolyte composition

NiSO, .6H,O ZnSO, 7H,O

Electrolyte (mol.dm - 3, (mol.dm - 3, Ni2+/Zn2+

1 - 0.84 0.00
2 0.84 0.84 0.90
3 1.36 0.84 1.45
4 1.87 0.84 2.00

Working rotating disc electrode of Pt with an area 3. RESULTS

of 0.071 cm2 was used. Rotation speeds up to
25OOrpm were used to investigate the influence of
mass transfer on the polarization curves and on the
impedance diagrams. The counter electrode was a
large area Pt gauze, whilst the reference used was a
mercury sulfate electrode made by Metrohm to
which all potentials are referred.
Polarization curves were obtained for all electro-
lytes shown in Table 1, using a Schlumberger
SI-1286 electrochemical interface. Impedance spec-
troscopy measurements were carried out by means of
a Schlumberger SI-1250 frequency response analyzer
coupled to a Schlumberger SI-1286 electrochemical
interface, controlled by a Compaq 486 micro-
computer.
The mass of the coating was determined by disso-
lution with HCl and the Zn and Ni contents were
analyzed using Atomic Absorption Spectroscopy
and Plasma Spectroscopy. These data were used to
calculate the efficiency of the process and the partial
polarization curves for nickel, zinc and hydrogen.
The surface morphology of the deposits was evalu-
ated by Scanning Electron Microscopy (SEM).
3.1 Steady-state polarization curves
The polarization curves were recorded for all elec-
trolytes showed in Table 1. Figure 1 shows the char-
acteristic potentiostatic polarization curve for the
electrolyte 3 (Table l), obtained with the Pt rotating
disc at 25°C and 625 rpm. The Pt free potential (E,,)
is around + lOOmV,,, . As the cathodic polarization
starts, the current density increases slightly until
- 1200 mV,sc. Following, the current density
increases abruptly reaching a maximum at
- 1400 mVsse, then reducing to a minimum at
- 1425 mVsse. After that, the current density varies
linearly with the cathodic polarization.
Chemical analyses were carried out for the depos-
its obtained at different potentials along the polar-
ization curves. The results are indicated in Fig. 1
(points A, B, C and D). The Zn-Ni anomalous code-
position occurs only in the linear part of the polar-
ization curves (part II). On the other hand, for part I,
the hydrogen reduction reaction and the Zn-Ni
normal codeposition, with low efficiency, coexist.

