Applied Surface Science 311 (2014) 635–642

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Applied Surface Science

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

Electrodeposition of single gamma phased Zn–Ni alloy coatings

from additive-free acidic bath
Soroor Ghaziof∗, Wei Gao
Department of Chemical & Materials Engineering, the University of Auckland, P.B 92019, Auckland 1142, New Zealand

a rti c l e i nf o a b s t r a c t

Article history: Zn–Ni alloy coatings were electrodeposited on mild steel substrate from acidic sulphate bath. The effect
Received 1 April 2014 of different electrodeposition parameters including temperature, current density, agitation speed and
Received in revised form 15 May 2014 Ni2+/Zn2+ ion ratio on the Zn–Ni coating’s physical, chemical and mechanical properties has been studied.
Accepted 15 May 2014
Results show that Ni content of coatings has a strong effect on the structure, morphology and microhard-
Available online 27 May 2014
ness of coatings. Increasing Ni2+/Zn 2+ ratio in the bath, higher temperature and higher deposition current
density increased the Ni content of coatings. However, higher agitation speed increased the Zn electrode-
Keywords:
position and the anomaly of deposits. The phase structure of the coatings was strongly affected by the
Zn–Ni alloy coatings
Single gamma phase Ni content in the coatings. It changed from Zn rich μ phase to Ni5Zn21 μ phase. Weak signal of 6-Ni3Zn22
Electrodeposition phase was rarely observed for some coatings deposited at different parameters. Single μ phase coatings
X-ray diffraction with optimum properties were electrodeposited at 40 ◦C and 80 mA/cm 2, under 600 rpm agitation speed
Mechanical properties from the bath with Ni2+/Zn2+ ratio equals 1. Wear resistance of coatings were also improved by Ni doping.

© 2014 Elsevier B.V. All rights reserved.

1. Introduction it is difficult to obtain a single-phase coating as Zn–Ni coatings are

Sacrificial metallic coatings such as zinc (Zn) and Zn alloy
coatings are widely used to protect steel components in different
industries such as automotive, electrical, house building, aerospace
and fasteners industries. For many years, traditional Zn plating was
used extensively as a corrosion resistant coating for steel. However,
in aggressive environments or higher temperature its corrosion
protection is not sufficient. Zn alloys are able to provide higher cor-
rosion resistance than that of pure Zn. This is obtained by alloying
Zn with more noble metals in the Fe group such as Ni, Co and Fe
[1,2].
Zn–Ni alloy coatings have attracted much attention because
they possess higher corrosion resistance and better mechanical
properties compared with pure Zn and other Zn alloy coatings. They
also offer an important eco-friendly alternative to toxic cadmium
(Cd) coatings. It has been reported that Zn–Ni coatings with single
Ni5Zn21 μ phase structure and Ni content in range of 10–14 wt.%
has shown five times better corrosion resistant compared to pure
Zn. Coatings of less than 10 wt.% Ni are a mixture of different phases
[3,4]. Therefore, to have a commercially attractive Zn–Ni deposits,
Ni content and phase structure are two important factors. However,
∗ Corresponding author. Tel.: +64 22 303 4073.
E-mail address: sgha108@aucklanduni.ac.nz (S. Ghaziof).
mostly mixture of intermetallic phases.
Different types of baths (acid type and alkaline type) have
been used for Zn–Ni electrodeposition. Zn–Ni deposits from acid
bath normally contain 8–15 wt.% Ni, which is higher compared to
coatings from alkaline bath with 5–9% Ni [5]. Generally, the acid
bath exhibits a high cathode current efficiency (CCE) but has poor
deposit distribution on the substrate [6]. It has another advantage of
being able to plate over hardened steel and cast iron. The electrode-
position of Zn–Ni alloys from sulfate baths with different H 2SO4
and NiSO4 concentrations has been studied by Abou-Krisha et al.
[7]. Their results showed that deposits are a mixture of μ-phase
and 6-phase. In addition, the Ni content and the thickness of the
deposit decreased when H2SO4 increased. On the other hand, with
the increase of Ni concentration in the bath, the Ni content and
amount of μ-phase increased. Tsybulskaya et al. [8] have used a
polyligand alkaline bath for electrochemical deposition of Zn–Ni
alloys. Their results showed that by changing the Zn 2+/Ni2+ ratio
from 0.1 to 12.0 in the alkaline bath in the presence of aminoacetic
acid (AAA) and triethanolamine (TEA), the Ni content in the coating
can be varied from 8 to 75 at.%. Based on their XRD results, deposits
consisted of μ-phase, solid solutions of Zn or Ni in the μ-phase, or
of a mixture of μ-phase and polycrystalline Ni or Zn. Muresan et al.
[9] have studied the effect of triethanolamine as complexing agent
and polyethyleneglicol (PEG), coumarin, piperonal and vanillin as
brightening agent on corrosion resistance of Zn–Ni coatings from

