Arabian Journal of Chemistry (2015) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

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REVIEW

Electrochemical behavior of Zn–Co–Fe alloy

electrodeposited from a sulfate bath on various
substrate materials
M.M. Abou-Krisha a,b, A.G. Alshammari a,*, F.H. Assaf b, F.A. El-Sheref b

a
College of Science, Chemistry Department, Al-Imam Mohammad Ibn Saud Islamic University (IMSIU), Riyadh 11623,
Saudi Arabia
b
Faculty of Science, Chemistry Department, South Valley University, Qena 83523, Egypt

Received 24 October 2014; accepted 13 October 2015

KEYWORDS Abstract Electrodeposition of ternary Zn–Co–Fe alloy, on copper (high purity 99.9%), AISI 4340
Electrodeposition; steel, 9021I steel rod (iron 99.98%) and 304-stainless steel substrates, from a sulfate bath was stud-
Corrosion resistance; ied. The electrodeposition of Zn–Co–Fe alloy on the various substrate materials was investigated by
Ternary Zn–Co–Fe alloy using cyclic voltammetric (CV) technique, to understand the reduction and oxidation processes
occurring at the different electrodes surfaces, and galvanostatic technique to detect the formation
of the initial deposits. Also potentiodynamic polarization method was used to assess the corrosion
performance of the coating on each substrate material. The results were confirmed using EDXF and
SEM analysis which show that the substrate material type influences the electrodeposition process
and morphology of the deposits. The obtained results using galvanostatic technique showed that the
substrate type affects the deposition potential. The cyclic voltammograms for steel substrate have
different behavior than the other used substrate materials; also a clear reduction was shown in
the associated charge for copper substrate. The corrosion resistance for Zn–Co–Fe alloy deposited
on stainless steel substrate was better corrosion resistant than for a steel rod, steel and copper sub-
strates.
Ó 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail address: agshammri@imamu.edu.sa (A.G. Alshammari).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