: o.oo it q,q;;;
~200.00 -300.00 -800.00
Potential (mVSSE)
Fig. 1. Steady-state potentiostatic polarization curve for Ni’+/Zn *+ = 1.45 sulfate electrolyte at 625 rpm
and 2s”C. Nickel content in anomalous deposit: (A) Ni = 18%; (B) Ni = 12%~;(C) Ni = 10%; (D)
Ni = 8%
 Electrodeposition of Zn-Ni alloys
+,~,:,:,:,:,t,?,t:)t:,,,,~
-300.00
Potential
Fig. 2. Steady-state potentiostatic polarization curves for Ni’+/Zn” = 1.45. Sulfate electrolyte at 25°C.
Rotation speeds: (0) IOOrpm; (0) 625 rpm; (A) 25OOrpm.
In order to study the influence of mass transport
on the Zn-Ni codeposition in sulfate solutions,
polarization curves were obtained at 25°C with dif-
ferent rotation speeds. Figure 2 shows, for the elec-
trolyte number 3, the polarization curves carried out
on Pt rotating disc at 25°C. The curves show the
same shape as discussed previously and they are
influenced by mass transport only in part I, where
prevails the hydrogen reduction. For part II of the
curve, the Zn-Ni anomalous codeposition is inde-
pendent of the mass transport. Surface analysis of
SEM was carried out as shown in Fig. 3, to verify
the influence of rotation speed on the morphology of
Zn-Ni alloy deposited. The deposits were obtained
on platinum electrode under galvanostatic condi-
tions (20mA.cm-2; 5min). It can be seen that rota-
tion speed has influence on the morphological
characteristics of the deposits. The nodules are the
typical morphology of Zn--Ni anomalous
codeposition[15], as shown in Fig. 3. At 100 rpm
Fig. 3(A) the deposit is more compact than at
2500rpm Fig. 3(B). However, the mass transport has
practically no influence on the polarization curves.
Figure 4 shows the influence of the temperature on
the behaviour of the polarization curve, for electro-
lyte 3. When the temperature is increased from 25°C
to 50°C both parts of the polarization curve change.
For part I, the maximum current density increases,
and for part II (Zn-Ni anomalous codeposition), the
curve is shifted towards less negative potentials and
exhibits a larger slope. These changes on the part II
is followed by an increase in the Ni content of the
alloy, as shown in Fig. 4. Figure 5 shows the effect of
the temperature on the morphology of Zn-Ni anom-
alous deposits. The deposits were obtained onto
platinum electrode under galvanostatic conditions
(20mA.cm*, 5min), maintained on the part II of
1043
A0
lso:
4
A0 @
._***
/II,,,]
- 800.00 -1300.00 -1800.00
(mVssE)
polarization curves. The Zn-Ni deposits show a
nodular morphology, but at 25°C the nodules are
coarse and less compact than at 50°C.
The influence of the electrolyte composition on the
polarization curves was also studied, as shown in
Fig. 6. The polarization curves were carried out for
the electrolytes 1 to 4 as shown in Table 1. For elec-
trolytes 2 to 4, the ratio Ni’+/Zn*+ changed from
0.9 to 2.0. Figure 6 shows that the electrolyte com-
position affects only the part I, where the ratio Ni2+/
Zn2+ = 0.9 produces the highest current densities.
As shown in part II (Zn-Ni anomalous codeposition)
the electrolyte composition has no influence on the
electrochemical process of alloy deposition.
3.2 Impedance measurements
The impedance diagrams were obtained for the
points A, B, C and D of the polarization curve
shown in Fig. 1.
The dependence of impedance on current density
are illustrated in Fig. 7, for the electrolyte with a
Ni2+/Zn2+ ratio of 1.45 (No. 3, Table l), at the elec-
trode rotation speed of 625rpm. The impedance
plots of Fig. 7 reveal a high-frequency loop corre-
sponding to the charge transfer resistance, R,, in
parallel with the double-layer capacitance. In the
low-frequency domain four or three features are
observed according to the current density. For a
current density of 1.5 mA.cmd2 (Fig. 7(A)) which is
close to the start of Zn-Ni anomalous codeposition,
four loops were obtained: one capacitive showing a
characteristic frequency around 4 Hz, one inductive
loop for the frequency of 0.71 Hz and two capacitive
loops with characteristic frequencies of 0.22Hz and
O.O30Hz, respectively. Figure 7(B) shows the imped-
ance diagram obtained at 3.5mA.cmT2, where four
loops are observed in the low frequency domain. The
 F. J. FABRIMIRANDA
et al.

Fig. 3. Morphology of deposits obtained in sulfate electrolyte with Ni’+/Zn’+ = 1.45 at 20mAcm-‘,
t = 5min and 25°C. (A) 100rpm; (B) 2500rpm.

