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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 r t i c l e i n f 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+ /Zn2+ 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-
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 ␩ phase to Ni5 Zn21 ␥ phase. Weak signal of ␦-Ni3 Zn22
Electrodeposition phase was rarely observed for some coatings deposited at different parameters. Single ␥ phase coatings
X-ray diffraction with optimum properties were electrodeposited at 40 ◦ C and 80 mA/cm2 , 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

mostly mixture of intermetallic phases.
Sacrificial metallic coatings such as zinc (Zn) and Zn alloy Different types of baths (acid type and alkaline type) have
coatings are widely used to protect steel components in different been used for Zn–Ni electrodeposition. Zn–Ni deposits from acid
industries such as automotive, electrical, house building, aerospace bath normally contain 8–15 wt.% Ni, which is higher compared to
and fasteners industries. For many years, traditional Zn plating was coatings from alkaline bath with 5–9% Ni [5]. Generally, the acid
used extensively as a corrosion resistant coating for steel. However, bath exhibits a high cathode current efficiency (CCE) but has poor
in aggressive environments or higher temperature its corrosion deposit distribution on the substrate [6]. It has another advantage of
protection is not sufficient. Zn alloys are able to provide higher cor- being able to plate over hardened steel and cast iron. The electrode-
rosion resistance than that of pure Zn. This is obtained by alloying position of Zn–Ni alloys from sulfate baths with different H2 SO4
Zn with more noble metals in the Fe group such as Ni, Co and Fe and NiSO4 concentrations has been studied by Abou-Krisha et al.
[1,2]. [7]. Their results showed that deposits are a mixture of ␥-phase
Zn–Ni alloy coatings have attracted much attention because and ␦-phase. In addition, the Ni content and the thickness of the
they possess higher corrosion resistance and better mechanical deposit decreased when H2 SO4 increased. On the other hand, with
properties compared with pure Zn and other Zn alloy coatings. They the increase of Ni concentration in the bath, the Ni content and
also offer an important eco-friendly alternative to toxic cadmium amount of ␥-phase increased. Tsybulskaya et al. [8] have used a
(Cd) coatings. It has been reported that Zn–Ni coatings with single polyligand alkaline bath for electrochemical deposition of Zn–Ni
Ni5 Zn21 ␥ phase structure and Ni content in range of 10–14 wt.% alloys. Their results showed that by changing the Zn2+ /Ni2+ ratio
has shown five times better corrosion resistant compared to pure from 0.1 to 12.0 in the alkaline bath in the presence of aminoacetic
Zn. Coatings of less than 10 wt.% Ni are a mixture of different phases acid (AAA) and triethanolamine (TEA), the Ni content in the coating
[3,4]. Therefore, to have a commercially attractive Zn–Ni deposits, can be varied from 8 to 75 at.%. Based on their XRD results, deposits
Ni content and phase structure are two important factors. However, consisted of ␥-phase, solid solutions of Zn or Ni in the ␥-phase, or
of a mixture of ␥-phase and polycrystalline Ni or Zn. Muresan et al.
[9] have studied the effect of triethanolamine as complexing agent
∗ Corresponding author. Tel.: +64 22 303 4073. and polyethyleneglicol (PEG), coumarin, piperonal and vanillin as
E-mail address: sgha108@aucklanduni.ac.nz (S. Ghaziof). brightening agent on corrosion resistance of Zn–Ni coatings from

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 to the desired point for those higher than room temperature. Mag-
phase with cubic structure. Based on their Tafel polarization mea- netic stirring was used for bath agitation.
surements, fine-grained coatings obtained in the presence of PEG Mild steel sheet with 25 mm × 25 mm dimension was used as
in combination with piperonal or with vanillin showed the best substrate, and two nickel plates as the anodes at both sides. Samples
corrosion resistance. were mechanically ground down with 600-grit SiC paper and then
Different kinds of additives have been used to improve quality, electropolished in a solution of 95 vol.% acetic acid and 5 vol.% per-
brightness and obtain grain refinement, such as amines, sodium choloric acid at 20 V for 3 min, followed by washing with distilled
lorylsulphate (SLS), and gelatin [10–12]. However, some additives water and immediately placed into the electrolyte. After electrode-
may also affect cathodic efficiency of deposition and decrease it. position, the plated specimens were washed with distilled water
Moreover, some additives such as different types of amines and and ethanol, and then dried with air.