http://dx.doi.org/10.1016/j.arabjc.2015.10.008
1878-5352 Ó 2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Abou-Krisha, M.M. et al., Electrochemical behavior of Zn–Co–Fe alloy electrodeposited from a sulfate bath on various substrate
materials. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.10.008
2 M.M. Abou-Krisha et al.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1. Cyclic voltammograms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2. Galvanostatic technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3. XRD and EDXF measurements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.4. Potentiodynamic measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.5. Surface morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.6. The chemical composition of Zn–Co–Fe deposit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction
The interest in zinc alloys electrodeposits; including Zn–Co
and Zn–Fe alloys that have drawn a lot of attention because
these alloys exhibit considerably higher corrosion resistance
than pure Zn (Fratesi et al., 1994; Zhang et al., 2001; Ortiz-
Aparicio et al., 2007; Gharahcheshmeh and Sohi, 2009) and
as a substitute for toxic and high price cadmium coatings
(Tomachuk et al., 1999; Abou-krisha and Abushoffa, 2007).
It is known that from the metallurgical point of view a result-
ing microstructure morphology strongly affects the material’s
properties [e.g. mechanical, electrical and corrosion resistance]
(Osorio et al., 2011a,b). Besides, the microstructure array is
also intimately associated with the anode/cathode area ratio,
and as a direct consequence, with the electrochemical corro-
sion behavior, as previously reported (Osorio et al., 2011a,b).
Furthermore, other properties such as weldability, hardness
and ductility of zinc also were enhanced. There is a growing
interest on the electrodeposited Zn–Co–Fe alloys because of
their superior protective properties (Lodhi et al., 2007a,b).
The electrodeposition of these Zn alloys is considered as code-
position of the anomalous type, according to Brenner (1963)
who defined the electrochemical deposition process as the less
noble metal is deposited preferentially compared to the more
noble metal. Although this phenomenon has been known since
1907, the codeposition mechanisms of zinc and metal are not
well understood (Growcock and Jasinski, 1989). Several theo-
ries have been developed to explain this anomalous behavior
(Peter et al., 2010; Chung and Chang, 2009; Koza et al.,
2008; Higashi et al., 1981; Lodhi et al., 2008; Chen and Sun,
2001; Matlosz, 1993; Zech et al., 1999).
The aim of the present work was to make a clear influence
varying the substrate type on the electrodeposition of
Zn–Co–Fe alloy from a sulfate bath by using cyclic voltamme-
try and galvanostatic measurements and also to investigate the
suitable substrate material, which can make the best corrosion
resistance and morphology.
2. Experimental
The compositions of the electrolyte used for Zn–Co–Fe alloy
electrodeposition consist of ZnSO4 (0.2 mol L
1), CoSO4
(0.2 mol L
1), FeSO4 (0.2 mol L
1), Na2SO4 (0.2 mol L
1),
H3BO3 (0.2 mol L
1) and H2SO4 (0.01 mol L
1). All reagents
were of analytical grade. Use of the acid sulfate bath is increas-
ing due to its relatively low cost, safety features and pollution
control characteristics (Loto, 2012). The pH of electrolyte was
2.50 ± 0.02, and deposition was carried out at 25.0 °C.
The coatings were deposited on various sheets: copper (high
purity 99.9%), AISI 4340 low alloy steel (0.41% C, 0.73% Mn,
0.8% Cr, 1.74% Ni, 0.25% Mo and 0.005% Si (wt%)) and
304-stainless steel (Fe, <0.08% C, 17.5–20% Cr, 8–11% Ni,
<2% Mn, <1% Si, <0.045% P, <0.03% S) with area
2 cm2, and also 9021I-steel rod (iron 99.98%) with a geometri-
cal area of 0.196 cm2 was used. Before each experiment the sur-
face of steel and stainless steel sheets were etched in 30% HCl
for 2 min and 20% HNO3 for copper sheet to activate the sur-
face. Steel rod was handed polish with emery paper (up to
1500 mesh) then immersed in anhydrous ethyl alcohol. Finally,
the substrate materials were rinsed with doubly distilled water
and then dried. After surface preparations the sheets were
immediately placed in the plating bath to prevent formation
of an oxide layer on their surfaces. The electrolytic cell was
used in the present work as detailed in Abou-Krisha (2005).
Before each run, the cell was cleaned with chromic/sulfuric
mixture, washed with singly and doubly distilled water and
filled with 50 cm3 of the electroplating solution of temperature
25.0 °C. During the experiment the cell was placed in an air
thermostat cabinet to make sure adjustment steady tempera-
ture of 25.0 °C.
Electrochemical experiments were carried out in a three
electrode cell using an EG&G potentiostat/galvanostat model
273A, controlled by a PC using corrosion analysis software
model 352. Platinum electrode and saturated calomel electrode
(SCE) were used as counter and reference electrodes, respec-
tively. Steel rod that had been placed in a Teflon mounting
material and copper, steel and stainless steel sheets were also
used as a working electrode. The electrodeposition was done
using the galvanostatic method and the potential-time depen-
dence for the deposition of Zn–Co–Fe alloy obtained on differ-
ent substrates at constant current density 10 mA cm
2 for
10 min at 25.0 °C.
The potential scan was started from 0.0 mV and reversed to

1300 mV in the opposite direction, while potential scan rate
was at 5 mV s
1. The potentiodynamic polarization resistance
measurements were performed in 0.05 mol L
1 HCl solution.
In an environment with the presence of chloride ions, localized

Please cite this article in press as: Abou-Krisha, M.M. et al., Electrochemical behavior of Zn–Co–Fe alloy electrodeposited from a sulfate bath on various substrate
materials. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.10.008
Electrochemical behavior of Zn–Co–Fe alloy 3

