SCT-20165; No of Pages 10

Surface & Coatings Technology xxx (2015) xxxxxx

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Surface & Coatings Technology

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

Electrodeposition of nanocrystalline ZnNi coatings with single gamma

phase from an alkaline bath
Zhongbao Feng, Qingyang Li, Jinqiu Zhang, Peixia Yang, Hailin Song, Maozhong An
State Key Laboratory of Urban Water Resource and Environment, School of Chemical Engineering and Technology, Harbin Institute of Technology, Harbin 150001, China

a r t i c l e

i n f o

Article history:
Received 6 December 2014
Accepted in revised form 13 March 2015
Available online xxxx
Keywords:
ZnNi alloy coatings
DMH
Cathode current efciency
Nanocrystalline
Single gamma phase
Hardness

a b s t r a c t
Nanocrystalline ZnNi (grain size about 26 nm) alloy coatings were electrodeposited on carbon steel substrates
in alkaline bath with 5,5-dimethylhydantoin (DMH) as the complexing agent. The coatings with 13 wt.%16 wt.% Ni
content and the electrolyte with high current efciency (N85%) were achieved at the optimized parameters,
i.e., Ni2+/(Zn2+ + Ni2+) ratio 0.32, current density 2 Adm2, temperature 50 C and agitation speed 1000 rpm.
The electrochemical behavior of the bath has been studied by cyclic voltammetry (CV), chronopotentiometry
(CE) and cathodic polarization. Results show that the deposition of ZnNi alloys occurs at moderate overpotential
and the rotation speed and bath temperature have a strong effect on cathodic polarization curves. The effects of
Ni2+/(Zn2+ + Ni2+) ratio, current density, temperature and agitation speed on Ni content and cathode current
efciency were investigated. Studies indicate that the phase structure, grain size, microhardness and corrosion
resistance of deposits are directly dependent on Ni content in deposits. The phase structure of deposits changes
from a mixture of -phase and -phase to single -phase with (411) plane orientation. Furthermore, the grain
size decreases with the increase of Zn content in deposits and the increase in current density can also lead to the
decrease in grain size. The increase in microhardness of deposits is strongly affected by the increase of Ni content
in deposits rather than the HallPetch relationship. ZnNi alloy coatings with about 13 wt.% Ni content present
best corrosion resistance and the bath has a good stability.
2015 Published by Elsevier B.V.

1. Introduction
Electrodeposited zinc is often used as the sacricial coatings to protect
steel substrates against corrosion. However, its corrosion resistance is
insufcient at high temperature and severe environments. According to
the literature [1,2], zinc alloy coatings can provide higher corrosion
resistance compared to pure zinc coatings. This is obtained by alloying
zinc with Fe group metals such as Fe, Co and Ni. In recent years, the
interest in ZnNi alloys has been increasing as a substitute for cadmium
coatings [3,4] due to its eco-friendly properties [5,6]. In addition, ZnNi
alloy coatings have attracted considerable attention in the aerospace
and energy generation owing to its excellent corrosion resistance at
high temperature and severe oxidizing conditions [7]. The properties
and characteristics of ZnNi coatings are mainly determined by their microstructure and phase composition [8]. It is reported that the corrosion
resistance of ZnNi alloy coatings with 8 to 14 wt.% of nickel and single
gamma phase structure is ve times higher than that of pure Zn coatings
[9]. Hammami et al. [10] have demonstrated the increase in corrosion
resistance with deposits electrodeposited under chronopotentiometry
conditions (18.32 mA/cm2 and 36.63 mA/cm2). Mosavat et al. [11] have
Corresponding author. Tel./fax: +86 451 86418616.
E-mail address: mzan@hit.edu.cn (M. An).

revealed that the Ni content was a major factor to the corrosion resistance
of deposits.
ZnNi alloys are commonly electrodeposited from acid, alkaline
cyanide and alkaline noncyanide (zincate type [12] and weak alkaline
type) baths. The acid bath is the rst commercial electrolyte [13],
which displays a high cathode current efciency but poor throwing
power. In contrast, the alkaline bath can be used for steel parts of
complex shape and exhibits more uniform Ni content in deposits. It is
noted that the commercial alkaline bath used for ZnNi alloy deposition
contains cyanide, which is toxic and carcinogenic to human health, and
a low current efciency [14,15] (60%80%) is obtained in the zincate
type alkaline bath. Therefore, it is necessary but difcult to develop an
eco-friendly alkaline bath with high current efciency.
The complexing agents are the key factors to obtain a stable alkaline
ZnNi bath. Conrad et al. [16] have used sodium acetate as a complexing
ligand to stabilize the Zn2 + and Ni2 + in weak alkaline bath. Mller
et al. [12] have investigated four amine alkaline baths. Their results
showed that all of those amines were good complexing agents and
a homogeneous composition of ZnNi alloy can be obtained. Up to
now, 5,5-dimethylhydantoin(DMH) is often used as a complexing
ligand in Au [17] or Ag [18] deposition. To the best of our knowledge,
there is no report on the application of DMH used as a complexing
ligand in ZnNi alloy deposition.

http://dx.doi.org/10.1016/j.surfcoat.2015.03.020
0257-8972/ 2015 Published by Elsevier B.V.