gelatin may decrease Ni content of Zn–Ni coatings and as a result The coating morphologies and composition were analyzed using
decreasing barrier corrosion resistance of coatings. The reason an environmental scanning electron microscope (ESEM) with an
could be the presence of strong chelating ligands bind Ni ions in energy-dispersive spectroscopy (EDS) system. A MiniPal 2 PW4025
very stable complexes and deposition of Ni is difficult from these X-ray spectrometer (XRF) with Rhodium tube and spinner was also
complexes [13–15]. On the other hand, the additives used for level- used for composition analysis. The phase structure of the coatings
ing and brightening purposes may also cause pollution and health was determined using X-ray diffraction (XRD, D2 Phaser, Bruker
hazards [16]. AXS, Germany) with Cu K␣ radiation at 30 kV and 10 mA. Diffraction
A number of researches in this field were aimed to study patterns were recorded in the 2Â range from 20 to 90◦ at a step size
and evaluate corrosion resistance for Zn–Ni coatings [1,10,17,18]. of 0.02◦ s−1 and scanning rate of 0.1 s/step.
In addition to the corrosion protection, it is essential for Zn–Ni Microhardness of coatings was measured using a load of 100 g
coatings to have sufficient wear resistance to tolerate the wear and with a holding time of 15 s by using a Vickers hardness tester. A
abrasion in their applications such as high strength steel fasten- NANOVEA Tribometer was used to carry out linear reciprocating
ers used in automotive and aerospace industries [19]. However, wear testing. An alumina ball with diameter of 6 mm was used as
few studies have focused on investigating the wear resistance of the abrasive ball. A load of 0.5 N and a sliding speed of 0.03 m/s
Zn–Ni coatings. Panagopoulos et al. have studied the sliding wear were used at room temperature with relative humidity of 50%; and
behavior of Zn–14 wt.%Ni coatings using two different alumina and the total elapsed time was 5 min. With the help of a PC, the fric-
mild steel pins [20]. Based on their results, the main wear mecha- tion coefficient was continuously monitored during the tests. No
nism of coating was the severe shearing and surface delamination lubrication was used during the wear tests.
for mild steel and alumina pin, respectively. In situ tribometry and
additional ex situ analyses were conducted on Zn–Ni coatings from 3. Results and discussion
commercially Zn–Ni plating solutions with commercial additives
by Sriraman et al. [19]. Their results revealed that Zn–Ni coatings 3.1. The effect of processing parameters
had superior resistance to adhesive wear compared to Cd coatings.
In addition, Zn–Ni coatings had higher microhardness than Zn and Fig. 1 shows the effect of different electrodeposition parameters
Cd coatings. on Ni content in coatings. All chemical compositions are quoted
In the present work, first attempt was made to produce Zn–Ni in weight percentage, and obtained by using XRF representing the
coatings with optimum Ni content (10–12 wt. %) and single ␥ phase average of at least three measurements. Fig. 2 shows one of the XRF
structure from a simple and additive-free sulphate bath. The effects results as a sample. Fe peaks came from the steel substrate.
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 3.1.1. Ni2+ /Zn2+ ratio in the bath
were investigated. At the second stage, wear resistance of Zn–Ni Fig. 1a indicates that by increasing Ni2+ /Zn2+ ratio from 0.1 to
coatings deposited at optimum parameters was studied. 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+
2. Materials and experimental ions, leading to more deposition of Ni when Ni2+ concentration
increases. Some researchers believe that this phenomenon sup-
An acidic sulphate bath was used for electroplating Zn–Ni ports the theory that the reduction of Ni ions in Zn–Ni bath is
alloy coatings. The composition of original bath and electroplat- controlled by diffusion [12]. Therefore, the Ni ion concentration
ing parameters are summarized in Table 1. The electrodeposition in bulk is critical in controlling the electrodeposition process in
experiments were carried out by varying one parameter (in Table 1) the diffusion controlled process. It was observed that by increas-
each time; with all other parameters being fixed. For each set of ing the Ni2+ /Zn2+ ratio in electrodeposition bath or increasing
experiments, electroplating time was calculated to have thickness Ni2+ concentration, hydrogen evolution on cathode surface was
about 10–12 ␮m for all coatings. 500 ml of electrodeposition bath increased (i.e. decreasing current efficiency), especially at sample’s
was used. After 1 h agitation, pH was adjusted by adding dilute edges. Tiny pores on surface of coatings were observed because
H2 SO4 (10 vol.%) from 4.8 to 2. Then the temperature was increased 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-
Table 1
The composition of electroplating bath and processing parameters.
ance occurred. Therefore, Ni2+ /Zn2+ = 1 was chosen for further
study as it provides better quality for the coating compared to
Bath composition Quantity Plating parameters Ni2+ /Zn2+ = 3 and higher Ni content compared to Ni2+ /Zn2+ = 0.1.