http://dx.doi.org/10.1016/j.apsusc.2014.05.127
0169-4332/© 2014 Elsevier B.V. All rights reserved.
636 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642
alkaline bath. Their XRD results showed coatings consisted of ZnNi
phase with cubic structure. Based on their Tafel polarization mea-
surements, fine-grained coatings obtained in the presence of PEG
in combination with piperonal or with vanillin showed the best
corrosion resistance.
Different kinds of additives have been used to improve quality,
brightness and obtain grain refinement, such as amines, sodium
lorylsulphate (SLS), and gelatin [10–12]. However, some additives
may also affect cathodic efficiency of deposition and decrease it.
Moreover, some additives such as different types of amines and
gelatin may decrease Ni content of Zn–Ni coatings and as a result
decreasing barrier corrosion resistance of coatings. The reason
could be the presence of strong chelating ligands bind Ni ions in
very stable complexes and deposition of Ni is difficult from these
complexes [13–15]. On the other hand, the additives used for level-
ing and brightening purposes may also cause pollution and health
hazards [16].
A number of researches in this field were aimed to study
and evaluate corrosion resistance for Zn–Ni coatings [1,10,17,18].
In addition to the corrosion protection, it is essential for Zn–Ni
coatings to have sufficient wear resistance to tolerate the wear and
abrasion in their applications such as high strength steel fasten-
ers used in automotive and aerospace industries [19]. However,
few studies have focused on investigating the wear resistance of
Zn–Ni coatings. Panagopoulos et al. have studied the sliding wear
behavior of Zn–14 wt.%Ni coatings using two different alumina and
mild steel pins [20]. Based on their results, the main wear mecha-
nism of coating was the severe shearing and surface delamination
for mild steel and alumina pin, respectively. In situ tribometry and
additional ex situ analyses were conducted on Zn–Ni coatings from
commercially Zn–Ni plating solutions with commercial additives
by Sriraman et al. [19]. Their results revealed that Zn–Ni coatings
had superior resistance to adhesive wear compared to Cd coatings.
In addition, Zn–Ni coatings had higher microhardness than Zn and
Cd coatings.
In the present work, first attempt was made to produce Zn–Ni
coatings with optimum Ni content (10–12 wt. %) and single μ phase
structure from a simple and additive-free sulphate bath. The effects
of different electrodeposition parameters including temperature
(T), current density (j), agitation speed (R) and Ni2+/Zn2+ ion ratio on
Ni content, phase structure, surface morphology and microharness
were investigated. At the second stage, wear resistance of Zn–Ni
coatings deposited at optimum parameters was studied.
2. Materials and experimental
An acidic sulphate bath was used for electroplating Zn–Ni
alloy coatings. The composition of original bath and electroplat-
ing parameters are summarized in Table 1. The electrodeposition
experiments were carried out by varying one parameter (in Table 1)
each time; with all other parameters being fixed. For each set of
experiments, electroplating time was calculated to have thickness
about 10–12 µm for all coatings. 500 ml of electrodeposition bath
was used. After 1 h agitation, pH was adjusted by adding dilute
H2SO4 (10 vol.%) from 4.8 to 2. Then the temperature was increased
Table 1
The composition of electroplating bath and processing parameters.
Bath composition Quantity Plating parameters
ZnSO4 ·7H2O 35 (g/l) Temperature (T): 24, 40 and
(source of Zn2+) 60 ◦ C
NiSO4 ·6H2O 35 (g/l) Current density (j): 20, 50, 80
(source of Ni2+) and 100 (mA/cm2)
Na2 SO4·(electrolyte 80 (g/l) Agitation speed (R): 0–600