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Table 1
The bath composition and process parameters of the bath.
Bath composition and process parameters

Optimum values

ZnSO4 7H2O (g/L)

NiSO4 6H2O (g/L)
DMH (g/L)
Na4P2O7 10H2O (g/L)
K2CO3 (g/L)
Additives (g/L)
PH
Cathode density (Adm2)
Temperature (C)
Agitation speed (rpm)

70
30
140
40
95
0.04
910
1, 2, 3, 4, 5
20, 30, 40, 50, 60
0, 200, 600, 1000, 1400

Nanocrystalline ZnNi alloy coatings are usually obtained by using

different plating modes [19] (PC, RPC, etc.) or adding additives. Alfantez
et al. [20] produced nanocrystalline ZnNi coatings from a chloridebased electrolyte and Tehrani et al. [21] presented nanocrystalline
single -Zn3Ni phase by cyclic voltammetry at a scan rate of 10 V/s.
Their coatings were both obtained from acid bath. By comparison, it is
difcult to obtain nanocrystalline ZnNi alloy coatings from alkaline
bath and there are a few reports about it. Li et al. [22] prepared nanocrystalline ZnNi alloy coatings with the grain size in the range of 14 nm to
33 nm in alkaline bath using a laboratory-made additive. Mosavat et al.
[23] also obtained nanocrystalline ZnNi alloy coatings with average
grain size ranging from 13 nm to 68 nm containing saccharin as additive
from alkaline bath. However, these works were complicated and the coatings had some disadvantages, e.g.: low microhardness. Brooks et al. [24]
electrodeposited nanocrystalline -phase ZnNi alloy coatings from a
chloride-based bath and their results indicated that the hardening of the
coatings was independent on grain size.

Fig. 2. EDS of ZnNi alloy deposits at the optimized parameters.

In this paper, a new alkaline ZnNi alloy bath with DMH as the
complexing agent was obtained. The effects of the Ni2+/(Zn2+ + Ni2+)
ratio, cathode current density, temperature and agitation speed on Ni
content and cathode current efciency were studied. Simultaneously,
electrochemical behavior was investigated by cyclic voltammetry (CV),
chronopotentiometry (CE) and cathodic polarization. The inuence of Ni
content on phase structure, surface morphology, grain size, microhardness and corrosion resistance of deposits and the relationship between
grain size and microhardness were also analyzed. Finally, the stability of
the bath was studied.

Fig. 1. Effects of bath composition and process parameters on Ni content and current efciency: a) Ni2+/(Zn2+ + Ni2+) ratio, electrodeposition was carried out at 2 Adm2, 50 C and
1000 rpm, b) cathode current density, electrodeposition was carried out at 50 C and 1000 rpm from bath with Ni2+/(Zn2+ + Ni2+) ratio = 0.32, c) temperature, electrodeposition was
carried out at 2 Adm2 and 1000 rpm from bath with Ni2+/(Zn2+ + Ni2+) ratio = 0.32, d) agitation speed, electrodeposition was carried out at 2 Adm2 and 50 C from bath with
Ni2+/(Zn2+ + Ni2+) ratio = 0.32.

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cathodic polarization were 100 mV/s and 1 mV/s, respectively, unless

special description.
2.2. Electrodeposition and coating characterization
The cathode current efciency () was estimated according to the
Faraday law, using deposit composition, charge passed and weight
gained of the deposit.

Fig. 3. Cyclic voltammograms of Zn, Ni and ZnNi alloy obtained from the bath with
optimized bath composition and process parameters at a scan rate of 100 mV/s from
0.7 V to -1.9 V vs. SSE.

2. Experimental
2.1. Electrochemical testing
The bath composition and process parameters are listed in Table 1.
The additives consist of two aromatic compounds and a wetting agent.
The non-soluble DSA electrode was used as the anode. 5 cm 4 cm of
carbon steel plates, polished to a mirror-like surface by different grades
of abrasive paper (from 1000 to 5000 Cw), degreased with 30 wt.%
sodium hydroxide solution at 50 C for 5 min, then activated with 50%
hydrochloric acid for few seconds, were used as the cathode, which
were weighted before and after electrodepositing. The required pH of
the bath was adjusted to 910 by 10% sodium hydroxide solution and
the bath temperature was controlled with thermostat water bath.
Mechanical stirring was used for bath agitation. The stirrer is PTFEcoated impeller 2-bladed and cylindrical cross-sectioned with 0.85 mm
screw pitched. During electrodepositing, the stirrer is located in the center
of the bath and the rotation speed is in the range of 0 rpm to 1400 rpm.
Cyclic
voltammetry
(CV),
cathodic
polarization
and
chronopotentiometry (CE) were carried out in a conventional threeelectrode glass cell on CHI750D and PARSTAT 2273 electrochemical workstations, respectively. A platinum foil (99.99%, 1 cm2) was used as the
counter electrode and a mercury/mercurous sulfate electrode (SSE), i.e.
Hg/Hg2SO4 was employed as the reference electrode. A Pt electrode
with a working surface of 7.1 mm2 ( = 3 mm) was used as the working
electrode. The bath temperature is 50 C. The scan rates of CV and

m2 m1 F X ci ni
 100%
It
Mi

Where m1 (g) and m2 (g) are the weight before and after
electroplating, I (A) is the total current passed in the plating time t (s),
ci is the weight fraction of the element in the ZnNi alloy deposit, ni is
the number of electrons transferred per atom of each metal, Mi is the
molar mass of metal (gmol1), and F is the Faraday's constant
(96,485 Cmol1).
Surface morphologies of the deposits were examined by the scanning
electron microscope (SEM, Helios Nanolab 600i). The composition of the
coatings was determined by an energy-dispersive spectroscopy (EDS).
X-ray diffraction (XRD, D/max-) was used to analyze the phase
structure and crystal orientation with Cu K radiation at 40 kV and
40 mA ( = 0.1546 nm). The 2 ranged from 20 to 100 at a scan
rate of 0.02 per second.
The average grain size of the coatings was calculated by using the
Scherrer's formula.
D k= cos