ZnSO4 ·7H2 O 35 (g/l) Temperature (T): 24, 40 and
(source of Zn2+ ) 60 ◦ C
NiSO4 ·6H2 O 35 (g/l) Current density (j): 20, 50, 80
3.1.2. Agitation speed
(source of Ni2+ ) and 100 (mA/cm2 ) Effect of agitation speed on Ni content is shown in Fig. 1b. It can
Na2 SO4 ·(electrolyte 80 (g/l) Agitation speed (R): 0–600 be seen that higher agitation speed resulted in Ni content reduction
support) (rpm) which implies that the deposition of Zn was facilitated more by the
pH = 2
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) Ni2+ /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- In addition, the kinetic behavior of Ni is slower compared to Zn.
ode surface under the combination of high current density and high Therefore, higher Ni content at higher temperature (Fig. 1c) can be
agitation speed. It should be mentioned that at low agitation speed attributed to the decrease in cathode polarization and enhanced
and high current density, the deposit tended to become powdery. temperature-dependent kinetic parameters [12].
However, increasing the stirring speed to 600 rpm improved the Observations showed some tiny pores on surface of coatings
production of an adherent uniform deposit. In addition, the deposits electrodeposited at high temperature (60 ◦ C) because of hydrogen
appear to be dull under static conditions. Thus, by changing the gas evolution on cathode surface which were not eliminated even
cathode rotation speed, it is possible to control the smoothness and under high agitation speed of 600 rpm. This could be caused as
uniformity of the deposit, and also directly affect the brightness of the higher temperature activates the evolution of hydrogen at low
the deposit. Therefore, a relatively high agitation speed (600 rmp) polarizations [22]. On the other hand, coatings deposited at 40 ◦ C
was chosen as the optimum agitation speed although it provided a showed more uniform surface without bubble effect. Therefore,
slightly lower Ni content compared to the lower agitation speeds. 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.
3.1.3. 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 3.1.4. Electrodeposition current density
from ∼5% to ∼10% with increasing temperature from 24 ◦ C to 60 ◦ C. Fig. 1d shows the effect of electrodeposition current density on
It is well-known that the deposition reactions of iron-group metals coatings’ Ni content at 40 ◦ C. As can be seen, the Ni content is almost
such as Ni are more polarized than the Zn deposition reaction [12]. 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 Ni2+ /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
speed, Electrodeposition was performed at 24 ◦ C and 100 mA/cm2 from original bath
Ni or hydrogen. Therefore, at the lower current densities, the mass
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/cm2 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) 635–642 639

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. 11. ESEM images of Zn–Ni alloy coatings deposited at: (a) 24 ◦ C, (b) 40 ◦ C. Elec-
trodeposition was performed at 80 mA/cm2 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)

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 ␩ phase. By increasing this ratio to
3, ␦ phase (Ni3 Zn22 ) 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 ␥ 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
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,
and agitation are shown in Fig. 7. It can be seen that coatings
20 mA/cm2 and 300 rpm. The insets show the surface morphologies at the higher deposited without agitation consisted mixture of pure Zn and
magnification (16,000×). intermetallic phases including ␦ and␩. On the other hand, alloys
deposited under 600 rpm agitation contained single ␩ 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/cm2 . Electrodeposition was performed at 40 ◦ C and 600 rpm from
original bath with Ni2+ /Zn2+ ratio = 1.
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
more uniform structure, which may have better corrosion resis-
from original bath with Ni2+ /Zn2+ ratio = 1.
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 than 10 wt.%. On the other hand, Ni content was only ∼6 wt.% for the
to 40 ◦ C, the phase structure changed from single ␩ phase to single 50 mA/cm2 deposited coating. It demonstrates again that Ni con-
␥ phase. These coatings were electrodeposited at a relatively high tent in the alloy plays an important role in the phase structure. By
current density (80 mA/cm2 ) and 600 rpm agitation for 10 min. XRF increasing the Ni content, Zn–Ni intermetallic phases with a higher
analysis revealed that the Ni content of these coatings were about Ni content will be formed.