support) (rpm)
pH = 2
to the desired point for those higher than room temperature. Mag-
netic stirring was used for bath agitation.
Mild steel sheet with 25 mm×25 mm dimension was used as
substrate, and two nickel plates as the anodes at both sides. Samples
were mechanically ground down with 600-grit SiC paper and then
electropolished in a solution of 95 vol.% acetic acid and 5 vol.% per-
choloric acid at 20 V for 3 min, followed by washing with distilled
water and immediately placed into the electrolyte. After electrode-
position, the plated specimens were washed with distilled water
and ethanol, and then dried with air.
The coating morphologies and composition were analyzed using
an environmental scanning electron microscope (ESEM) with an
energy-dispersive spectroscopy (EDS) system. A MiniPal 2 PW4025
X-ray spectrometer (XRF) with Rhodium tube and spinner was also
used for composition analysis. The phase structure of the coatings
was determined using X-ray diffraction (XRD, D2 Phaser, Bruker
AXS, Germany) with Cu Ka radiation at 30 kV and 10 mA. Diffraction
patterns were recorded in the 2& range from 20 to 90◦ at a step size
of 0.02◦ s−1 and scanning rate of 0.1 s/step.
Microhardness of coatings was measured using a load of 100 g
with a holding time of 15 s by using a Vickers hardness tester. A
NANOVEA Tribometer was used to carry out linear reciprocating
wear testing. An alumina ball with diameter of 6 mm was used as
the abrasive ball. A load of 0.5 N and a sliding speed of 0.03 m/s
were used at room temperature with relative humidity of 50%; and
the total elapsed time was 5 min. With the help of a PC, the fric-
tion coefficient was continuously monitored during the tests. No
lubrication was used during the wear tests.
3. Results and discussion
3.1. The effect of processing parameters
Fig. 1 shows the effect of different electrodeposition parameters
on Ni content in coatings. All chemical compositions are quoted
in weight percentage, and obtained by using XRF representing the
average of at least three measurements. Fig. 2 shows one of the XRF
results as a sample. Fe peaks came from the steel substrate.
3.1.1. Ni2+/Zn2+ ratio in the bath
Fig. 1a indicates that by increasing Ni2+/Zn2+ ratio from 0.1 to
3, Ni content of the deposits increased from 1.3% to 6.3%. This
could be due to the competitive deposition between Ni2+ and Zn2+
ions, leading to more deposition of Ni when Ni2+ concentration
increases. Some researchers believe that this phenomenon sup-
ports the theory that the reduction of Ni ions in Zn–Ni bath is
controlled by diffusion [12]. Therefore, the Ni ion concentration
in bulk is critical in controlling the electrodeposition process in
the diffusion controlled process. It was observed that by increas-
ing the Ni2+/Zn2+ ratio in electrodeposition bath or increasing
Ni2+ concentration, hydrogen evolution on cathode surface was
increased (i.e. decreasing current efficiency), especially at sample’s
edges. Tiny pores on surface of coatings were observed because
of severe hydrogen evolution. Although the coatings deposited at
Ni2+/Zn2+ = 3 had higher Ni content compared to coatings deposited
at Ni2+/Zn2+ = 1, a loss in the quality of the deposit and its appear-
ance occurred. Therefore, Ni2+/Zn2+ = 1 was chosen for further
study as it provides better quality for the coating compared to
Ni2+/Zn2+ = 3 and higher Ni content compared to Ni2+/Zn2+ = 0.1.
3.1.2. Agitation speed
Effect of agitation speed on Ni content is shown in Fig. 1b. It can
be seen that higher agitation speed resulted in Ni content reduction
which implies that the deposition of Zn was facilitated more by the
electrolyte rotation speed than that of Ni. According to literatures
 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642 637

