Materials Chemistry and Physics 125 (2011) 621–627

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Influence of Ni2+ concentration and deposition potential on the characterization

of thin electrodeposited Zn–Ni–Co coatings
Mortaga M. Abou-Krisha ∗
Faculty of Science, Chemistry Department, South Valley University, Qena 83523, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: The electrodeposition of Zn–Ni–Co alloys from sulphate electrolytes was studied on steel rod. In order
Received 2 February 2010 to elucidate the characteristics of the layer formation, a complementary approach was used based on
Received in revised form the combination of various electrochemical techniques. The cyclic voltammetry and galvanostatic tech-
10 September 2010
niques for electrodeposition, while potentiodynamic polarization resistance and anodic linear sweeping
Accepted 7 October 2010
voltammetry techniques were used for corrosion study. Under the examined conditions, electrochemical
and surface analysis indicate that the deposition has taken place with the formation of three structures
Keywords:
have a composition corresponding to pure Zn, ␥-Ni5 Zn21 and pure Co phases. The influence of nickel
Electrochemical studies
Zn–Ni–Co alloy
concentration as well as the effect of potential on the surface appearance and the deposits composition
Deposition potential was examined. Under these experimental conditions the electrodeposition of the alloys is of anomalous
Corrosion resistance type. The results indicate that the addition of Ni to the Zn–Co alloy, Zn–Ni–Co alloy formed which is
Sulphate bath more corrosion resistance than Zn–Co alloy. Also, the amount of ␥-phase increased and the amount of
pure Zn decreased with the increase of nickel concentration in the bath. The corrosion resistance of the
zinc–nickel–cobalt alloy had been improved with the more concentration of nickel. The Ni content in the
deposition layer had been increased at high deposition potential, whereas, pure Zn deposition had been
decreased.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction pure zinc but does not reaches Zn–Ni alloys [16,17]. Instead of being
used as promising anti-corrosion coatings, electrodeposited Zn–Co
The development of new materials, particularly electrode- alloys with controlled morphology and composition have also been
posited alloys with properties superior to those of pure metals, the subject of many studies as a consequence of their observed
is of increasing technological interest because such thin films catalytic activity, very similar to Zn–Ni alloys [16–19].
can be of great industrial value, particularly in the computer and On the other hand, the mechanical, physical and electrochemi-
electronics industries, as well as being used as decorative and cal properties can be improved by alloying zinc with nickel [20–22].
protective coatings [1–3]. According to the literature [4,5], zinc Zn–Ni alloys are mostly used because of their high degree of corro-
alloys can provide improved corrosion resistance compared to sion resistance and good mechanical properties [23]. Zn–Ni alloys
pure zinc in the protection of ferrous-based metals. This is easily with Ni content in the range of 12–14 wt.% exhibit the best corro-
achieved by alloying Zn with more noble metals, mostly with sion properties and can be several times better than a pure zinc
metals of the iron group (Ni, Co and Fe) [6–11]. In recent years, coating of the same thickness [24]. Zinc–nickel alloys exist in vari-
the interest in zinc alloy coatings, such Zn–Ni, Zn–Fe and Zn–Co, ous phases and their structure and morphology also determine the
has been increasing as a consequence of their better mechanical corrosion resistance of a deposit [25]. Therefore, it was interest-
and anti-corrosion properties than pure zinc coatings, and as a ing to investigate the effect codeposition of a Ni on improving the
substitute for toxic and high-cost cadmium coatings [12–14]. It Zn–Co alloy characteristics.
was found that Zn–Ni and Zn–Co alloys deposits are generally of The literatures concerning the ternary alloys are very few in
anomalous type according to Brenner’s definition [15]. comparison with binary alloys. Consequently, the objective of this
The electrodeposition of Zn–Co alloys exhibits a significant work is to study the electrodeposition of bright Zn–Ni–Co alloy in an
higher corrosion resistance and better surface morphology than acidic sulphate bath. The influence of nickel codeposition on cor-
rosion resistance properties, surface brightness and alloy deposit
composition as well as cathodic current efficiency on the obtained
Zn–Ni–Co alloy was studied. The effect of the plating parameters
∗ Tel.: +20 143830041; fax: +20 965212738. such as, Ni2+ concentration and deposition potential, were also
E-mail address: m abou [email protected] examined.