where D is the average grain size of the coatings, is the full width at the
half maximum (FWHM) and is the reectance angle.
The microhardness of the coatings was measured by a Vickers
microhardness tester (HV-1000A) with a load of 200 gf applying for
15 s. The average of ve hardness values at different points was
determined as the microhardness of deposit.
The corrosion behavior of nanocrystalline ZnNi alloy coatings
was measured by potentiodynamic polarization techniques. A three
electrode system containing 3.5 wt.% sodium chloride (NaCl) solution
was used. A saturated calomel electrode (SCE) and platinum foil
(1 1 cm2) were employed as the reference electrode and counter
electrode, respectively. 1 cm2 area of carbon steel plates, ZnNi alloy
and Zn coatings were used as the working electrodes. High purity nitrogen was used for deaeration of the solution. The bath temperature is
25 C. The scan rate of the curves was 1 mV/s with the scan range
from 0.25 V to +0.25 V of open circuit potential.
The stability of the bath was examined in two ways. One way was to
put the bath in the sealed state at room temperature for one week or at

Fig. 4. (a) Et curves of ZnNi for Pt electrode at different current densities. (b) Et curves of Zn at different current densities, Ni and only DMH + K2CO3 for Pt electrode from the bath with
optimized bath composition and process parameters.

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Fig. 5. (a) Cathodic polarization curves on Pt rotating disk electrode at different rotation speeds (b) Cathodic polarization curves on Pt electrode at different temperatures from the bath
with optimized bath composition and process parameters.

65 C for 1 h to observe whether there was a phenomenon of turbidity

or decomposition of the bath and whether the electrolyte can be
electroplated normally after that. The other way was to record the
charge (Ah) passed through the bath (1 L) when the bright coatings
are obtained during electrodepositing.
3. Results and discussion
3.1. The effects of bath composition and process parameters
The effects of bath composition and process parameters on Ni
content and cathode current efciency are shown in Fig. 1.

3.1.1. The Ni2+/(Zn2+ + Ni2+) (at.%) ratio in the bath

As seen in Fig. 1a, the composition curve for the more noble Ni in
deposits lies below content reference line (CRL) in the bath, indicating
that the co-deposition of ZnNi alloy coatings shows an anomalous
behavior in which the less noble metal Zn is deposited preferentially.
Ni content in deposits increases from 9.57 wt.% to 19.11 wt.% with the
increase of Ni2 +/(Zn2 + + Ni2 +) ratio from 0.16 to 0.48 in the bath.
This can be explained by the competitive deposition between Zn2 +
and Ni2+. The reduction of Ni2+ controlled by diffusion leads to more
deposition of Ni at the cathode as Ni2 + concentration increases [25].
When Ni2+/(Zn2+ + Ni2+) ratio in the bath increases above 0.48, Ni
content in the coatings remains nearly constant (19 wt.%21 wt.%).

Fig. 6. XRD patterns of ZnNi alloy coatings electrodeposited at different conditions: a) Ni2+/(Zn2+ + Ni2+) ratio, b) current density, c) temperature, d) agitation speed. Other electrodeposition
parameters for each experiment are at the optimized conditions. (For interpretation of the references to color in this gure, the reader is referred to the web version of this article.)

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Fig. 7. Effect of Ni2+/(Zn2+ + Ni2+) ratio on surface morphologies: a) 0.16, b) 0.32, c) 0.48. Electrodeposition was carried out at 2 Adm2, 50 C and 1000 rpm.

Some researchers have revealed that only nickel complexing ions

formed by Ni2+ and complexing agents can electrodeposit in deposits
and the superuous nickel ions in the independent state, which do not
have enough complexing agents to coordinate with, cannot co-deposit
with Zn2+ [22]. In addition, the increase in Ni2+/(Zn2+ + Ni2+) ratio
in the bath results in the decrease of current efciency. According to
Tsybulakaya's [15] research, this behavior can be due to the higher overvoltage of hydrogen production on Zn than on Ni. Thus, the reaction of
hydrogen generation occurs more intensively with the increase of Ni
content in deposits. Therefore, 0.32 is chosen for Ni2+/(Zn2+ + Ni2+)
ratio due to its higher current efciency.

the increase of current density from 2 Adm 2 to 5 Adm 2. This

can be described by the large increase of cathode polarization at
high current densities. Moreover, it is well-known that the decrease in
current efciency results in the improvement of uniform distribution
of deposits on the substrates.
The electrodeposition rate of the coatings is relatively low and the
surface of the coatings tends to be dull when cathode current density
is 1 Adm 2. Furthermore, a low current efciency is obtained and
some tiny pores can be seen after a long time deposition at high current
densities, which is due to the severe hydrogen evolution. Therefore,
2 Adm2 is chosen for further investigations.

3.1.2. Cathode current density

The cathode current efciency is too low to be studied when current
density is larger than 5 Adm 2. As seen from Fig. 1b, Ni content in
deposits increases with the increase of current density. This can be
explained by the fact that the local pH of the cathode surface changes
by increasing the applied current density, thus affecting the stability of
nickel complexes and resulting in a difference of Ni content in deposits.
Meanwhile, this behavior is related to the hydroxide suppression
mechanism (HSM) of anomalous co-deposition. Zn can form the
hydroxide and behave as a more noble metal than Ni. Therefore, at
low current densities, the mass deposition of Zn leads to the low content
of Ni in deposits. In addition, the chemical formation rate of Zn hydroxide
decreases with the rapid consumption of Zn ions at high current densities.
Thus, the amount of adsorbed Zn hydroxide decreases at the cathode,
leading to the increase of Ni deposition at high current densities.
A small increase in Ni content is observed in the approximate range
of 25 Adm 2 , which is also associated with the anomalous codeposition [26]. In this case, the qualied coatings can be obtained
within a broad range of current densities and this behavior is good
for industrial production. On the other hand, the current efciency
is above 99% and close to 100% when current density is lower than
2 Adm 2. A sharp decrease of current efciency is observed with