Fig. 1. Effect of different electroplating parameters on Ni content: (a) Ni 2+/Zn2+ ratio in the bath, (b) agitation speed, (c) temperature, (d) current density. Other electrode-
position parameters for each set of experiments are shown in the figures.

[21], this behavior could be due to the change of chemistry on cath-
ode surface under the combination of high current density and high
agitation speed. It should be mentioned that at low agitation speed
and high current density, the deposit tended to become powdery.
However, increasing the stirring speed to 600 rpm improved the
production of an adherent uniform deposit. In addition, the deposits
appear to be dull under static conditions. Thus, by changing the
cathode rotation speed, it is possible to control the smoothness and
uniformity of the deposit, and also directly affect the brightness of
the deposit. Therefore, a relatively high agitation speed (600 rmp)
was chosen as the optimum agitation speed although it provided a
slightly lower Ni content compared to the lower agitation speeds.
3.1.3. Temperature
Fig. 1c shows the effect of temperature on Ni percentage of the
coatings. It can be seen that the coating’s Ni content was increased
from ∼5% to ∼ 10% with increasing temperature from 24 ◦C to 60 ◦C.
It is well-known that the deposition reactions of iron-group metals
such as Ni are more polarized than the Zn deposition reaction [12].
In addition, the kinetic behavior of Ni is slower compared to Zn.
Therefore, higher Ni content at higher temperature (Fig. 1c) can be
attributed to the decrease in cathode polarization and enhanced
temperature-dependent kinetic parameters [12].
Observations showed some tiny pores on surface of coatings
electrodeposited at high temperature (60 ◦C) because of hydrogen
gas evolution on cathode surface which were not eliminated even
under high agitation speed of 600 rpm. This could be caused as
the higher temperature activates the evolution of hydrogen at low
polarizations [22]. On the other hand, coatings deposited at 40 ◦C
showed more uniform surface without bubble effect. Therefore,
40 ◦C was chosen for further investigation as it provides higher Ni
content compared to lower temperature and better quality surface
compared to those produced at higher temperatures.
3.1.4. Electrodeposition current density
Fig. 1d shows the effect of electrodeposition current density on
coatings’ Ni content at 40 ◦C. As can be seen, the Ni content is almost
doubled by increasing the current density from 50 to 80 mA/cm2.

Fig. 2. XRF result for Zn–Ni coating. Electrodeposition parameters: original bath with Ni 2+/Zn2+ ratio = 1, 600 rpm, j = 80 mA/cm2 at 40 ◦ C.
638 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642

Fig. 3. Effect of Ni2+/Zn2+ ion ratio in the bath on microhardness of Zn–Ni alloy
coatings. Electrodeposition was performed at 24 ◦C, 20 mA/cm2 and 300 rpm.

Fig. 6. XRD pattern of Zn–Ni alloy coatings from bath with different Ni2+/Zn2+ ratios.
Electrodeposition was performed at 24 ◦C, 20 mA/cm2 and 300 rpm.

Fig. 4. Effect of temperature on microhardness of Zn–Ni alloy coatings, deposited

at 50 mA/cm2 and 600 rpm from original bath with Ni2+/Zn2+ ratio = 1.

Smaller increase was observed in the range of 80–100 mA/cm2.

This behavior is related to the hydroxide suppression mechanism
of anomalous deposition of Zn–Ni alloy coatings. Based on this
mechanism, activity of Ni (more noble metal ion) in the bath is sig-
nificantly decreased by a stable complex formation. It is believed
that Zn forms a hydroxide and behaves as a more noble metal than Fig. 7. XRD pattern of Zn–Ni alloy coating electrodeposited under different agitation
Ni or hydrogen. Therefore, at the lower current densities, the mass speed, Electrodeposition was performed at 24 ◦C and 100 mA/cm2 from original bath
with Ni2+/Zn2+ ratio = 1.
discharge of Zn ions occurs. This is accompanied by decreasing
Ni content in deposits [21]. On the other hand, electrochemical
and 100 mA/cm2) the deposition of Ni is facilitated in preference to
consumption rate of Zn ions is increased with increasing current
hydrogen, resulting in the increase in Ni content.
densities. Therefore, the chemical formation rate of Zn hydroxide
is reduced because of decreasing Zn ions available at the cathode.
Thus, the amount of adsorbed Zn hydroxide decreases, resulting in 3.2. Microhardness
the gradual depolarisation of the apparent equilibrium potential
of Ni. This leads to an increase in the driving force for the deposi- The microhardness results are presented in Figs. 3–5, show-
tion of hydrogen and Ni [21,23]. At higher current densities (e.g. 80 ing the change in hardness as a function of the electrodeposition