0254-0584/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2010.10.007
622 M.M. Abou-Krisha / Materials Chemistry and Physics 125 (2011) 621–627

Table 1
Values of Ni, Co and Zn amount in the deposit, total mass of the deposit, % (Ni, Co and Zn content), current efficiencies % (Ni, Co, Zn and Zn–Ni–Co deposits), thickness and
electrochemical corrosion measurements of the deposit on steel (0.196 cm2 ) deposited galvanostatically from a bath containing 0.20 M ZnSO4 , 0.2 M CoSO4 , 0.01 M H2 SO4 ,
0.2 M Na2 SO4 , 0.2 M M H3 BO3 and different concentration of NiSO4 at 10 mA cm−2 for 10 min at 30 ◦ C.

Ni2+ concentration in the bath (M)

0.05 0.1 0.2 0.3 0.4 0.5

−6
Zn amount in the deposit (×10 g) 650 574 522 480 446 389
Ni amount in the deposit (×10−6 g) 11 24 39 46 61 75
Co amount in the deposit (×10−6 g) 10 12 13 16 18 21
Total mass of the deposit (×10−6 g) 671 610 594 542 525 485
Zn content (%) 96.87 94.11 91.2 88.56 84.95 80.20
Ni content (%) 1.64 3.93 6.56 8.48 11.61 15.46
Co content (%) 1.49 1.96 2.18 2.96 3.44 4.34
Zn current efficiency, eZn (%) 81.2 72 67 60 54.5 48.2
Ni current efficiency, eNi (%) 3 6.7 11 12.6 17 21
Co current efficiency, eCo (%) 2.8 3.3 3.6 4.4 5 5.8
Zn–Ni–Co deposit current efficiency, eZn–Ni–Co ) (%) 87 82 81.6 77 76.5 75
Thickness of the deposit (␮m) 4.76 4.3 4.08 3.77 3.6 3.3
Rp (K ) 1.9 1.917 1.933 1.95 1.986 2.02
icorr. (×10−6 A cm−2 ) 0.71 0.63 0.57 0.53 0.51 0.479
Ecorr. (mV) −1016 −983 −948 −936 −820 −703

2. Experimental 3. Results and discussion

The electrolytes used for electrodeposition of Zn–Ni–Co alloy have been freshly
3.1. Comparison between the electrodeposited Zn–Co and
prepared by using Analar grade chemicals, without further purification, and doubly
distilled water. The standard chemical compositions of the basic electrolyte is 0.20 M Zn–Ni–Co alloys
ZnSO4 , 0.20 M NiSO4 , 0.20 M CoSO4 , 0.01 M H2 SO4 , 0.20 M Na2 SO4 and 0.20 M H3 BO3 .
The pH of bath was measured at 30.0 ± 1 ◦ C and was found 2.5 ± 0.02. All experi- The electrodeposition of each Zn–Co and Zn–Ni–Co codeposi-
ments were carried out in duplicate and the reproducibility of these measurements tion on steel rod in bath solution at 30.0 ◦ C were studied by cyclic
was found to be satisfactory. The electrolytic cell was used for the present work as
detailed in Ref. [26].
voltammetry (Fig. 1). The cyclic voltammograms are convenient
In each experiment, the cell was cleaned with a mixture of chromic/sulphuric for depicting the various phases of exposure during corrosion of
acids and, then washed with first and second distilled water. The cell was filled with the deposit [29]. In the negative scan, the deposition potential of
50 cm3 of the electroplating solution and placed in air thermostat to ensure tempera- Zn–Co and Zn–Ni–Co alloys are at about −1063 mV and −1049 mV
ture stability at 30.0 ◦ C. Series of experiments have been carried out and the influence
respectively. This means that the Zn–Ni–Co alloy deposition poten-
of variation of NiSO4 concentrations (0.05–0.50 M) and deposition potential (−500
to −1200 mV) have been investigated. tial is nobler than Zn–Co deposition potential; this may be due to
All electrochemical experiments were carried out using an EG&G Princeton codeposition of nickel into the alloy. This position suggested that
Applied Research potentiostat/galvanostat Model 237A controlled by a PC using the codeposition enable Zn to deposit at more positive potential
352 corrosion software. To verify the influence of different conditions on the depo- (i.e. shifts the deposition potential of Zn to less negative values)
sition process, a cyclic voltammetry and galvanostatic measurement have been used.
Potentiodynamic polarization resistance analysis and anodic linear sweep voltam-
due to the presence of Co2+ and Ni2+ which facilitates Zn deposi-
metry for corrosion resistance studies has been also used. Zn–Ni–Co alloys were tion. However, the codeposition of Co and Ni shifted negatively in
stripped under potentiodynamic conditions in: (i) the same electrolyte of elec- the presence of Zn2+ which reduces Co and Ni deposition. Similar
trodeposition for cyclic measurements, (ii) 0.5 M Na2 SO4 + 0.05 M EDTA solution for behavior is observed in the deposition of Zn–Ni alloy [27]. During
anodic linear sweep voltammetry [13], (iii) 5% NaCl solution for potentiodynamic
the negative scan there is a cathodic peak which started at about
polarization resistance measurements.
In order to determine the composition of deposit, it was stripped in 30% (v/v) HCl −574 mV. This cathodic peak ascribed to the codeposition of sul-
solution and analyzed to ascertain the % of Zn, Ni and Co contents in the deposited phur, which liberated from the reduction of sulphate group at the
alloy using atomic absorption spectroscopy (Varian SpectrAA 55). The Zn, Ni and cathode in the presence of H2 SO4 in the plating bath as follows [26]:
Co contents in the deposit were confirmed by EDS (energy-dispersive X-ray spec-
trometer) system with link Isis® software and model 6587 X-ray detector (Oxford,
UK). Using the resultant analysis, the film thickness [27] and the cathode current SO4 2− + 8H+ + 6e− → S + 4H2 O
efficiency of the deposit from the selected baths on steel were calculated.
To measure the corrosion resistance of the deposited [28], the potentiody-
namic polarization resistance technique was used. In this technique, steel with the 0.010
deposited alloy (galvanostatically or potentiostatically) was washed and transferred
into an electrolytic cell containing 50.0 cm3 of 5% NaCl in order to dissolve the coat-
0.005
ing anodically. To begin the measurements, the sample was introduced into the cell
immediately after electroplating, rinsed with double distilled water and was allowed
until a steady-state was achieved when the corrosion potential was reached. The 0.000
i / A cm-2