(a) 30
Table 1 Values of Zn, Co and Fe amount in the deposit, total
mass of the deposit determined by Atomic Absorption
Spectrophotometer, and Zn, Co and Fe content (%), and 20
Zn–Co–Fe deposits current efficiencies (%), thickness and
A1 A2
electrochemical corrosion measurements of the deposit on
copper, steel and stainless steel sheets (2 cm2) deposited 10 A
/ A3

galvanostatically from Zn–Co–Fe bath at 10 mA cm
2 for

-2
i/ mA cm
10 min at 25.0 °C. 0
Parameter Zn–Co–Fe alloy deposit C1

Copper Steel Stainless a

-10
sheet sheet steel sheet
a- copper sheet
Zn amount in the deposit 46.9 49 46.5 b b- steel sheet
(10
5 g) -20 c- steel rod
Co amount in the deposit 6.2 10 18.5 c d- stainless steel sheet
(10
5 g) d
Fe amount in the deposit 17.9 17 22 -30
-1300 -1200 -1100 -1000 -900 -800 -700 -600 -500 -400
(10
5 g)
Total mass of the deposit 71 76 87 E vs. SCE/ mV
(10
5 g)
2
Zn content (%) 66.05 64.47 53.44 (b)
Co content (%) 8.73 13.15 21.26 A1
Fe content (%) 25.21 22.36 25.28
Zn–Co–Fe deposit current 36.76 39.35 45.64 1 A2
A3

efficiency (eZn–Co–Fe) (%)

Thickness of the deposit (lm) 0.47 0.50 0.56
Rp (Ohms) 67.8 74 91 /
A
0
icorr. (A cm
2  10
4)
-2

9.25 6.72 5.77

i/ mA cm

(Ecorr.) Corrosion potential (mV)
962
943
924

C1

-1 b
a c
corrosion such as pitting and crevice corrosion is still a serious
problem for the steel. For this reason, the research study of the
passive film of steels and their stability, particularly in chloride -2 a- copper sheet
d b- steel sheet
solutions has a technological importance. c- steel rod
The surface morphology of the coatings was characterized d- stainless steel sheet

by Scanning Electron Microscope (SEM) model JSM-5500 -3

LV (JEOL, Japan). The qualitative and semiquantitative -1300 -1200 -1100 -1000 -900 -800 -700 -600 -500 -400

chemical analysis of the Zn–Co–Fe alloy was determined via
Energy Dispersive X-ray Fluorescence (EDXRF) model JEOL
JSX 3222 (JEOL, Japan). The chemical composition of each
deposit has been determined by Atomic Absorption Spec-
trophotometer AA-6701F (SHIMADZU). For this analysis,
the deposits were dissolved in 50 cm3 of 30% HCl then diluted
with doubly distilled water up to 100 cm3, and analyzed to get
the Zn, Co, and Fe contents in the deposits.
The film thickness (Abou-Krisha, 2005) of the deposited
alloy layer is valued from the mass of the deposit, the densities
of Zn (dZn = 7.14 g cm
3), Co (dCo = 8.90 g cm
3) and Fe
(dFe = 7.87 g cm
3) and the surface area (2 cm2). Using the
following equation,
h ¼ ðmt Þ=ðda Xsa Þ
the thickness can be calculated as the height of the film
(h), where mt = total mass of the deposit, sa = surface
area, and da = alloy density = [dZn (mZn/mt) + dCo
(mCo/mt) + dFe (mFe/mt)], where mZn = Zn amount in the
deposit, mCo = Co amount in the deposit and mFe = Fe amount
in the deposit. The cathode current efficiency
was calculated using the following equation for n as an example of
eZn ¼ ððmZn  96; 487Þ  100=ðcurrent  time  32:685ÞÞ
¼ ððmZn  96; 487Þ  100=ð0:02 A  600 s  32:685ÞÞ
E vs. SCE/ mV
Figure 1 (a and b) i–E curves (cyclic voltammograms)
for Zn–Co–Fe alloy deposited from Zn–Co–Fe bath obtained
on various substrate materials between Ei = 0.0 mV and
Ef =
1300 mV and at a scan rate of 5 mV s
1. The cathodic
part of (a) is shown in (b).
The values of the electrochemical corrosion measurements
of the coatings, the corrosion potential (Ecorr.), the polariza-
tion resistance (Rp) and the corrosion current (icorr.) were
obtained using the software model 352 and are given in Table 1.
The crystalline constituents of the coatings were analyzed by
XRD model Bruker Axs-D8 Advance with Cu Ka radiation
(k = 1.5406 Å and 40 mA).
All experiments have been carried out in duplicate; the mea-
surements have shown good reproducibility. For a standard
bath deposition, a series of experiments on electrodeposition
on steel sheet, as an example, at different times were carried
out and the relative standard deviation (RSD%) was found
to be 3.5%, 5.2% and 4.3% for the Zn, Fe and Ni contents
in the deposit, respectively, and 1.1%, 0.8% and 0.9% for
the electrochemical measurements (Ecorr.), (Rp) and (icorr.)
respectively.