3.1.3. Temperature
Ni content in deposits rst increases and then decreases with the
increase of the temperature (Fig. 1c). This is due to the increase in
hydrogen overvoltage or cathode depolarization. The same result is
also obtained in NiCo co-deposition [27]. When the temperature
increases from 20 C to 60 C, current efciency increases obviously
and it is over 85% at 50 C. The appearance of the coatings becomes a
little blushing and some pinholes can be observed on the cathode
surface as the temperature is higher than 50 C. In addition, the smooth
and mirror-bright appearance of deposits can be obtained at low
temperatures. Therefore, 50 C is chosen for further studies owing to
its good appearance and high current efciency.
3.1.4. Agitation speed
The Ni content decreases by increasing the rotation speed from
0 rpm to 1400 rpm (Fig. 1d), suggesting the easier deposition of Zn2+
than that of Ni2+ by rotation speed [28]. This is related to the anomalous
co-deposition of ZnNi alloy. According to hydrogen suppression
mechanism [29], the consumption of Zn2 + is supplied quickly with
the increase of rotation speed and the formation of zinc hydroxide
hinders the deposition of Ni2+ in the electrolyte, resulting in the decrease
of Ni content in deposits. Moreover, the concentration polarization of the

Fig. 8. Effect of cathode current density on surface morphologies: a) 1 Adm2, b) 3 Adm2, c) 5 Adm2. Electrodeposition was carried out at 50 C and 1000 rpm from the bath with
Ni2+/(Zn2+ + Ni2+) ratio = 0.32. The insets show the surface morphologies at the lower magnication (10,000).

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the metal ion concentration in the bath indicate that ZnNi alloys follow
anomalous co-deposition mechanism.
3.2. Electrochemical studies

Fig. 9. The effect of current density on crystallite size.

electrolyte decreases with the decrease of the diffusion layer thickness

when the agitation speed increases, resulting in the increase of current
efciency. This behavior is also conrmed by the RDE analysis (Fig. 5a).
The current plateau disappears by increasing the rotation speed. It should
be mentioned that some tiny pores can be observed at low rotation
speeds because of the severe hydrogen evolution. Therefore, 1000 rpm
is chosen for further investigations.
Based on the above analysis, the optimized bath composition and
process parameters are as follows: Ni2 +/(Zn2 + + Ni2 +) ratio 0.32,
current density 2 Adm 2, temperature 50 C and agitation speed
1000 rpm.
The coating deposited at the optimized parameters is analyzed by
EDS spectroscopy. As shown in Fig. 2, the height of ZnNi signals and

3.2.1. Cyclic voltammetry

In order to probe the deposition behavior of the ZnNi alloy electrolyte, cyclic voltammetry (CV) is used to identify the kinetic behavior of
various electroactive species at the optimized bath composition and
process parameters as mentioned above. Fig. 3 shows the cyclic voltammograms of Zn, Ni and ZnNi alloy on Pt electrode at a scan rate of
100 mV/s. The curves all sweep from the rest potential to the negative
direction. The literature [18] has revealed that DMH is easy to absorb on
electrode surface. The cathodic peak c1 appears in all three curves
although it is very small in Ni voltammogram. This indicates that c1 can
be attributed to the absorption of DMH on Pt electrode. Therefore, the
peaks c2 and c2 are related to ZnNi alloy and Zn deposition, respectively.
Beyond the peaks c2 and c2, the increase in current density at more
negative potentials corresponds to hydrogen evolution reaction. When
the potential switches to the positive direction, a crossover of ZnNi
alloy curve appears, indicating a nucleation and growth process at the
electrode surface [30]. In Ni voltammogram, the current density increases
from about 1.2 V, which is due to the reduction of nickel complexes.
When the potential is lower than 1.6 V, bulk Ni deposition and hydrogen evolution reaction occur. The anodic peak a1, centered at 0.7 V,
corresponds to the oxidation of Ni to Ni2+. In Zn curve, only one anodic
peak a1 is related to the dissolution of Zn, indicating a single phase
growth mechanism. The anodic peak a2 does not appear in ZnNi alloy
curve. This may be due to desorption of DMH on surplus Zn coating,
which is not stripped totally before a2. Two anodic peaks are observed
for ZnNi alloy deposition corresponding to the appearance of two phases
(Fig. 6), -phase (the rst anodic peak a1) and -phase ((Ni5Zn21) the
second anodic peak a2). The third peak a3 is attributed to the stripping

Fig. 10. Microhardness of ZnNi alloy coatings electrodeposited at different conditions: a) Ni2+/(Zn2+ + Ni2+), b) current density, c) temperature, d) agitation speed. Other electrodeposition
parameters for each experiment are at the optimized conditions.

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of Ni from these two phases. The behavior of Zn deposition is similar to

that of ZnNi deposition in the negative direction and the cathodic
peaks c2 and c2 are close to each other. In addition, the potential
of anodic peak a1 (-phase) is slightly more positive compared
with the anodic peak a1 in Zn deposition. This can be explained by
the fact that ZnNi alloy coatings mainly consist of Zn. The ZnNi
alloy deposition (red line) lies between the Zn (blue line) and Ni
(black line) depositions, indicating that ZnNi alloy coatings with
different Ni contents can be obtained. There is no deposition of Ni
at 1.2 V in ZnNi deposition as mentioned before. This can be associated
to the presence of Zn2+, which inhibits the deposition of Ni2+.
There are three zinc-DMH complexes and three nickel-DMH complexes in the electrolyte, respectively, i.e., [Zn(DMH)]+, Zn(DMH)2,
[Zn(DMH)3] and [Ni(DMH)]+, Ni(DMH)2, [Ni(DMH)3]. Here
we assume that the main complexing agents in the electrolyte are
[Zn(DMH)3] and [Ni(DMH)3]. This is due to the fact that the formation constants (log10()) of zinc-DMH complexes and nickel-DMH
complexes are 2.48, 5.82, 8.18 and 3.05, 4.94, 6.18, respectively [31] and
the bath pH is 910. Although only one cathodic peak c2 is observed in
ZnNi alloy CV curve, it is generally accepted that the discharge of the
single metal M (Zn or Ni) occurs via a two-step mechanism in which
only one electron is transferred in each step [32]. The deposition can
proceed as follows:



MDMH 3 e M DMH  2DMH

MDMH  e M DMH :

3
4

Abd El Rehim believed that the mechanism of ZnNi alloy deposition

is associated with the formation of the mixed intermediate surface
species (ZnNi)+
ad, which can be reduced at the cathode surface.

ZnNiad e Zn Ni
The height of the peaks gives an indication about the quantity of its
phase in deposits [10]. It should be mentioned that the height of the
anodic peak a1 of the Zn dissolution is larger than that of the anodic
peak a1 of ZnNi alloy dissolution. This reveals that the amount of Zn
content in the alloy coatings is less than that in single metal coatings,
indicating the appearance of Ni in the alloy coatings.
3.2.2. Chronopotentiometry
Chronopotentiometry is used to study the initial deposition of ZnNi
alloy on Pt electrode. Fig. 4 shows the potential-time curves of ZnNi
alloy and Zn at different current densities for 10 min, Ni and only
DMH + K2CO3 at 2.0 Adm 2 for 10 min. The initial decrease in the
potential is related to the ohmic potential drop and the charging of
the double-layer capacitance. After that, a sudden change in slope is
observed in ZnNi alloy at 1.0 Adm2 and it changes into a potential
peak with the increase of current density from 1.5 Adm 2 to
2.5 Adm2. This behavior is an indication of diffusion controlled reduction [33]. The nucleation potential (E) and nucleation time (T) are
where the potential peaks fall. When the applied current density
increases, the formation of the nucleation needs larger overpotential
to grow. Therefore, the E shifts to more negative potential and the T
decreases with the increase of the applied current density. Moreover,
after the potential peak, a slow decrease of the potentials corresponds
to the decrease in the concentration of electroactive species at the electrode surface caused by the diffusion process. The plateau of the potentials
appears with the extension of the time, which is related to the deposition
of metal ions and hydrogen evolution reaction. It is clear that hydrogen
evolution reaction occurs severely by increasing the overpotential at
larger current density, which can lead to the sharp decrease of current
efciency. The same behavior is also obtained in Zn deposition at different
current densities.

Fig. 11. Microhardness of nanocrystalline coatings as a function of inverse square root of

grain size (d1/2).

The potential-time curve of DMH + K2CO3 is very close to the curve

of Ni deposition. Compared with the potential-time curves of Zn, Ni and
ZnNi alloy on Pt electrode at 2 Adm2, it can be seen that the deposition
of Ni needs low overpotential to form the initial nucleus and grows at low
potential [34]. Whereas the nucleation of Zn deposition take place with
high overpotential and the deposits grow at high overpotential. The
deposition of ZnNi alloy occurs at moderate overpotential, which lies
between the deposition of Zn and Ni. This behavior indicates that the
deposition of Ni is inhibited by the presence of Zn2+, while the deposition
of Zn is induced by the presence of Ni2+.
3.2.3. Polarization curves
RDE is used to investigate the mass transport condition of the
electrolyte. Fig. 5a reveals the cathodic polarization curves at different
rotation speeds in ZnNi alloy bath. It is noted that the current density
increases with the increase of rotation speed, indicating that the
deposition process of ZnNi alloy is under mixed rate control. The
limiting current plateau (b2 Adm 2) is observed at the rotation
speed of 400 rpm and 600 rpm and it is not easy to be identied at high
rotation speeds. When the rotation speed increases from 400 rpm to
800 rpm, the increase in current density is obvious. This is caused by
the rapid supplement of electroactive species Zn2+ and Ni2+ at high
rotation speeds. However, the increase in current density is slight by
increasing rotation speed from 1000 rpm to 1200 rpm. According to the
above analysis, it can be concluded that in order to obtain a high current
efciency of the ZnNi alloy bath, a high rotation speed (N800 rpm)
should be used.

Fig. 12. The effect of Ni content on microhardness of ZnNi alloy coatings.

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phase is not detected in the XRD patterns while Ni content is over

12.94 wt.%.
It is concluded that the coatings consist of -phase and -phase
when Ni content is below 11.73 wt.% and single -phase is obtained
with the increase of Ni content from 12.87 wt.% to 19.11 wt.%. As a
result, Ni content has a direct effect on the phase structure of ZnNi
alloys. ZnNi intermetallic phases containing high Ni content can be
formed with the increase of Ni content in deposits. It is known that
alkaline ZnNi alloy bath has more homogeneous Ni content in the
usual range of current densities compared to the acid bath [14]. Similarly,
uniform chemical and phase compositions of ZnNi alloys are obtained in
the present investigation. Moreover, the peak value of -phase with (411)
plane orientation is higher than that of -phase with other orientations,
which reveals that -phase with (411) plane orientation plays a
dominant role in the coatings and the coatings with single -phase
with (411) plane orientation can exhibit better corrosion resistance [9].
Fig. 13. Polarization curves obtained for the ZnNi alloy at different Ni contents and Zn
coatings in a 3.5% NaCl solution.