nature of the loops was maintained, but the charac-
teristic frequencies changed for the first capacitive
loop from 4 Hz to 40 Hz. For the current density of
lOmA.cm-‘, four loops were observed showing the
same nature as the formers, however, the sizes of the
first capacitive loop and second inductive loop
changed. Besides, the characteristic frequency of the
inductive loop increases with the polarization, from
0.71 Hz on plot A to 7.1 Hz on plot C. For
50mA.cn-2 (Fig. 7(D)) only three loops were
detected since the first capacitive loop (40 Hz) disap-
peared. The other loops maintained the same charac-
teristic frequencies, but their size increased. The
chemical analysis of the deposits performed at the
same current densities where the impedance dia-
grams were obtained, showed that the nickel content
in deposits is high at low polarization (Fig. 7(A)) and
decreases when the polarization increases (Fig. 7(D)).
In order to verify the influence of mass transport
on the Zn-Ni codeposition, impedance diagrams
 Electrodeposition of Zn-Ni alloys
0.00
+200.00 -300.00
Potential
Fig. 4. Steady-state potentiostatic polarization curves for sulfate electrolyte with Ni*+/Zn’+ = 1.45 at
16OOrpm. Temperature: (0) 25°C: (m) 50°C. Nickel content in anomalous deposit: (A) Ni = 8%; (B)
Ni = 12%.
were obtained at different rotation speeds. The
results showed that the diagrams had the same
pattern and characteristic frequencies as those shown
in Fig. 7, for all rotation speeds. The impedance
results confirmed that the mass transport has no
effect on the Zn-Ni anomalous codeposition.
4. DISCUSSION
The polarization curves obtained for the Zn-Ni
codeposition in sulfate electrolytes have a character-
istic shape, as seen in Fig. 1. Such curves can be
divided into two parts. In the first part, the Zn-Ni
normal codeposition, where nickel is deposited pref-
erentially to zinc and where the hydrogen reduction
prevails. The efficiency of the deposition is very low,
around l%, so that the maximum current density is
practically due to the hydrogen reduction. In the
transition region between part I and II, the current
density reduces abruptly and the efficiency grows
rapidly reaching around 98%. In this domain,
hydrogen reduction decreases and the Zn-Ni anom-
alous codeposition prevails. The nickel content in
the deposit is relatively high (18%) at the beginning
of Zn-Ni anomalous codeposition (part II) and
decreases when the polarization increases.
According to the experiments performed by
Chassaing and Wiart[14] for Zn-Ni anomalous
codeposition in chloride electrolytes, the polarization
curves were found to be independent of the electrode
nature and of its rotation speed. Those results are in
good agreement with these obtained in the present
study. Although not shown in this paper, the polar-
ization curves obtained using carbon steel rotating
electrodes showed the same behaviour as those
obtained for platinum, mainly on part II of curves
1045
- 800.00 -1300.00 -1800.00
(mV&
where the Zn-Ni anomalous codeposition occurs.
That fact suggests that anomalous codeposition is
preceded by normal codeposition that produces a
previous deposit onto the surface of the materials
before starting the anomalous codeposition.
The influence of temperature on the Zn-Ni anom-
alous codeposition (Fig. 4) shows that an increase in
the temperature induces changes in both parts of the
polarization curves. On part I, the temperature
causes an increase in the hydrogen reaction and as a
consequence an increase in the maximum current
density and on part II the nickel deposition is facili-
tated since the nickel content in deposit increases by
50%. Therefore, the temperature causes a reduction
on the inhibiting effect of zinc on the nickel electro-
deposition. The temperature influences also the
deposit morphology of Zn-Ni anomalous codeposi-
tion as shown in Fig. 5. With increasing temperature,
the compactness of Zn-Ni deposits also increases
and the size of nodules reduces, due to an improve-
ment in the nucleation rate.
According to Chassaing and Wiart[14] experi-
ments, the polarization curves in chloride electro-
lytes are shifted towards negative potentials when
the ratio Ni2+/Zn2+ increases from 0 to 3. In the
sulfate solutions, the polarization curves obtained for
electrolytes with Ni2+/Zn2+ ratio ranging from 0 to
2 did not show the same results (Fig. 6).
The electrolyte composition affects only the part I
of the polarization curves and has no influence on
the anomalous codeposition region. On the part I
the current densities are increased when the Nil+/
Zn2+ ratio is low, then the maximum current density
that is reached at the transition between part I and
II is increased. Therefore, the transition current
density between Zn-Ni normal codeposition to
anomalous codeposition is affected by electrolyte
1046 F. J. FABRI MIRANDA et al.

Fig. 5. Morphology of deposited obtained in sulfate electrolyte with Niz’/Zn2’ = 1.45 at 20rnAc~K~,
t = 5 min and 1600rpm. (A) 25°C; (B) 50°C.