Please cite this article in press as: Abou-Krisha, M.M. et al., Electrochemical behavior of Zn–Co–Fe alloy electrodeposited from a sulfate bath on various substrate
materials. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.10.008
4 M.M. Abou-Krisha et al.

3. Results and discussion surface. The anodic peak A2 which is ascribed to dissolution
of Fe from FeCo phase shifts to more positive direction for
3.1. Cyclic voltammograms either SS or S otherwise S rod and Cu substrates. Also, the
height of the anodic peak A2 for SS, S rod, S and Cu, shows
that the amount of the deposits changes by changing the sub-
Fig. 1a shows the cyclic voltammogram curves for Zn–Co–Fe
strate. The anodic peak A3 which is ascribed to dissolution of
alloy electrodeposited on various substrate materials: Cu, S, S
Co from FeCo phase shifts to more positive direction for either
rod and SS with scan rate 5 mV s
1 and at 25.0 °C. The catho-
SS or S rod but shifts to more negative direction with Cu sub-
dic scan shows two reduction peaks: the first reduction peak
strate. An interesting behavior has occurred on S substrate, in
(C1), which appears with a small current density (faint peak)
the negative direction, the onset of the cathodic process; cyclic
with SS, S and S rod substrates, but does not appear with
voltammogram starts with high anodic current density. Also,
copper substrate, and relates to the codeposition of sulfur from
from the positive scan; in the last of the anodic process, a sharp
reduction of sulfate group (Abou-Krisha et al., 2008). In
increase in the current density occurs. The low alloy steel
Fig. 1b, the cathodic part C1 of (a) is shown in (b), which
nature, due to its chemical composition, may be responsible
reveals that there is a reduction peak C1 for copper that is
for the positive potential of the anodic dissolution peaks in
attributed to sulfur, but smaller than for others substrates.
the cyclic voltammograms. This behavior appears in the pres-
The second reduction peak relates to the massive deposition
ence or absence of metallic ions (Zn, Co and Fe), as can be
of Zn–Co–Fe alloy which occurs simultaneously with the
seen in Fig. 2.
hydrogen evolution reaction (HER). HER appears as a further
The cyclic voltammetry measurement in aqueous solution
increase in the cathodic current density at more negative
containing solely the bath composition obtained on steel sub-
potentials. The use of SS, S rod, S and Cu substrates affects
strate is presented in Fig. 2. As can be seen in the cathodic
the deposition potential. The potential necessary to begin the
scan, an anodic peak is observed with high current density
alloy deposition shifted to more negative values for SS, S
46.5 mA cm
2 which could be attributed to the dissolution of
rod, S and Cu substrates.
iron with bath. At more negative potential a deposition peak
Several oxidation peaks appeared in the positive scan and
is observed at
760 mV which may be due to the deposition
their relative size depend on the amount of the deposits
of sulfur from the sulfate group (Abou-Krisha et al., 2008).
(Lodhi et al., 2007a,b) and the type of substrate. These anodic
In the following reverse scan, the cyclic voltammogram does
peaks are assigned as follows: shoulder A0 and peak A1 corre-
not show well-defined dissolution peaks due to decrease in
spond to zinc oxidation to Zn2+, peak A2 to oxidation of iron
the current density of corresponding cathodic peak (C1). A
from FeCo phases and peak A3 to cobalt matrix oxidation of
sharp increase in the current density takes place starting from
these phases. During the anodic scan, the cyclic voltammo-