anodic dissolution of deposits in a voltammetric mode was conducted at a potential

scan rate of 2 mV s−1 . The values of electrochemical corrosion measurements for the
coatings are presented in Table 1. -0.005 (d) Zn-Co
The deposits phase structures were characterized by a Brucker Axs-D8 Advance (e) Zn-Ni-Co
X-ray diffractometer using CuK␣ radiation ( = 1.5406 Å). In order to identify the
different deposited alloy phases, a comparison between the obtained XRD patterns -0.010
and appropriate JCPDS-cards were carried out. The grain size was determined using
Scherrer equation, D = 0.9/ˇ cos  where D is the grain size,  is the incident radia-
-0.015
tion wavelength, ˇ is the corrected peak width at half maximum intensity and  is
the angular position.
The qualitative and semiquantitative chemical analyses of the Zn–Ni–Co alloys
-1200 -1050 -900 -750 -600 -450 -300 -150 0
were performed by energy dispersive X-ray (EDX) in a model QX 2000 (Link Analyti- E vs. Ag / AgCl / mV
cal) device using Zn, Ni and Co standards (99.998%) from Micro-Analysis Consultants
Ltd. (Cambridgeshire, UK). Scanning electron microscopy (SEM, JSM-5500 LV, JEOL, Fig. 1. i–E curves (cyclic voltammograms) for steel in (a) 0.20 M ZnSO4 and 0.20 M
Japan) has been used to study the surface structure of the alloys and to measure the CoSO4 , (b) 0.20 M ZnSO4 , 0.20 M NiSO4 and 0.20 M CoSO4 with 0.01 M H2 SO4 , 0.20 M
thickness of the deposits. Na2 SO4 , 0.20 M H3 BO3 and scan rate 5 mV s−1 at 30.0 ◦ C.
 M.M. Abou-Krisha / Materials Chemistry and Physics 125 (2011) 621–627 623