Fig. 8. XRD pattern of Zn–Ni alloy coating electrodeposited at different tempera-

Fig. 5. Effect of electrodeposition current density on microhardness of Zn–Ni alloy tures. Electrodeposition was performed at 80 mA/cm 2 and 600 rpm from original
coatings, deposited at 40 ◦C and 600 rpm from original bath with Ni2+/Zn2+ ratio = 1. bath with Ni2+/Zn2+ ratio = 1.
 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642
Fig. 9. XRD pattern of Zn–Ni alloy coating electrodeposited at different curent den-
sities, Electrodeposition was performed at 40 ◦C and 600 rpm from original bath with
Ni2+/Zn2+ ratio = 1.
Fig. 10. ESEM images of Zn–Ni alloy coatings deposited at different Ni2+/Zn2+ ion
ratio in the bath: (a) 0.1, (b) 1 and (c) 3. Electrodeposition was performed at 24 ◦C,
20 mA/cm2 and 300 rpm. The insets show the surface morphologies at the higher
magnification (16,000×).
639
Fig. 11. ESEM images of Zn–Ni alloy coatings deposited at: (a) 24 ◦ C, (b) 40 ◦ C. Elec-
trodeposition was performed at 80 mA/cm 2 and 600 rpm from original bath with
Ni2+/Zn2+ ratio = 1.
parameters. It can be seen that by increasing the Ni ion concentra-
tion in the bath, temperature and electrodeposition current density,
hardness of Zn–Ni alloy coatings has been increased. This is because
that the hardness of Ni is greater than Zn, and by increasing these
parameters the Ni content increases in the deposits (Fig. 1). There-
fore, higher Ni content in the coating provides higher hardness.
The hardness of Zn–Ni coatings varies in the range of 130–250 HV,
which is significantly higher compared to pure Zn coating (∼65 HV)
[24].
3.3. Phase structure
The phase structure of coatings was studied using XRD. The
phase structure of the Zn–Ni alloys depends on the type of the plat-
ing bath and Ni content in the coatings [25]. Fig. 6 shows that phase
structures of the coatings as a function of Ni content in the bath. As
discussed before, Ni content of these coatings has been increased
from 1.3% to 6.3% when the bath Ni2+/Zn2+ ratio increased from 0.1
to 3. For low Ni ion ratio, the coatings consist of mixture of pure
Zn and hexagonal structured μ phase. By increasing this ratio to
3, 6 phase (Ni3Zn22) with a monoclinic structure appears in the
deposits. While pure Ni was not found in the XRD patterns, the
intermetallic compounds were detected, indicating that Ni took up
the position in Zn crystal lattice and formed the intermetallic com-
pounds. It is also noted that single μ phase was not observed in
these coatings because of low Ni content (below 8%).
XRD patterns of two Zn–Ni alloy coatings deposited under static
and agitation are shown in Fig. 7. It can be seen that coatings
deposited without agitation consisted mixture of pure Zn and
intermetallic phases including 6 andμ. On the other hand, alloys
deposited under 600 rpm agitation contained single μ phase with
640 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642
Fig. 12. ESEM images of Zn–Ni alloy coatings, electrodeposited at: (a) 50, (b) 80,
and (c) 100 mA/cm 2. Electrodeposition was performed at 40 ◦C and 600 rpm from
original bath with Ni2+/Zn2+ ratio = 1.
more uniform structure, which may have better corrosion resis-
tance even they have lower Ni contents.
The effect of temperature on the phase structure of Zn–Ni alloy
coating is shown in Fig. 8. By increasing the temperature from 24 ◦C
to 40 ◦C, the phase structure changed from single μ phase to single
μ phase. These coatings were electrodeposited at a relatively high
current density (80 mA/cm2) and 600 rpm agitation for 10 min. XRF
analysis revealed that the Ni content of these coatings were about
6 and 10 wt.% for 24 ◦C and 40 ◦C, respectively, indicating that Ni
content increased with increasing temperature. This also changed
the phase structure of coating from μ with hexagonal close packing
structure to μ with a composition of Ni5Zn21 and body-centered
cubic structure.
Based on the above XRD results with desirable Ni content and
single μ phase, the effect of different current densities (50, 80 and