6 and 10 wt.% for 24 ◦ C and 40 ◦ C, respectively, indicating that Ni
content increased with increasing temperature. This also changed 3.4. Surface morphology
the phase structure of coating from ␩ with hexagonal close packing
structure to ␥ with a composition of Ni5 Zn21 and body-centered Surface morphology of Zn–Ni alloy coatings electroplated at dif-
cubic structure. ferent parameters is illustrated in Figs. 10 and 11. The coatings are
Based on the above XRD results with desirable Ni content and compact and no cracks can be seen on the surface. The surface of
single ␥ phase, the effect of different current densities (50, 80 and 2% Ni coating (Fig. 10a) presents platelet hexagonal morphology
100 mA/cm2 ) on the phase structures of alloy coatings were inves- of a rich Zn layer. For the coatings with more Ni (Fig. 10b and c),
tigated at 40 ◦ C. XRD patterns of coatings at these current densities more nodular morphology is appeared, showing the Ni content has
have been shown in Fig. 9. It can be seen that with j = 50 mA/cm2 , significant influence on the coating morphology.
the phase structure of coating is mixture of ␩ and ␥ phases, while Fig. 11 shows the effect of temperature on surface morphol-
coatings deposited at 80 and 100 mA/cm2 consist of single ␥ phase. ogy of Zn–Ni alloy coatings. The images illustrate that the surface
Based on XRF results (Fig. 1), both coatings have Ni content more morphology changed from rough platelet hexagonal morphology of
S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642 641

single ␩ phase (Fig. 11a) to a smoother nodular fine-grained mor- Table 2

Wear track widths and wear volume loss of Zn–Ni coatings deposited at three differ-
phology of single ␥ phase (Fig. 11b). It again shows that the deposit
ent current densities (50, 80 and 100 mA/cm2 ) at 40 ◦ C, 600 rpm and Ni2+ /Zn2+ = 1.
morphology is strongly dependent on the Ni content and phase
structure of coatings [26]. Deposition current Wear track Wear volume loss
density (mA/cm2 ) (␮m) (10−3 mm3 )
The effect of electroplating current density on the surface
morphology of coatings deposited at 40 ◦ C is shown in Fig. 12. 50 336 10.5
The coating deposited at 50 mA/cm2 has fine grain morphology 80 292 7
100 327 9.7
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
Zn–Ni coating deposited at 80 mA/cm2 possesses a minimum vol-
(∼8.45 wt.% Ni compared to ∼6 wt.% Ni of matrix). As indicated
ume of wear loss, showing the best wear resistance compared to
before by XRD studies, these coatings have a mixed structure
Zn–Ni coatings deposited at 50 and 100 mA/cm2 .
of two phases; zinc rich-␩ phase and ␥ phase with higher Ni
Wear resistance is dependent on a number of factors including
content. By comparison, deposits produced at higher current den-
the hardness, microstructure and surface morphology of materials,
sities have larger nodules on surface. Fig. 12b shows that the ␥
operation temperature, contact pressure, wear mode, and lubrica-
phase coatings are uniform and compact, with a fine-grained mor-
tion [27]. Since the coatings were tested under identical conditions,
phology and clear boundaries. Coatings deposited at 100 mA/cm2
then the materials surface property plays a main role in wear
(Fig. 12c) have a similar morphology, but have larger colony size and
behavior of tested Zn–Ni coatings. The lower wear resistance of
coating deposited at 50 mA/cm2 could be due to the decrease of
Based on the all results described above, considering Ni
the hardness value as a result of decreasing Ni content. Further-
content and phase structure of coatings, we can suggest the
more, coatings deposited at 80 mA/cm2 showed a smoother and
following optimized electrodeposition parameters: operation tem-
more uniform surface compared to the coatings deposited at 50 and
perature 40 ◦ C, agitation speed 600 rpm, and bath composition of
100 mA/cm2 (Fig. 12), which may provide lower friction coefficient
Ni2+ /Zn2+ = 1.
and better wear resistance [24].
Fig. 14 shows the friction coefficient of the Zn–Ni coatings slid-
3.5. Wear resistance analysis 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
Wear tests were performed on Zn–Ni alloy coating deposited at of friction coefficient was lower (0.52) than that for the other two
three different current densities (50, 80 and 100 mA/cm2 ) at 40 ◦ C. coatings. The steady state value of friction coefficients for coatings
The thickness of coatings was about 12 ␮m measured from cross deposited at 50 and 100 mA/cm2 were about 0.83 and 0.68, respec-
section image. Fig. 13 shows worn surfaces of coatings observed tively. The frictional behavior of materials is of great importance
under optical microscope. Results from the comparison experi- in tribology not only because of frictional force between sliding
ments showed that the wear track on the coating deposited at surfaces but also because it generally affects the wear behavior
80 mA/cm2 was the narrowest and the plough lines were shal- [28]. Changing in the surface morphology can cause changes in the
lowest. However, wear track of coatings deposited at 50 and friction and wear behavior of materials.