Cathodic polarization curves obtained at different temperatures are

shown in Fig. 5b. As can be seen, the reduction current increases with
the increase in temperature from 20 C to 60 C. This indicates that
the kinetics of deposition is higher at higher temperatures [35]. The
difference between the cathodic peak potentials shows that the ZnNi
co-deposition is favored at high temperatures. The cathodic peaks
become well dened as the temperature increases, indicating enhanced
deposition kinetics at high temperatures. In addition, the peak potentials are shifted to more positive direction with the increase of the
temperature from 20 C to 60 C. Such behavior is primarily the result
of intrinsically slow nickel kinetics [4]. This means that the deposition
potentials of ZnNi alloy at high temperatures are far from the potential
of hydrogen evolution compared with these at low temperatures, indicating a higher current efciency at higher bath temperature. Moreover,
the experimental results shown in Fig. 1c are also in accordance with the
analysis of the cathodic polarization curves.
3.3. The effect of Ni content in deposit
3.3.1. The phase structure of deposit
For determination of crystalline phases, XRD results are presented
for illustration purposes. X-ray diffraction patterns of the coatings are
shown in Fig. 6. According to earlier [36] study, ZnNi alloy coatings
mainly consist of four phases: -phase, a solid solution of nickel in
zinc with less than 1% nickel; -phase, an intermediate phase with a
composition Ni3Zn22; -phase, an intermediate phase with a composition Ni5Zn21; and -phase, a solid solution of zinc in nickel with an
equilibrium solubility of about 30% Zn. It is noted that ZnNi alloys
are a mixture of -phase and -phase, which are obtained from
low Ni2 +/(Zn2 + + Ni 2 +) ratio (0.16) and small current density
(1 Adm 2), respectively (Fig. 3a and b). Ni content in these coatings
ranges from 9.57 wt.% to 11.72 wt.% as mentioned before. By increasing
the Ni2+/(Zn2+ + Ni2+) ratio and current density, the single -phase
structure with body-centered cubic structure can be obtained and the
EDS analysis shows that Ni content in these coatings is in the range
from 13.23 wt.% to 19.11 wt.%.
Fig. 6c shows X-ray diffraction patterns of deposits as a function of
temperature. The deposits consist of -phase and -phase with low Ni
content (11.26 wt.% and 11.73 wt.%) at 20 C and 60 C, respectively.
Single -phase can be deposited in the coatings with high Ni content
(12.87 wt.%) at 40 C.
The effect of rotation speed on phase structure of deposits is shown
in Fig. 6d. It can be seen that the coatings with Ni content ranging from
14.62 wt.% to 12.94 wt.% are characterized by single -phase structure
when the rotation speed increases from 0 rpm to 1400 rpm. The -

3.3.2. The surface morphology of deposit

The surface morphologies of ZnNi alloy coatings obtained at different
Ni2+/(Zn2+ + Ni2+) ratios are shown in Fig. 7. The deposits are compact,
ne grained and covered the substrates completely without any cracks on
the surface. Some dendritic grains can be seen in Fig. 7a, which reveals the
rich Ni content in this area compared to the matrix according to the EDS
analysis. Based on XRD results, this is attributed to a mixture of -phase
and -phase in deposits. The surface of the coating (Fig. 7a) is nodular
morphology on a nanoscale, indicating that the formation of crystal
nucleus is easier than the growth of it. By comparison, the morphology
of deposits changes from rectangular pyramid (Fig. 7b) to cauliowerlike (Fig. 7c). The grain size increases with the increase of Ni2+/
(Zn2+ + Ni2+) ratio and the deposits with high Zn content have the
ne grain compared to those with low Zn content, indicating that Zn
renes the grain size [35]. Meanwhile, it was reported that the decrease
in grain size led to an improvement of passive lm's protective performance and the increase of the corrosion resistance of deposits [37].
These observations show that the Ni content has a signicant inuence
on the morphology and grain size of the coatings.
Fig. 8 shows the surface morphologies of ZnNi alloy coatings
obtained at different cathode current densities. The micro-morphologies
of the coatings can be divided into two microcosmic sizes: nanocrystalline
grains (shown in Figs. 8 and 9) and micron-sized colonies (shown in the
insets of Fig. 8). The surface of nanocrystalline grain and colony is rectangular pyramid morphology and nodular morphology, respectively. When
the current density is relatively higher, the coatings have the larger colony
size and clearer colony boundary but ner grain size on nanoscale. This
result is in accordance with El-Sherik's investigation [38]. Moreover, the
rapid nucleation rate at high current densities results in the decrease in
grain size of deposits. This behavior indicates that the current density
has a strong inuence on grain size and surface morphology of ZnNi
alloy deposits.
According to the results shown in Fig. 8, the current density has a
strong effect on the coating's grain size rather than the Ni content in deposits. Fig. 9 illustrates the effect of current density on average size of
nanocrystalline deposits, which is calculated by Scherrer's formula according to XRD results. The grain size decreases from 27.2 nm to
20.7 nm by increasing the current density from 1 Adm 2 to
Table 2
The electrochemical parameters (Ecorr, jcorr, Rp) of coating samples in a 3.5 wt.% NaCl
solution.
Coatings

Ecorr vs. SCE/V

jcorr/Acm2

Rp/

a: Zn-19.54 wt.%Ni
b: Zn-15.91 wt.%Ni
c: Zn-13.31 wt.%Ni
d: Zn-9.62 wt.%Ni
e: Pure Zn
Carbon steel

0.860
0.826
0.792
0.935
1.039
0.464

56.55
50.99
40.14
52.73
144.20
20.59

450.8
616.4
703.7
365.
243.4
703.2

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Z. Feng et al. / Surface & Coatings Technology xxx (2015) xxxxxx