100 mA/cm2) on the phase structures of alloy coatings were inves-
tigated at 40 ◦C. XRD patterns of coatings at these current densities
have been shown in Fig. 9. It can be seen that with j = 50 mA/cm2,
the phase structure of coating is mixture of μ and μ phases, while
coatings deposited at 80 and 100 mA/cm2 consist of single μ phase.
Based on XRF results (Fig. 1), both coatings have Ni content more
Fig. 13. Wear track of Zn–Ni coatings deposited at different current densities: (a) 50,
(b) 80, and (c) 100 mA/cm2. Electrodeposition was performed at 40 ◦C and 600 rpm
from original bath with Ni2+/Zn2+ ratio = 1.
than 10 wt.%. On the other hand, Ni content was only∼6 wt.% for the
50 mA/cm2 deposited coating. It demonstrates again that Ni con-
tent in the alloy plays an important role in the phase structure. By
increasing the Ni content, Zn–Ni intermetallic phases with a higher
Ni content will be formed.
3.4. Surface morphology
Surface morphology of Zn–Ni alloy coatings electroplated at dif-
ferent parameters is illustrated in Figs. 10 and 11. The coatings are
compact and no cracks can be seen on the surface. The surface of
2% Ni coating (Fig. 10a) presents platelet hexagonal morphology
of a rich Zn layer. For the coatings with more Ni (Fig. 10b and c),
more nodular morphology is appeared, showing the Ni content has
significant influence on the coating morphology.
Fig. 11 shows the effect of temperature on surface morphol-
ogy of Zn–Ni alloy coatings. The images illustrate that the surface
morphology changed from rough platelet hexagonal morphology of
 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642
single μ phase (Fig. 11a) to a smoother nodular fine-grained mor-
phology of single μ phase (Fig. 11b). It again shows that the deposit
morphology is strongly dependent on the Ni content and phase
structure of coatings [26].
The effect of electroplating current density on the surface
morphology of coatings deposited at 40 ◦C is shown in Fig. 12.
The coating deposited at 50 mA/cm2 has fine grain morphology
as a background and some grown deposits on the surface with
cauliflower-like morphology (Fig. 12a). EDS analysis on these areas
showed that they are richer in Ni content compared to the matrix
(∼8.45 wt.% Ni compared to ∼ 6 wt.% Ni of matrix). As indicated
before by XRD studies, these coatings have a mixed structure
of two phases; zinc rich-μ phase and μ phase with higher Ni
content. By comparison, deposits produced at higher current den-
sities have larger nodules on surface. Fig. 12b shows that the μ
phase coatings are uniform and compact, with a fine-grained mor-
phology and clear boundaries. Coatings deposited at 100 mA/cm2
(Fig. 12c) have a similar morphology, but have larger colony size and
coarser.
Based on the all results described above, considering Ni
content and phase structure of coatings, we can suggest the
following optimized electrodeposition parameters: operation tem-
perature 40 ◦C, agitation speed 600 rpm, and bath composition of
Ni2+/Zn2+ = 1.
3.5. Wear resistance analysis
Wear tests were performed on Zn–Ni alloy coating deposited at
three different current densities (50, 80 and 100 mA/cm2) at 40 ◦C.
The thickness of coatings was about 12 µm measured from cross
section image. Fig. 13 shows worn surfaces of coatings observed
under optical microscope. Results from the comparison experi-
ments showed that the wear track on the coating deposited at
80 mA/cm2 was the narrowest and the plough lines were shal-
lowest. However, wear track of coatings deposited at 50 and
100 mA/cm2 was wider; indicating that the wear resistance has
been decreased. Table 2 summarized the results of wear track
widths and wear loss volume of these coatings. As can be seen,
Fig. 14. Friction coefficient versus sliding distance for Zn–Ni coatings deposited at different current densities: (a) 50, (b) 80, and (c) 100 mA/cm 2. Electrodeposition was
performed at 40 ◦C and 600 rpm from original bath with Ni2+/Zn2+ ratio = 1.
641
Table 2