0.010

0.005

0.000

i/A cm-2
-0.005
0.10 M
-0.010 0.20 M
0.30 M
-0.015 0.40 M

-0.020
Fig. 2. XRD patterns of electrodeposited Zn–Ni–Co alloy on steel from a bath con- -1200 -1050 -900 -750 -600 -450 -300 -150
taining 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.20 M NiSO4 , 0.01 M H2 SO4 , 0.20 M Na2 SO4 , E vs. Ag / AgCl / mV
0.20 M H3 BO3 at 10 mA cm−2 for 20 min at 30.0 ◦ C.
Fig. 3. i–E curves (cyclic voltammograms) for steel in 0.20 M ZnSO4 , 0.2 M CoSO4 ,
0.01 M H2 SO4 , 0.20 M Na2 SO4 , 0.20 M H3 BO3 and different concentration of NiSO4
It was found previously that the deposition potential of sulphur at scan rate 5 mV s−1 and 30.0 ◦ C.
is shifting to more noble with the decrease in pH [30]. Fortunately,
the codeposition of sulphur leads to more improvement of the crys- tration, ranging from 0.1 M to 0.4 M. It is clear from the cathodic
tallinity of the deposits [31]. polarization part of the cyclic voltammograms that the deposition
From the positive scan of the cyclic voltammograms (Fig. 1), that potentials are shifted positively with increasing Ni2+ concentration
corresponds to Zn–Co voltammogram, there are three peaks cor- in the plating bath. Also, the first cathodic peak, that is attributable
responding to the dissolution of the constituents of two phases, to the formation of sulphur, is not significantly affected with the
␩-phase (CoZn13 ) and ␥-phase (Co5 Zn21 ). The first and second increase in Ni2+ concentration.
anodic peaks correspond to the dissolution (dealloying) of Zn from The anodic part of the cyclic voltammetry (Fig. 3) consists of
␩- and ␥-phases respectively. The third peak corresponds to Co several oxidation peaks. It can be seen that there is a change in the
matrix oxidation of these phases [32]. However, for Zn–Ni–Co height of peaks. Furthermore, increasing the Ni2+ concentration in
voltammogram, there are four anodic current peaks; the first disso- the electrolyte was accompanied with disappearance of some peaks
lution anodic peak attributed to the dissolution of zinc from pure Zn and growth of others. The first dissolution anodic peak which corre-
phase and the second anodic peak corresponds to dissolution of Zn sponds to the dissolution of Zn from pure Zn-phase shifts positively
from ␥-Ni5 Zn21 phase which was verified by XRD (Fig. 2). The X-ray and its height decreases with increasing the Ni2+ concentration.
diffraction reveals that ␥-Ni5 Zn21 phase, Co matrix phase and pure The second anodic peak which attributed to the oxidation of Zn
zinc phase, are observed in the deposition of Zn–Ni–Co alloy. The from ␥-(Ni5 Zn21 ) phase increases with increasing Ni2+ concentra-
third and fourth anodic peaks, however, are at more noble poten- tion [29,33]. Moreover, increasing Ni2+ concentration up to 0.4 M
tials. These potentials were −451 mV and −319 mV, respectively, in the plating bath the first peak height decreases and finally dis-
that correspond to the dissolution of pure cobalt from the deposit appears. However at the same time, a new current peak appears
and nickel from its phase. at −779 mV that may be attributed to the dissolution of Zn from
The height of any peak gives an indication about the quantity of ␦-Ni3 Zn22 phase [34] and its height increases with increasing Ni2+
its phase in the deposit. Therefore, by comparing the anodic scan concentration in the plating bath. The third and fourth anodic peaks
of the two tested alloys (Fig. 1), there was variation between the at more noble potential (−436 and −350 mV respectively) corre-
heights of the first peak (decreases) and second peak (increases) as spond to the dissolution of pure cobalt and nickel from its phase.
it shifts to more noble direction for Zn–Ni–Co alloy. This reflects that The height of the cobalt dissolution peak decreased with increasing
the amount of pure Zn decreases and the formation of ␥-Ni5 Zn21 Ni2+ concentration in the bath; while for the nickel dissolution peak,
phase in the deposit (Zn and Co content (%) were 92.8 and 7.2 for the height increased and shifted to more noble potential. At higher
Zn–Co alloy respectively). Also the height of the third peak, that cor- Ni2+ concentration (0.3 M), there was a very small peak appeared
responds to the dissolution of pure cobalt from Zn–Ni–Co, is lower at nobler potential (−166 mV) which may be due to the dissolution
than the third peak for Zn–Co dissolution. This may be ascribed of pure Ni phase in the deposits. The height of this peak increases
to the presence of Zn and/or Ni in the plating bath which inhibits with the increase in Ni2+ concentration. It was concluded from pre-
the codeposition of Co (Table 1). In addition, the appearance of vious studies that the formation of gamma and delta phases, the
the fourth anodic peak, only for Zn–Ni–Co alloy, that attributed increase in its peaks height and the shift of the peaks positively
to nickel oxidation from ␥-Ni5 Zn21 phase. All these results confirm enhanced the corrosion resistance of the deposit. Therefore, the
the transformation from the formation of ␥-Co5 Zn21 phase in case above results indicated that the ternary Zn–Ni–Co deposits possess
of Zn–Co deposition to the formation of ␥-Ni5 Zn21 phase that have more corrosion resistance accompanied with the increase in nickel
high corrosion resistance in case of Zn–Ni–Co alloy (Ecorr. was −997 concentration. The increase in corrosion resistance of the ternary
and −948 mV for Zn–Co and Zn–Ni–Co alloys respectively). There- Zn–Ni–Co deposits is not only due to the formation of a high nickel
fore, these results revealed that the ternary Zn–Ni–Co deposits ␥-alloy phase, but also, due to the codeposition of ␦-alloy phase and
exhibit higher corrosion resistance [12] due the codeposition of pure nickel, with increasing of nickel concentration in the bath.
nickel with respect to Zn–Co deposits. Stripping analysis allows the in situ characterization of the
deposits. The electrodeposits were obtained potentiostatically or
3.2. Effect of Ni2+ concentration in electrolyte on Zn–Ni–Co alloy galvanostatically, so as to favor the alloy formation. The galvano-
deposition static deposits were mostly used because of the simplicity of
reaching a given electrodeposition charge. The results of galvano-
Fig. 3 shows the cyclic voltammograms of Zn–Ni–Co alloys that static measurements (Fig. 4) show that there is some potential
were electrodeposited on the steel rod at different Ni2+ concen- trembling at high Ni2+ concentration (especially of the E–t curve
624 M.M. Abou-Krisha / Materials Chemistry and Physics 125 (2011) 621–627