100 mA/cm2 was wider; indicating that the wear resistance has Regarding wear mechanism of Zn–Ni coatings, it has been
been decreased. Table 2 summarized the results of wear track reported [19] that the initially rough coating becomes smooth by
widths and wear loss volume of these coatings. As can be seen, ploughing at the first stages of wear. The worn Zn–Ni debris adheres

Fig. 14. Friction coefficient versus sliding distance for 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.
642 S. Ghaziof, W. Gao / Applied Surface Science 311 (2014) 635–642

to the counterface simultaneously. As wear continues, transferred [6] S. Srinivasan, M. Pushpavanam, Properties of zinc alloy electrodeposits pro-
material is detached and regained in various regions. In progressing duced from acid and alkaline electrolytes, J. Solid State Electrochem. 13 (2009)
toward higher cycles, the contact area grows wider, the wear track [7] M. Abou-Krisha, F. Assaf, A. Toghan, Electrodeposition of Zn–Ni alloys from
becomes deep enough to appear continuous; and some shearing sulfate bath, J. Solid State Electrochem. 11 (2007) 244–252.
and mechanical deformations of loose wear debris are observed. [8] L.S. Tsybulskaya, T.V. Gaevskaya, O.G. Purovskaya, T.V. Byk, Electrochemicalde-
position of zinc–nickel alloy coatings in a polyligand alkaline bath, Surf. Coat.
Therefore, wear behavior of coatings is affected not only by the Technol. 203 (2008) 234–239.
hardness of material but also by the surface morphology and condi- [9] L.M. Muresan, J. Eymard, D. Blejan, E. Indrea, Zn–Ni alloy coatings from alkaline
tions. Based on the above experimental results, it can be concluded bath containing triethanolamine. Influence of additives, Studia Universitatis
Babes-Bolyai Chemia LV (1) (2010) 37–44.
that better wear resistance of Zn–Ni alloy coatings deposited at
[10] M.E. Soares, C.A.C. Souza, S.E. Kuri, Corrosion resistance of a Zn–Ni electrode-
80 mA/cm2 was attributed to smoother and more uniform surface posited alloy obtained with a controlled electrolyte flow and gelatin additive,
morphology as well as higher hardness and lower friction coeffi- Surf. Coat. Technol. 201 (2006) 2953–2959.
[11] H. Ashassi-Sorkhabi, A. Hagrah, N. Parvini-Ahmadi, J. Manzoori, Zinc–nickel
cient compared to coatings deposited at 50 and 100 mA/cm2 .
alloy coatings electrodeposited from a chloride bath using direct and pulse
current, Surf. Coat. Technol. 140 (2001) 278–283.
4. Conclusion [12] A.M. Alfantazi, J. Page, U. Erb, Pulse plating of Zn–Ni alloy coatings, J. Appl.
Electrochem. 261 (1996) 225–234.
[13] V.G. Roev, R.A. Kaidrikov, A.B. Khakimullin, Zinc–nickel electroplating from
In summary, Zn–Ni alloy coatings with ∼10 wt.% Ni and sin- alkaline electrolytes containing amino compounds, Russ. J. Electrochem. 37
gle ␥ phase structure were successfully deposited from simple (2001) 756–759.
additive-free sulphate bath. Ni content of coatings has a strong [14] C. Muller, M. Sarret, M. Benballa, Complexing agents for a Zn–Ni alkaline bath,
J. Electroanal. Chem. 51 (2002) 85–92.
effect on the structure, morphology and microhardness of coatings. [15] N. Eliaz, K. Venkatakrishna, A.C. Hegde, Electroplating and characteriza-
Increasing Ni2+ /Zn2+ ratio in the bath, relatively high tempera- tion of Zn–Ni, Zn–Co and Zn–Ni–Co alloys, Surf. Coat. Technol. 205 (2010)
ture and deposition current density increase the Ni content in the 1969–1978.
[16] B. Praveen, T. Venkatesha, New brightener for Zn–Ni alloy plating from sulfate
coatings. However, high agitation speed resulted in reduction of bath, Chem. Eng. Commun. 199 (2012) 812–822.