Wear track widths and wear volume loss of Zn–Ni coatings deposited at three differ-
ent current densities (50, 80 and 100 mA/cm2) at 40 ◦C, 600 rpm and Ni2+/Zn2+ = 1.
Deposition current Wear track Wear volume loss
density (mA/cm2) (µm) (10−3 mm3)
50 336 10.5
80 292 7
100 327 9.7
Zn–Ni coating deposited at 80 mA/cm2 possesses a minimum vol-
ume of wear loss, showing the best wear resistance compared to
Zn–Ni coatings deposited at 50 and 100 mA/cm2.
Wear resistance is dependent on a number of factors including
the hardness, microstructure and surface morphology of materials,
operation temperature, contact pressure, wear mode, and lubrica-
tion [27]. Since the coatings were tested under identical conditions,
then the materials surface property plays a main role in wear
behavior of tested Zn–Ni coatings. The lower wear resistance of
coating deposited at 50 mA/cm2 could be due to the decrease of
the hardness value as a result of decreasing Ni content. Further-
more, coatings deposited at 80 mA/cm2 showed a smoother and
more uniform surface compared to the coatings deposited at 50 and
100 mA/cm2 (Fig. 12), which may provide lower friction coefficient
and better wear resistance [24].
Fig. 14 shows the friction coefficient of the Zn–Ni coatings slid-
ing against alumina ball as a function of the sliding distance. For
the Zn–Ni coating deposited at 80 mA/cm2, the steady state value
of friction coefficient was lower (0.52) than that for the other two
coatings. The steady state value of friction coefficients for coatings
deposited at 50 and 100 mA/cm2 were about 0.83 and 0.68, respec-
tively. The frictional behavior of materials is of great importance
in tribology not only because of frictional force between sliding
surfaces but also because it generally affects the wear behavior
[28]. Changing in the surface morphology can cause changes in the
friction and wear behavior of materials.
Regarding wear mechanism of Zn–Ni coatings, it has been
reported [19] that the initially rough coating becomes smooth by
ploughing at the first stages of wear. The worn Zn–Ni debris adheres
642 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642
to the counterface simultaneously. As wear continues, transferred
material is detached and regained in various regions. In progressing
toward higher cycles, the contact area grows wider, the wear track
becomes deep enough to appear continuous; and some shearing
and mechanical deformations of loose wear debris are observed.
Therefore, wear behavior of coatings is affected not only by the
hardness of material but also by the surface morphology and condi-
tions. Based on the above experimental results, it can be concluded
that better wear resistance of Zn–Ni alloy coatings deposited at
80 mA/cm2 was attributed to smoother and more uniform surface
morphology as well as higher hardness and lower friction coeffi-
cient compared to coatings deposited at 50 and 100 mA/cm2.
4. Conclusion
In summary, Zn–Ni alloy coatings with ∼10 wt.% Ni and sin-
gle μ phase structure were successfully deposited from simple
additive-free sulphate bath. Ni content of coatings has a strong
effect on the structure, morphology and microhardness of coatings.
Increasing Ni2+/Zn2+ ratio in the bath, relatively high tempera-
ture and deposition current density increase the Ni content in the
coatings. However, high agitation speed resulted in reduction of
Ni content. Coatings deposited at 40 ◦C under an agitation speed
of 600 rpm showed bright metallic surface with uniform appear-
ance. The phase structure of the coatings was strongly affected by
the Ni content in the coatings. It changes from Zn rich μ phase to
Ni5Zn21 μ phase by increasing Ni content in the coatings from 6
to 10 wt. %. Zn–Ni coatings with∼10 wt.% Ni content and single
μ phase structure deposited at 40 ◦C and 80 mA/cm2 showed the
lowest friction coefficient and best wear resistance compared to
the coatings deposited at 50 and 100 mA/cm2 because of the higher
hardness and smoother surface morphology.
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