-900
0.05 M -1.4
0.10 M
-950 -2.1
E vs. Ag / AgCl / mV

0.20 M
0.30 M -2.8

log i / A cm-2
-1000 0.40 M
-3.5
0.05 M
-1050 -4.2 0.10 M
0.20 M
-4.9
-1100 0.30 M
-5.6 0.40 M
0.50 M
-1150 -6.3
0 1 2 3 4 5 6 7 8 9 10
-1100 -1000 -900 -800 -700 -600 -500 -400
t / minute
E vs. Ag / AgCl / mV
Fig. 4. E–t curves for steel in 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.01 M H2 SO4 , 0.20 M
Na2 SO4 , 0.20 M H3 BO3 and different concentration of NiSO4 at 10 mA cm−2 for Fig. 6. log i–E curves of Zn–Ni–Co alloy, electrodeposited on steel from a bath con-
10 min at 30.0 ◦ C. taining 0.20 M ZnSO4 , 0.2 M CoSO4 , 0.01 M H2 SO4 , 0.20 M Na2 SO4 , 0.20 M H3 BO3 and
different concentration of NiSO4 at 10 mA cm−2 for 10 min at 30.0 ◦ C, in 5% NaCl at
scan rate 2 mV s−1 at 30.0 ◦ C.
at 0.5 M) which is probably bound up with bubbles of hydrogen
blocked part of the electrode surface [35]. The potential trembling
ing Zn oxidation from this phase. Also, an increase in the oxidation
decreases when Ni2+ concentration decreases. Inspection of Fig. 4
of Ni from ␥-phase is observed which is characterized by increasing
reveals an appreciable shift to more noble deposition potential of
the height of the third anodic peak with the increase in Ni2+ concen-
the alloy as the Ni2+ concentration increases in the plating bath.
tration. Moreover, from the same figure, there is a clear shift of the
This agrees with other studies [24] in which, during the deposition
second and third anodic peaks in the positive direction, indicating
of Ni, low overpotential is needed to create the initial nucleus with
the more formation of a high nickel ␥-alloy phase and an increase
the increase of Ni2+ concentration.
in the content of the nobler component of the alloy, i.e. Ni. These
Fig. 5 shows the anodic linear sweep voltammograms obtained
results give rise to more improvement in corrosion resistance of
during the dissolution of the deposits, which exhibit the phase
the alloy with increasing the Ni2+ concentration in the plating bath
structures of Zn–Ni–Co alloys at different Ni2+ concentration. As
[36].
can be seen in the figure, at different concentration of nickel sul-
The corrosion resistance of the deposits was determined by
phate in the plating bath, there are three peaks corresponding to
measuring the potentiodynamic polarization curves (Fig. 6). These
several phases in the alloy. The phase structure of these peaks
curves were obtained for Zn–Ni–Co alloys, that deposited gal-
corresponds to dissolution of zinc from pure Zn phase which is char-
vanostatically on steel rod from sulphate bath at different Ni2+
acterized by the first dissolution anodic peak −696.6 mV, and the
concentrations, in aerated 5% NaCl solution. The corrosion poten-
second anodic peak at about −407.6 mV that corresponds to disso-
tial Ecorr. , the polarization resistance Rp and corrosion current icorr.
lution of Zn from ␥-Ni5 Zn21 phase which was also verified by XRD
values were determined from this figure and cited in Table 1. The
(Fig. 2). The third anodic peak appears at nobler potential −172 mV
corrosion resistance of Zn–Ni–Co alloy is related to Ni content of
which corresponds to the dissolution of nickel from its phase and to
the alloy. Considering the barrier role for the corrosion factors, that
the dissolution of cobalt from the deposit. The increase in the Ni2+
the increases in the Ni content induce a growth of the corrosion
concentration, leads to more decrease in the height of the first dis-
resistance. The corrosion potential is an indication of the deposit
solution peak, corresponding to a more diminish of pure Zn content
activity in a corrosive environment. It can be seen that, with increas-
in the deposit, that disappear at high concentration of Ni. However,
ing nickel content, the corrosion potential and the passive range of
a more increase in the height of the second peak is observed giving
Zn–Ni–Co deposits shift to more noble direction [37]. This may be
rise to (␥-Ni5 Zn21 ) phase formation, which was verified by increas-
due to the increase of the amount of nobler component in the alloy
(i.e. Ni) by increasing Ni2+ concentration in the plating bath. It is
also observed from this figure, that at high Ni2+ concentration the
0.08 0.05 M corrosion potential shifts to more noble overpotential than others
0.10 M at low concentration, this may be attributed to the high formation
0.20 M of ␥-Ni5 Zn21 phase [36].
0.06
0.30 M Some structural differences between the investigated coatings
0.40 M can also be detected from morphological studies. Fig. 7a and b
i / A cm-2