Ni content. Coatings deposited at 40 ◦ C under an agitation speed [17] S.H. Mosavat, M.H. Shariat, M.E. Bahrololoom, Study of corrosion performance
of 600 rpm showed bright metallic surface with uniform appear- of electrodeposited nanocrystalline Zn–Ni alloy coatings, Corros. Sci. 59 (2012)
ance. The phase structure of the coatings was strongly affected by [18] K.R. Baldwin, M.J. Robinson, C.J.E. Smith, Corrosion rate measurements of elec-
the Ni content in the coatings. It changes from Zn rich ␩ phase to trodeposited zinc–nickel alloy coatings, Corros. Sci. 36 (1994) 1115–1131.
Ni5 Zn21 ␥ phase by increasing Ni content in the coatings from 6 [19] K.R. Sriraman, H.W. Strauss, S. Brahimi, R.R. Chromik, J.A. Szpunar, J.H. Osborne,
Tribological behavior of electrodeposited Zn, Zn–Ni, Cd and Cd–Ti coatings on
to 10 wt. %. Zn–Ni coatings with ∼10 wt.% Ni content and single
low carbon steel substrates, Tribol. Int. 56 (2012) 107–120.
␥ phase structure deposited at 40 ◦ C and 80 mA/cm2 showed the [20] C.N. Panagopoulos, K.G. Georgarakis, P.E. Agathocleous, Sliding wear behavior
lowest friction coefficient and best wear resistance compared to of zinc–nickel alloy electrodeposits, Tribol. Int. 36 (2003) 619–623.
[21] M.R. Kalantary, G.D. Wilcox, D.R. Gabe, The production of compositionally mod-
the coatings deposited at 50 and 100 mA/cm2 because of the higher
ulated alloys by simulated high speed electrodeposition from a single solution,
hardness and smoother surface morphology. Electrochim. Acta 40 (1995) 1609–1616.
[22] F.J.F. Miranda, O. Barcia, O. Mattos, R. Wiart, Electrodeposition of Zn–Ni alloys in
sulfate electrolytes: I. Experimental approach, J. Electrochem. Soc. 144 (1997)
[23] A.C. Hegde, K. Venkatakrishna, N. Eliaz, Electrodeposition of Zn–Ni, Zn–Fe and
[1] R. Ramanauskas, P. Quintana, L. Maldonado, R. Pomés, M.A. Pech-Canul, Corro- Zn–Ni–Fe alloys, Surf. Coat. Technol. 205 (2010) 2031–2041.
sion resistance and microstructure of electrodeposited Zn and Zn alloy coatings, [24] A.M. Alfantazi, U. Erb, Microhardness and thermal stability of pulse-plated
Surf. Coat. Technol. 92 (1997) 16–21. Zn–Ni alloy coatings, Mater. Sci. Eng. A 212 (1996) 123–129.
[2] M. Rahman, S. Sen, M. Moniruzzaman, K. Shorowordi, Morphology and prop- [25] J.B. Bajat, M.D. Maksimović, V.B. Mišković-Stanković, S. Zec, Electrodeposition
erties of electrodeposited Zn–Ni alloy coatings on mild steel, J. Mech. Eng. 40 and characterization of Zn–Ni alloys as sublayers for epoxy coating deposition,
(2009) 9–14. J. Appl. Electrochem. 31 (2001) 355–361.
[3] Y. Boonyongmaneerat, S. Saenapitak, K. Saengkiettiyut, Reverse pulse elec- [26] A.M. Alfantazi, A.M. El-Sherik, U. Erb, The role of nickel in the morphology
trodeposition of Zn–Ni alloys from a chloride bath, J. Alloys Compd. 487 (2009) evolution of pulse plated Zn–Ni alloy coatings, Scr. Metall. Mater. 30 (1994)
479–482. 1245–1250.
[4] M.M. Abou-Krisha, Effect of pH and current density on the electrodeposition of [27] Y. Riddle, T. Bailerare, Friction and wear reduction via an Ni–B electroless bath
Zn–Ni–Fe alloys from a sulfate bath, J. Coat. Technol. Res. 9 (2012) 775–783. coating for metal alloys, JOM 57 (2005) 40–45.
[5] G.D. Wilcox, D.R. Gabe, Electrodeposited zinc alloy coatings, Corros. Sci. 35 [28] N.P. Suh, H. Sin, The genesis of friction, Wear 69 (1981) 91–114.
(1993) 1251–1258.