502 mV which may be due to oxygen evolution reaction.
gram for Zn–Co–Fe alloy obtained on Cu substrate has very
low current density, which means that content of the deposit
3.2. Galvanostatic technique
is low in comparison with SS, S rod and S substrates.
The anodic peak A1 which is attributed to the dissolution of
zinc shifts to more positive direction only with S substrate; The use of the galvanostatic deposition is most useful in detect-
otherwise, the anodic peak A1 of SS, S rod and Cu substrates ing the formation of the initial deposits (Gomez et al., 2001).
does not change. Also, the height of the anodic peak A1 for SS, The potential-time dependence for the deposition of
S rod, S and Cu, shows that the type of substrate has a clear Zn–Co–Fe alloy obtained on SS, S rod, S and Cu substrates
effect on the amount of the deposits formed on the substrate at constant current density 10 mA cm
2 for 10 min at

50 -1000
Steel Sheet
40 -1050
a- copper sheet
b- steel sheet
-1100 c- steel rod
30 d- stainless steel sheet
E vs. SCE/ mV
i/ mA cm-2

-1150

20 d
-1200 c
b
a
10 -1250

-1300
0
C1
-1350
-1200 -1000 -800 -600 -400 -200 0 0 1 2 3 4 5 6 7 8 9 10 11
E vs. SCE/mV t/ minute

Figure 2 i–E curves (cyclic voltammograms) for steel substrate Figure 3 Galvanostatic deposition and the chronopotentiomet-
in solely sulfate bath containing; 0.01 mol L
1 H2SO4, ric curves for Zn–Fe–Co electrodeposits in the deposition bath
0.20 mol L
1 Na2SO4 and 0.20 mol L
1 H3BO3 at 25.0 °C, obtained on various substrate materials at 10 mA cm
2 for
Ei = 0.0 mV and Ef =
1300 mV and at a scan rate of 5 mV s
1. 10 min at 25.0 °C.

Please cite this article in press as: Abou-Krisha, M.M. et al., Electrochemical behavior of Zn–Co–Fe alloy electrodeposited from a sulfate bath on various substrate
materials. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.10.008
Electrochemical behavior of Zn–Co–Fe alloy
Figure 4 XRD patterns for Zn–Co–Fe alloy, electrodeposited
galvanostatically on (a) copper, (b) steel and (c) stainless steel
substrate materials from Zn–Co–Fe bath at 10 mA cm
2 for
10 min at 25.0 °C.
25.0 °C is represented in Fig. 3. It could be seen that the depo-
sition potential greatly depends on the substrate type. Low
overpotential is needed to create the initial nucleus during
the deposition of Zn–Co–Fe alloy on SS substrate. Deposition
potential is
1215 mV which takes place at 40 s. On the other
hand, high overpotential is needed to create the initial nucleus
on copper substrate and grows at high cathodic potential