0.04 shows the SEM images of electrodeposited alloys at different Ni2+

concentrations. The deposit is rough, contains some pores, with
0.02 less-uniform surface and the grain size is about 34 nm at 0.10 M Ni2+
concentration in the plating bath (Fig. 7a). This is probably due to
the higher Zn content in the deposited film with respect to nickel
0.00
and cobalt contents. Increasing Ni2+ concentration in the plating
bath to 0.40 M gives a uniform, small grain size (about 21 nm) and
-0.02 compact deposit (Fig. 7b). This is not only due to the increase of Ni
-1200 -1000 -800 -600 -400 -200 0 content in the deposit but also due to the slight increase in cobalt
E vs. Ag / AgCl / mV content. Also, it was stated that the decrease in grain size result in
an improvement of passive film’s protective performance and thus,
Fig. 5. ALSVs of Zn–Ni–Co alloy, electrodeposited on steel from a bath contain-
increasing the corrosion resistance [38].
ing 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.01 M H2 SO4 , 0.20 M Na2 SO4 , 0.20 M H3 BO3 and
different concentration of NiSO4 at 10 mA cm−2 for 10 min at 30.0 ◦ C, in 0.50 M The electrodeposits were subjected to a semiquantitative X-ray
Na2 SO4 + 0.05 M EDTA solution at scan rate 5 mV s−1 at 30.0 ◦ C. dispersion analysis to verify the correlation between the bath com-
 M.M. Abou-Krisha / Materials Chemistry and Physics 125 (2011) 621–627 625

Fig. 7. SEM photograph of electrodeposited (a) 0.10 M NiSO4 , (b) 0.40 M NiSO4 , with
0.20 M ZnSO4 , 0.20 M CoSO4 , 0.01 M H2 SO4 , 0.20 M Na2 SO4 and 0.20 M H3 BO3 at
10 mA cm−2 for 10 min at 30.0 ◦ C.

position and the amount of codeposited zinc, nickel and cobalt.

Fig. 8a and b presents EDX spectra for both 1:0.25:1 and 1:2.25:1
alloys of Zn:Ni:Co obtained for 10 mA cm−2 final current density.
The results for all the Zn–Ni–Co alloys are compiled in Table 2. For
the first Fig. 8a, a comparison between the height of Zn–Ni–Co sig-
nals and the metal ion concentration in the electrolytic solutions
reveals that Zn–Ni–Co codeposition follows anomalous mecha-
nism, under all the experimental conditions used. Cobalt content
was also present in smaller quantities with respect to nickel con-
tent, although the Co2+ concentration is four times higher than Ni2+
concentration in the plating bath (Fig. 8a). But for the second fig-
ure, increase of the Ni2+ concentration leads to an increase in cobalt
content. EDX dot-mapping experiments were performed to visual-
ize the distribution of alloy components in the Zn–Ni–Co layer. It
was noted that the deposition is nearly homogeneous, with no pref-
erential surface region for zinc, nickel or cobalt deposition for all
Zn–Ni–Co compositions.The influence of Ni2+ concentration on the
percentage of Zn, Ni and Co in Zn–Ni–Co alloys from sulphate bath