composition. This result is in disagreement with the
experiments obtained by Fukushima et al.[9], since
they found that the Ni2+/Zn2+ ratio had no influ-
ence on the transition current density between
normal and anomalous codeposition.
Chassaing and Wiart[14] studied also the Zn-Ni
anomalous codeposition by electrochemical imped-
ance. Their results showed one high-frequency
capacitive loop which corresponds to the charge
transfer resistance, R,, in parallel with the double-
layer capacitance. In addition, three main features
were observed in the low-frequency domain. Firstly,
an inductive loop exists, with a characteristic fre-
quency which increases quasi-exponentially with
polarization, from 6.3 Hz at 5 mA.cm- ’ to 63 Hz at
i’5mA.cm-2. The second loop has a characteristic
frequency around 250mHz. According to those
authors[14], its size is related to the nickel content
in the deposit. The size of this loop is large when the
nickel content is higher. Its size decreases when the
 Electrodeposition of Zn-Ni alloys
Fig. 6. Steady-state potentiostatic polarization curves for sulfate electrolytes obtained at 1600rpm and
25°C. (m) Ni’+/Zn*+ = 0.00 (Pure zinc). (0) Ni*+/Zn’+ -- 0.90; (A) Ni’+/Zn*+ = 1.45; (a) Ni”/
’ Zn2+ = 2.00.
polarization increases since the nickel content in the
deposit varies from 22% at 5mA.cm-* to 12% at
75mA.cm-*. The third loop at the lowest fre-
quencies is an inductive loop which appears at a
characteristic frequency close to 40mHz and inde-
pendent of the potential.
In the present paper, the impedance diagrams in
sulfate electrolytes showed four loops in the low-
frequency domain for current densities lower than
lOmA.cn-* (Fig. 7). For high polarization
(50mA.cm-*), only three loops were detected. One
capacitive, which was not observed in chloride
medium, has a characteristic frequency of 4Hz at
l.SmA.cm-* and of 4OHz at lOmA.cm-*, and
finally disappears when the polarization increases.
The inductive loop has a characteristic frequency of
0.71 Hz at lSmA.cm- *. This frequency increases to
7.2Hz when the current density increases to
10mA.cm-2. From lOmA.cm-* up to 50mA.cm-*,
the frequency is constant. The size of this loop
increases when the polarization increases, as in the
case of chloride electrolytes. The next loop shows the
same capacitive nature and the same frequency of
0.25 Hz as for chloride electrolytes. However, its size
increases with the polarization in sulfate medium, a
fact which has not been observed for chloride elec-
trolytes. The last loop obtained at the lowest fre-
quencies has a characteristic frequency around
30mHz and is capacitive in sulfate medium. On the
other hand, for chloride electrolytes the loop
occurring at frequencies around 30mHz was induc-
tive in nature.
As observed for chloride electrolytes, an increase
in polarization implies the reduction of nickel
content in the deposits obtained in sulfate solutions.
At 1.5mA.cm-Z the nickel content was 18% which
reduces to 8% at 50mA.cm-*.
1047
The impedance diagrams obtained at different
rotation speeds showed that the mass transport had
no influence on the Zn-Ni anomalous codeposition,
in agreements with the results of polarization curves.
5. CONCLUSIONS
The Zn-Ni anomalous codeposition in sulfate
electrolytes has been studied using polarization
curves, electrochemical impedance and morphologi-
cal analysis. The main electrodeposition parameters
were investigated such as rotation speed, tem-
perature and electrolyte composition.
The polarization curves for Zn-Ni alloy codeposi-
tion showed a shape that can be divided in two
parts. The first one is related to the Zn-Ni normal
codeposition where the hydrogen reduction prevails,
as a consequence of the low efficiency process. The
second part is associated to the Zn-Ni anomalous
codeposition and it presents an I-E linear relation-
ship.
The mass transport influences only the Zn-Ni
normal codeposition (part I) and has no influence on
the kinetics of anomalous codeposition (part II).
The temperature has a great influence on the
Zn-Ni alloy deposition and affects both parts of
polarization curves. The temperature shifted the
beginning of anomalous codeposition towards less
negative potential and increased the nickel content
in the deposit. When increasing the temperature the
deposits become more compact and reveal finer
nodules.
The electrolyte composition had no influence on
the Zn-Ni anomalous codeposition, but affected the
transition current density between normal codeposi-
tion (part I) and anomalous codeposition (part II).
 1048 F. J. FABRI MIRANDA et al.

RI l ohm. cm21 Re (ohm. cme)

1111111111111111111
2,CI &I) *
RI (ohm. cm21 Ro (ohm. cm21

Fig. 7. Impedance diagrams of Zn-Ni anomalous codeposition in a sulfate electrolyte with Ni”/
Zn2+ = 145 at 625rpm and 25°C recorded at the points A, B, C and D in Fig. 1. (A) i = lSmA.cm-*,
Ni = l&,;(B) i = 3.5mA.cmZ, Ni = 12%; (C) i = lOmA.cm’, Ni = 10; (D) i = 50mA.cm2, Ni = 8%.

The impedance diagrams were obtained in sulfate
electrolytes and showed, at the beginning of anom-
alous codeposition, four loops at low frequency
domain: three capacitive loops and one inductive.
For the high polarization, one of the capacitive loops
disappears.
Acknowledgemenls-The authors wish to thank Mr J. G. de
Sousa and Miss M. Kokke for their helpful comments in
the preparation of this paper, and also USIMINAS S. A.,
FINEP, CNPq and CAPES.
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