1260 mV at time about 2 min. Deposition potential for
Zn–Co–Fe alloy on S rod and S substrates lies between SS
and Cu substrates
1233 mV and
1253 mV, respectively
and a moderate overpotential needed to create the initial
nucleus. Also deposition of Co and Fe increases by using SS,
S rod, S and Cu, respectively in comparison with the deposi-
tion of zinc (Table 1).
Please cite this article in press as: Abou-Krisha, M.M. et al., Electrochemical behavior of Zn–Co–Fe alloy electrodeposited from a sulfate bath on various substrate
materials. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.10.008
5
Figure 5 EDXF peaks for Zn–Co–Fe alloy, electrodeposited
galvanostatically on (a) copper, (b) steel and (c) stainless steel
substrate materials from Zn–Co–Fe bath at 10 mA cm
2 for
10 min at 25.0 °C.
3.3. XRD and EDXF measurements
X-ray diffraction measurements are carried out on Zn–Co–Fe
electrodeposits which deposited galvanostatically from a
sulfate bath, on SS, S and Cu substrates and are presented in
Fig. 4a–c. The deposits are composed mainly of Zn and
Fe/FeCo phase. Overlay of pure Fe and FeCo phase is
observed on XRD analysis (Bai et al., 2003; Zhang and
Douglas, 2007). Some researchers have shown that the X-ray
analysis is not always able to identify the deposited phases
because Zn–Co–Fe alloy is poorly crystallized in a wide
range of composition (Alfantazi et al., 1996; Li et al., 2005).
6 M.M. Abou-Krisha et al.

(a)
-1.5 a- copper sheet
b- steel sheet
-2.0 c- steel rod
d- stainless steel sheet
-2.5
-2
log i/ A cm

-3.0

-3.5

-4.0

a
-4.5 c
b
d

-5.0
-1000 -980 -960 -940 -920 -900 -880 -860
E vs. SCE/ mV

(b) a
0.05 a- copper sheet
b- steel sheet
c- steel rod
0.04 d- stainless steel sheet
b

0.03
-2

c
i / A cm

d
0.02

0.01

0.00

-1.0 -0.8 -0.6 -0.4 -0.2 0.0

E vs. SCE/ mV

Figure 6 (a) Log i–E and (b) i–E curves for Zn–Co–Fe alloy,
electrodeposited galvanostatically on a – copper, b – steel, c – steel
(rod) and (d) – stainless steel substrate materials from Zn–Co–Fe
bath at 10 mA cm
2 for 10 min at 25.0 °C, in 0.05 mol L
1 HCl
solution at a scan rate of 5 mV s
1 at 25.0 °C.

Previously (Alfantazi et al., 1997) the effect of S and Cu sub-

strates on electrodeposited Zn–Ni alloy, was found do not
have a significant effect on the deposit characteristics.
The grain size of the deposited Zn–Co–Fe alloy was calcu-
lated using Scherrer’s equation (1) (Sartale and Lokhande,
2001):
Kk
D¼
b cos h
where K is taken as 1, k the wavelength of X-ray used and b the
full width of half maximum of the peak. The grain size was cal-
culated around the most intense peak. The calculated grain size
for Zn–Co–Fe films obtained on Cu, S and SS substrates is
small and exists in the nanosize range, 44.8, 29 and
23.37 nm, respectively.
The surface chemical composition was obtained by EDX.
The EDX spectrums of deposited Zn–Co–Fe alloy obtained
on SS, S and Cu substrates are shown in Fig. 5. The presence
and the amount of deposited metal depend on the used sub-
strate material. SS substrate has the highest amount of the
Figure 7 SEM photograph for Zn–Co–Fe alloy, electrode-
posited galvanostatically on copper, steel and stainless steel
substrate from Zn–Co–Fe bath at 10 mA cm
2 for 10 min at
ð1Þ 25.0 °C. (a) Electrodeposited Zn–Co–Fe on copper sheet. (b)
Electrodeposited Zn–Co–Fe on steel sheet. (c) Electrodeposited
Zn–Co–Fe on stainless steel substrate.
more noble components cobalt and iron. Cu substrate has
the highest amount of the more negative component zinc, so
deposition of Zn–Co–Fe alloy is preferable on SS substrate.
3.4. Potentiodynamic measurements
The potentiodynamic polarization curves for Zn–Co–Fe
deposits in 0.05 mol L
1 HCl solution at i = 10 mA cm
2 that
deposited galvanostatically on SS, S rod, S and Cu substrates