Table 2 Fig. 8. EDX peaks for the electrodeposit Zn–Ni–Co alloy on steel from a bath con-
Comparison between theoretical and experimental values for Zn, Ni and Co in the taining (a) 0.10 M NiSO4 , (b) 0.50 M NiSO4 , with 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.01 M
electrolytic solutions with the metallic percentage in the electrodeposits, found H2 SO4 , 0.20 M Na2 SO4 and 0.20 M H3 BO3 at 10 mA cm−2 for 10 min at 30.0 ◦ C.
by EDX, which deposited galvanostatically from a bath containing 0.01 M H2 SO4 ,
0.2 M Na2 SO4 , 0.2 M M H3 BO3 and (a) 1:0.25:1 and (b) 1:2.25:1 of Zn2+ :Ni2+ :Co2+ at
10 mA cm−2 for 10 min at 30 ◦ C. is shown in Table 1. Zinc content in the deposit gradually decreased
SystemZn:Ni:Co Theoretical Experimental and cobalt content in the deposit slightly increased with increas-
ing Ni2+ concentration. Cobalt content reached 4.34% when the bath
%Zn %Ni %Co %Zn %Ni %Co
contains were 0.2/0.2 M of Zn2+ /Co2+ molar ratio with 0.50 M NiSO4 .
1:0.25:1 44.44 11.11 44.44 88.99 7.09 3.92 However, nickel content in the alloy increased to 15.46%, indicat-
1:2.25:1 23.5 53 23.5 66.47 23.94 9.59
ing the formation of ␥-Ni5 Zn21 phase. This is in agreement with
626 M.M. Abou-Krisha / Materials Chemistry and Physics 125 (2011) 621–627

0.00 -0.040
-0.035
-0.01 Part I
-0.030 Normal

i / A cm -2
-0.02 -0.025
i / A cm-2

-0.03 -0.020
-0.015 Part II
-0.04 Anomalous
-0.50 V -0.010
-1.00 V
-0.05 -1.05 V -0.005
-1.10 V
0.000
-0.06 -1.20 V
-400 -600 -800 -1000 -1200 -1400
-1.30 V
E vs. Ag/AgCl/mV
0 1 2 3 4 5 6 7 8 9 10 11
t / minute
Fig. 10. Potentiostatic cathodic polarization for the electrodeposition of Zn–Ni–Co
alloy from bath containing 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.20 M NiSO4 , 0.01 M H2 SO4 ,
Fig. 9. i–t curves for steel in 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.20 M NiSO4 , 0.01 M
0.20 M Na2 SO4 and 0.20 M H3 BO3 for 10 min at 30.0 ◦ C.
H2 SO4 , 0.20 M Na2 SO4 and 0.20 M H3 BO3 at different deposition potential for 10 min
at 30.0 ◦ C.
deposition with low efficiency. The normal Zn–Ni–Co codeposition
the Zn–Ni equilibrium diagram, that was obtained previously [39]. occurred in this part I, where nickel and cobalt are deposited pref-
A similar behavior was reported in the investigation of the elec- erentially to zinc. Anomalous codeposition may be according to
trodeposition of Zn–Ni-Fe alloy [40]. Also, the ␥-Ni5 Zn21 was found Ni and Co ions (or its monovalent intermediate) adsorbed first;
in Zn–Ni–Co electrodeposits containing more than 9% Ni, in earlier followed by adsorption of Zn2+ (or its monovalent intermediate)
investigation [36] under the same conditions. This decrease in zinc onto the freshly adsorbed and deposited nickel and cobalt. The
content was replaced by an increase in the cobalt and nickel con- adsorption of zinc ions inhibits subsequent deposition of nickel and
tents in the deposit when NiSO4 concentration was increased in cobalt but does not block it completely. This may be attributed to
the bath. This leads to a decrease in the alloy current efficiency, the competitive adsorption between Zn2+ and Ni2+ and/or Co2+ (or
corrosion potential, corrosion current and thickness. The decrease its monovalent intermediate) to occupy active sites leading to the
in thickness may be due to the decrease in Zn content of the preferential deposition of Zn.
alloy (the main alloy component). Finally, the polarization resis- The anodic linear sweep voltammograms obtained during
tance increased from 1.9 to 2.02 K  when the Ni2+ concentration the dissolution of Zn–Ni–Co deposits (Fig. 11) show the phase
increased from 0.05 M to 0.5 M in the plating bath. Depending upon structures of alloys that deposited potentiostatically at different
the above results, one may select appropriate operating conditions deposition potential. On the basis of the ALSVs, an identification of
to obtain an optimum nickel amount in the range of 11–15% that the phase structures present in the Zn–Ni–Co alloys obtained was
provides acceptable corrosion resistance for these types of alloy on made. A Zn–Ni–Co alloy consists of several intermediate phases
steel substrate [36]. and/or intermetallic compounds of different crystallographic ori-
entations. It is clear from the figure; at deposition potential
<−1000 mV, there is no noticeable anodic dissolution peaks. But
3.3. Effect of deposition potential on the electrodeposition of
at deposition potential −1000 mV, only a very small anodic disso-
Zn–Ni–Co alloy
lution peak at −120 mV has appeared which indicates the presence
of pure nickel and/or cobalt giving rise to normal codeposition. The
Deposition potential is one of the important variables in the
low height of this peak indicates the low content of the alloy having
electrodeposition process because it is directly related to economic
good adhesion. Also, as can be seen from the figure, the deposition
efficiency and the alloy properties. The change in composition and
potential of pure Zn starts at −1050 mV which observed from the
quality of the alloys is a result of the deposition potential.
first dissolution peak. However, at the deposition potentials −1050
Fig. 9 shows the current-time dependence for the deposition of
and −1100 mV, the dissolution of the Zn–Ni–Co alloy takes place
Zn–Ni–Co alloys on steel rod at different potentials. The cathodic
current density decreased rapidly during the first few seconds and
then, reached constancy during deposition relax time (Fig. 9). On -0.50 V
the other hand, an increase in the deposition potential results in 0.08 -1.00 V
an increase in the deposition rate in terms of current density. The -1.05 V
curves clarify that as the deposition potential was made less neg- 0.06 -1.10 V
ative, causes instant shift in the current to more cathodic side -1.20 V
i / A cm-2