5 Adm2. This is related to an increased nucleation rate caused by larger

overpotential at higher current density. The same results were also
obtained by Li et.al [22]. Li et.al showed that nanocrystalline ZnNi alloys
were electrodeposited in alkaline bath in their investigations. As a result,
the larger current density can be used to obtain the ner grain size of
deposits. The result is in accordance with the SEM analysis shown in Fig. 8.
3.3.3. The microhardness of deposit
The microhardness of ZnNi alloy coatings electrodeposited at
different conditions is shown in Fig. 10ad. It can be seen that the hardness of deposits increases with the increase of the Ni2+/(Zn2+ + Ni2+)
ratio and current densities, respectively. In contrast, by increasing rotation
speed from 0 rpm to 1400 rpm, the hardness decreases from 363.2 HV to
288.2 HV. When the temperature increases, the hardness of the coatings
rst increases then decreases. It is noted that the hardness of deposits is
signicantly higher than that of other nanocrystalline ZnNi alloy
coatings obtained in general alkaline bath [23].
The grain size of deposits is calculated by the Scherrer's equation.
Only the coatings with single -phase are used for the study to eliminate
the interference of the phase structure. It is well-known that the microhardness of the materials mainly depends on the crystalline size, which
can be represented by the HallPetch equation.
1=2

HV H0 kd

Where HV is the measured hardness, H0 and k are constants, and d

is the average grain size. Indeed, the HallPetch equation is one of
the main reasons why the materials with ultra-ne crystallite grain
sizes are considered for enhanced strength and hardness. In this
way, nanocrytalline materials will have the optimized properties.
As is evidenced in Fig. 11, there are some points far from the tting
line, indicating that the HallPetch relationship is not true in this
study. The same results were also obtained in nanocrystalline ZnNi
alloy deposition electrodeposited from alkaline bath by Mosavat [23].
Indeed, some researchers revealed the negative hardness trend in the
relationship between HV and d1/2 [24].
Fig. 12 represents the change in microhardness as a function of Ni
content in deposits. It is noted that the microhardness increases with
the increase of Ni content in deposits, which is due to the higher
hardness of Ni than that of Zn. This indicates that Ni content is the
predominating factor of the hardening mechanism in ZnNi alloy
coatings.
3.3.4. Corrosion examination
The potentiodynamic polarization curves for different Ni contents of
ZnNi alloys and pure Zn nanocrystalline coatings on carbon steel using
a 3.5 wt.% NaCl solution are shown in Fig. 13. The electrochemical
parameters (Ecorr, icorr, Rp) for both ZnNi alloys and Zn coatings are
summarized in Table 2. It should be noted that the corrosion potentials
of all deposits remain negative compared to the carbon steel, which
means that all deposits can provide the corrosion protection to the carbon
steel. On the other hand, the corrosion potential of nanocrystalline Zn
coating is more negative ( 1.034 V) compared to nanocrystalline
ZnNi alloys ( 0.792 V to 0.935 V), indicating better corrosion
resistance of ZnNi alloys coatings. Moreover, there is a smaller difference
in the corrosion potentials of nanocrystalline ZnNi alloys with different
Ni contents. The ZnNi alloy coatings with 13.31 wt.% and 15.91 wt.% Ni
content display lower icorr and more positive Ecorr values, suggesting an
improvement of corrosion resistance.
It can be concluded that Ni content of ZnNi alloy coatings plays an
important role in corrosion resistance behavior. The deposits with Ni
content in the range of about 13 wt.% to 16 wt.% show better corrosion
resistance. This is in accordance with the study of Mosavat [11].

3.4. The stability of the bath

The stability of the bath has been examined in details. There is no
precipitation occurred in the electrolyte and the behaviors of the coatings
and bath are good when the bath is sealed for 2 months at room temperature or heated for 1 h at 65 C. On the other hand, the appearance of
coatings is bright after electroplating for 80 Ah/L, indicating that the
electrolyte can be electroplated for a long time. These results reveal that
the alkaline bath has a high stability.
4. Conclusion
An alkaline bath with DMH as the complexing agent was used to
electroplate ZnNi alloy coatings. The results from this work indicated
that ZnNi alloy coatings with 13 wt.%16 wt.% Ni content and single
-phase are obtained on a nanoscale (about 26 nm). The appearance
of the coatings is mirror-bright and the cathode current efciency is
over 85% at the optimized parameters, i.e., Ni2+/(Zn2+ + Ni2+) ratio
0.32, current density 2 Adm 2, temperature 50 C and agitation
speed 1000 rpm. The phase structure, grain size, microhardness and
corrosion resistance of deposits are directly dependent on the Ni content
in deposits.
Cyclic voltammetry and chronopotentiometry analysis show that
ZnNi alloy deposition occurs at moderate overpotential and the
deposition of Ni is inhibited by the presence of Zn2+, while the deposition
of Zn is induced by the presence of Ni2+. RDE results indicate a mixed
controlled process. In addition, the temperature has a strong effect on
cathodic polarization and ZnNi co-deposition is easy to be obtained at
high temperatures.
Increasing Ni2+/(Zn2+ + Ni2+) ratio in the electrolyte, high cathode
current density and relatively low agitation speed increase the Ni
content in deposits. Whereas the Ni content rst increases and then
decreases when the temperature increases. On the other hand, The
current efciency decreases with the increase of Ni2+/(Zn2+ + Ni2+)
ratio and current density, respectively. However, the high temperature
and high agitation speed result in the high current efciency.
The phase structure of deposits changes from a mixture of -phase
and -phase to single -phase with (411) plane orientation by increasing
Ni content in deposits. The grain size decreases with the increase of Zn
content, and higher current density can also lead to the decrease in
grain size. The microhardness of the coatings increases with the increase
of Ni content in deposits, which does not follow the HallPetch relationship. Moreover, ZnNi alloy coatings with 13 wt.% Ni content present
best corrosion resistance compared to the coatings with other Ni content
and pure Zn coating. The bath has a good stability.
Acknowledgments
The authors are grateful for nancial support from the State Key
Laboratory of Urban Water Resource and Environment (Harbin Institute
of Technology) (2012DX03).
References
[1] R. Fratesi, G. Roventi, G. Giuliani, C.R. Tomachuk, J. Appl. Electrochem. 27 (1997)
10881094.
[2] I.H. Karahan, H.S. Guder, Trans. Inst. Met. Finish. 87 (2009) 155158.
[3] A. Tozar, .H. Karahan, Appl. Surf. Sci. 318 (2014) 1523.
[4] Z.D. Wu, L. Fedrizzi, P.L. Bonora, Surf. Coat. Technol. 85 (1996) 170174.
[5] K.R. Sriraman, S. Brahimi, J.A. Szpunar, J.H. Osborned, S. Yue, Electrochim. Acta 105
(2013) 314323.
[6] P. Ganesan, S.P. Kumaraguru, B.N. Popov, Surf. Coat. Technol. 201 (2007)
78967904.
[7] R.M. Gnanamuthu, S. Mohan, G. Saravanan, C.W. Lee, J. Alloys Compd. 513 (2012)
449454.
[8] A. El Hajjami, M.P. Gigandet, M. De Petris-Wery, J.C. Catonne, J.J. Duprat, L. Thiery, F.
Raulin, N. Pommier, B. Starck, P. Remy, Appl. Surf. Sci. 254 (2007) 480489.
[9] Y. Boonyongmaneerat, S. Saenapitak, K. Saengkiettiyut, J. Alloys Compd. 487 (2009)
479482.
[10] O. Hammami, L. Dhouibi, E. Triki, Surf. Coat. Technol. 203 (2009) 28632870.