Please cite this article in press as: Abou-Krisha, M.M. et al., Electrochemical behavior of Zn–Co–Fe alloy electrodeposited from a sulfate bath on various substrate
materials. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.10.008
Electrochemical behavior of Zn–Co–Fe alloy
from a sulfate bath are shown in Fig. 6a and b. The corrosion
potentials (Ecorr.) measured from Fig. 6a for Zn–Co–Fe
deposit on SS, S rod, S and Cu substrates are
924,
930,

943 and
962 mV, respectively. Fig. 6b indicates that there
is a difference between Tafel’s slopes for different substrates.
These differences in Ecorr. may be attributed to the nature of
each substrate surface or to the changes in the electrode poten-
tials of each substrate. SS substrate exhibits enhanced corro-
sion performance, with the noblest (less negative) corrosion
potential. The improvement was achieved in the corrosion
resistance of deposits due to the use of various substrate
materials, which may be responsible for increasing the content
of the nobler elements in the coating and increasing the thick-
ness of the deposit. Also, the corrosion resistance of the
deposits on SS substrate increases may be attributed to the
noble nature of SS which resulted in a little interaction with
its surface and the alloy components.
3.5. Surface morphology
Fig. 7 shows the SEM images for Zn–Co–Fe alloy deposits
from the plating bath, and the morphology of the deposit indi-
cates a clear difference in each substrate material. The deposit
of the alloy on S substrate is clusters and on Cu substrate is not
compact and without any homogeneity. The surface morphol-
ogy of SS substrate represents the compact and homogeneous
deposits.
The SEM pictures of the deposit corresponding to SS, S
and Cu show that the morphology of the final deposits varies
significantly with the use of different substrates and illustrate
that SS minimizes the dendrite formation and leads to more
homogeneous deposits.
3.6. The chemical composition of Zn–Co–Fe deposit
Influence of Cu, S and SS substrate materials on the chemical
composition of Zn–Co–Fe alloy deposit is shown in Table 1.
SS substrate has the lowest zinc percentage in the deposit
(53.44%), and the highest cobalt and iron contents in the
deposit (21.26% and 25.28%, respectively) otherwise with Cu
and S substrates, the zinc percentage of the deposit (66.05%
and 64.47%, respectively), iron percentage (8.73% and
13.15%, respectively) and cobalt percentage (25.21% and
22.36%, respectively). This decrease in zinc content and the
increase in cobalt and iron contents on SS substrate lead to
an increase in the alloy current efficiency 45.64% and increase
in the thickness of the deposit 0.56 lm, and according to these
results Zn–Co–Fe alloy deposits on SS substrate produce
higher corrosion resistance in comparison with Cu and S
substrates.
4. Conclusions
The main conclusions of this research investigation are the
following:
 The type of substrate influences both the electrodeposition
process and the alloy morphology.
 The cyclic voltammograms of steel substrate have different
behavior than the other substrate materials, at which the
onset of the cathodic process takes place in the anodic scan
Please cite this article in press as: Abou-Krisha, M.M. et al., Electrochemical behavior of Zn–Co–Fe alloy electrodeposited from a sulfate bath on various substrate
materials. Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.10.008
7
at the more positive potential and the final of the anodic
process increases the current density violently. The low
alloy steel nature, due to its chemical composition, may
be responsible for these manners. This behavior appears
in the presence or absence of metallic ions (Zn, Co and Fe).
 SEM micrographs demonstrated that stainless steel exhib-
ited more preferred surface morphology and high quality
deposits.
 XRD analysis showed that the deposits are composed
mainly of Zn and Fe/FeCo phase.
 EDXF patterns and AAS analysis indicated that the stain-
less steel substrate has higher amount of Fe and Co than
steel and copper substrates but copper substrate has the
highest amount of Zn. This is may be due to that SS
enhanced the normal codeposition.
 The corrosion resistance of the deposited Zn–Co–Fe alloy
on stainless steel substrate was better corrosion resistant
than for a steel rod, steel and copper substrates. The high
corrosion resistance of SS substrate is attributed to that
can help in the defect areas of the electrodeposit in addition
to the morphology and chemical composition of the
electrodeposit on SS.
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