and then reaches constancy, giving rise to more deposition of the 0.04
less noble metals. It can be seen also as the deposition potential
increases the cathodic current increases with the fluctuations of 0.02
low frequency and magnitude. This may be attributed to more plat-
ing out of Ni and/or Co at the electrode surface forming dendritic 0.00
deposits. The formation of these dendritic deposits appears to be
associated with the deposition of Ni and/or Co at an insulating -0.02
zinc surface. The similar trend of potentiostatic curves have been
observed during the addition of Sn2+ to Al and Al–Sn alloys in a -1200 -1000 -800 -600 -400 -200 0 200
chloride solution [41]. E vs. Ag / AgCl / mV
Part II in Fig. 10 indicated that the Zn–Ni–Co anomalous code-
Fig. 11. ALSVs of Zn–Ni–Co alloy, electrodeposited on steel from a bath contain-
position occurs only in the linear part of the polarization curves,
ing 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.20 M NiSO4 , 0.01 M H2 SO4 , 0.20 M Na2 SO4 and
where preferential deposition of less noble Zn occurs. On the other 0.20 M H3 BO3 at different deposition potential for 10 min at 30.0 ◦ C, in 0.50 M
hand, part I of the same figure represents the normal type of alloy Na2 SO4 + 0.05 M EDTA solution at scan rate 5 mV s−1 at 30.0 ◦ C.
 M.M. Abou-Krisha / Materials Chemistry and Physics 125 (2011) 621–627 627

also due to the formation of a high nickel ␥-alloy phase. Increasing

-1
the Ni2+ concentration in the plating bath increases the corrosion
-2 resistance of the deposit. This may be due to the increase in the
␥-phase and decrease in the pure Zn phase of the alloy. Also the
-3 surface morphology of the deposits was improved with increasing
Ni2+ concentration.
log i / A cm-2

-4 The results revealed that, at low deposition potential

(<−1050 mV), a relatively high nickel and cobalt contents were
-5 -0.50 V obtained, which result from the more noble nature of Ni and Co
-1.00 V (normal-codeposition). On the other hand, the higher potential
-6
-1.05 V (>−1050 mV) enhances the rate of Zn deposition and suppresses
-7 -1.10 V that of Ni and Co deposition (anomalous-codeposition). More-
-1.20 V over, the more the increase in the deposition potential through
-8 this region, the more the protection properties of the deposited
-1100 -1000 -900 -800 -700 -600 -500 -400 -300 -200 Zn–Ni–Co alloy is exhibited. In the present work, anomalous code-
position may be attributed to the competitive adsorption between
E vs. Ag / AgCl / mV
Zn2+ , Ni2+ and Co2+ (or its monovalent intermediate) to occupy
Fig. 12. log i–E curves of Zn–Ni–Co alloy, electrodeposited on steel from a bath con- active sites, resulting in the preferential deposition of Zn.
taining 0.20 M ZnSO4 , 0.20 M CoSO4 , 0.20 M NiSO4 , 0.01 M H2 SO4 , 0.20 M Na2 SO4
and 0.20 M H3 BO3 at different deposition potential for 10 min at 30.0 ◦ C, in 5% NaCl
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