Please cite this article as: Z. Feng, et al., Surf. Coat. Technol. (2015), http://dx.doi.org/10.1016/j.surfcoat.2015.03.020

10
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]

Z. Feng et al. / Surface & Coatings Technology xxx (2015) xxxxxx

S.H. Mosavat, M.H. Shariat, M.E. Bahrololoom, Corros. Sci. 59 (2012) 8187.
E. Garca, M. Sarret, C. Mller, J. Electrochem. Soc. 149 (2002) C284C288.
K. Kondo, M. Yokoyama, K. Shinohara, J. Electrochem. Soc. 142 (1995) 22562260.
C. Mller, M. Sarret, M. Benballa, J. Electroanal. Chem. 519 (2002) 8592.
L.S. Tsybulskaya, T.V. Gaevskaya, O.G. Purovskaya, T.V. Byk, Surf. Coat. Technol. 203
(2008) 234239.
H. Conrad, J. Corbett, T.D. Goldenz, Electrochem. Soc. 159 (2012) C29C32.
X.W. Yang, M.Z. An, Y.W. Zhang, L. Zhang, Electrochim. Acta 58 (2011) 516522.
A.M. Liu, X.F. Ren, B. Wang, J. Zhang, P.X. Yang, J.Q. Zhang, M.Z. An, RSC. Adv. 4
(2014) 4093040940.
M. Ilayaraja, S. Mohan, R.M. Gnanamuthu, Trans. Inst. Met. Finish. 87 (2009)
145148.
A.M. Alfantazi, U. Erb, J. Mater. Sci. Lett. 15 (1996) 13611363.
R.M.A. Tehrani, S. Ab Ghani, J. Electrochem. Soc. 155 (2008) K199K204.
G.Y. Li, J.S. Lian, L.Y. Niu, Z.H. Jiang, Surf. Coat. Technol. 191 (2005) 5967.
S.H. Mosavat, M.E. Bahrololoom, M.H. Shariat, Appl. Surf. Sci. 257 (2011) 83118316.
I. Brooks, U. Erb, Scr. Mater. 44 (2001) 853858.
S. Ghaziof, W. Gao, Appl. Surf. Sci. 311 (2014) 635642.

[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]

J.B. Bajat, V.B. Mikovi-Stankovi, Prog. Org. Coat. 49 (2004) 183196.

C. Lupi, D. Pilone, Miner. Eng. 14 (2001) 14031410.
H.Y. Lee, S.G. Kim, Surf. Coat. Technol. 135 (2000) 6974.
A. Brenner, Electrodeposition of Alloys; Principles and Practice, Academic, New
York, 1963.
A. Gomes, M.I. da Silva Pereira, Electrochim. Acta 52 (2006) 863871.
G.Z. Pavlovich, R.G. Luthy, Water Res. 22 (1988) 327336.
S.S. Abd El Rehim, E.E. Fouad, S.M. Abd El Wahab, H.H. Hassan, Electrochim. Acta 41
(1996) 14131418.
M.G. Hosseini, H. Ashassi-Sorkhabi, H.A.Y. Ghiasvand, Surf. Coat. Technol. 202
(2008) 28972904.
M.M. Abou-Krisha, Appl. Surf. Sci. 252 (2005) 10351048.
S. Fashu, C.D. Gu, X.L. Wang, J.P. Tu, Surf. Coat. Technol. 242 (2014) 3441.
D.E. Hall, Surf. Finish. 70 (1983) 5965.
M.M. Abou-Krisha, Mater. Chem. Phys. 125 (2011) 621627.
A.M. El-Sherik, U. Erb, J. Page, Surf. Coat. Technol. 88 (1997) 7078.

Please cite this article as: Z. Feng, et al., Surf. Coat. Technol. (2015), http://dx.doi.org/10.1016/j.surfcoat.2015.03.020