ISIJ International, Vol. 62 (2022), No. 7, pp.

1522–1531
https://doi.org/10.2355/isijinternational.ISIJINT-2022-076

Effect of Solution Temperature on Electrodeposition Behavior of

Zn–Ni Alloy from Alkaline Zincate Solution

Sung Hwa BAE,1) Satoshi OUE,2) Yu-ki TANINOUCHI,2) Injoon SON3) and Hiroaki NAKANO2)*

1) Graduate School of Engineering, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka-shi, 819-0395 Japan.
2) Faculty of Engineering, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka-shi, 819-0395 Japan.
3) Department of Materials Science and Metallurgy, Kyungpook National University, 80 Daehak-ro, Sangyeok-dong, Buk-gu,
Daegu, 41566 Korea.
(Received on February 21, 2022; accepted on March 25, 2022; originally published in Tetsu-to-Hagané,
Vol. 108, 2022, No. 2, pp. 120–130)

Zn–Ni alloys were electrodeposited on a Cu electrode at 10–500 A·m − 2 and 5 × 104 C·m − 2 in an
unagitated zincate solution at 293, 313, and 333 K. The effect of solution temperature on the electrodepo-
sition behavior of Zn–Ni alloys from alkaline zincate solutions was investigated. The transition current
density at which the deposition behavior shifted from a normal to an anomalous co-deposition was almost
identical at 293 and 313 K but increased at 333 K, due to enhanced H2 evolution and Ni deposition at
333 K. The current efficiency for alloy deposition increased with solution temperature in both the normal
(10–50 A·m − 2) and anomalous (500 A·m − 2) co-deposition regions. In the normal co-deposition region, Ni
deposition and H2 evolution mainly occurred, and the current efficiency increased with solution tempera-
ture due to the stronger promotional effect of increase in solution temperature on Ni deposition. In the
anomalous co-deposition region at 500 A·m − 2, Zn deposition and H2 evolution mainly occurred, and Zn
deposition appeared to proceed based on a mixed rate-determining process comprising the charge trans-
fer and diffusion of Zn ions. The current efficiency increased with solution temperature due to the accel-
eration of the Zn ions diffusion. The Ni content in the deposited films increased with the solution tem-
perature at all the current densities, since Ni deposition was accelerated to a greater degree than Zn
deposition by increasing the solution temperature in the region where the charge transfer process was
rate-limiting. The γ-phase of the deposited films also increased with increasing solution temperature.

KEY WORDS: zincate; zinc–nickel alloy; electrodeposition; solution temperature; anomalous co-deposition;
polarization curve; current density; transition current; current efficiency; charge transfer.

over noble Ni in the practical current density range.9–15)

1. Introduction
Although the effect of current density,16–19) total concentra-
Zn electrodeposition has long been used to prevent the tion of metal ions,20) agitation of solution,19) concentration
corrosion of steel sheets, while Zn alloy electrodeposition of Ni complexing agent19) and solution composition17,19–21)
has been used to further improve the corrosion resistance of and the effect of current density18,20) on the current efficiency
the deposited films.1–8) Among Zn alloy depositions, Zn–Ni for alloy deposition were reported in Zn–Ni alloy deposition
alloy coatings are often applied on the various industrial from the zincate solutions, few studies on the deposition
fields such as automobile parts, and building materials, mechanism22) have been reported compared with those on
owing to their superior thermal stability and corrosion sulfate and chloride.
resistance. Zn–Ni alloys are usually deposited in a sulfate Solution temperature is known to affect the overpotential,
or chloride solution; however, considering the throwing throwing power, metal salt solubility, and solution con-
power on small parts, the use of a zincate solution is pref- ductivity.23) Increasing the solution temperature increases
erable. Zn–Ni alloy depositions from sulfate and chloride the diffusion coefficient of ions in solution and solubility
solutions have been studied a lot so far, and are known of the metal salt, as well as conductivity of the solution,
to lead to anomalous co-deposition behavior, in which the which consequently increases the diffusion-limiting cur-
electrochemically less-noble Zn is preferentially deposited rent density. In contrast, when the solution temperature is
decreased, the crystal grain of the deposits becomes finer,
* Corresponding author: E-mail: [email protected] and the throwing power is improved, based on the increases

© 2022 The Iron and Steel Institute of Japan. This is an open access article under the terms of the Creative Commons
Attribution-NonCommercial-NoDerivs license (https://creativecommons.org/licenses/by-nc-nd/4.0/).

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in the deposition overpotential. Thus, solution temperature films was observed by SEM, and the phase identification
is a highly important factor in electrodeposition. However, was carried out by XRD (Cu-Kα, tube voltage = 40 kV,
the effect of solution temperature on the deposition behavior tube current = 15 mA).
of the Zn–Ni alloys from zincate solutions has rarely been
reported.19) In the present study, this topic is discussed,
3. Results
based on the partial polarization curves of Zn and Ni deposi-
tions and H2 evolution. 3.1. Effect of Solution Temperature on the Deposition
Behavior of Zn–Ni Alloys
Figure 1 shows the total polarization curve of the Zn–
2. Experiment
Ni alloy deposition and the partial polarization curves of
Table 1 shows the zincate solution composition and elec- Zn and Ni depositions and H2 evolution. The equilibrium
trolysis conditions for the Zn–Ni alloy deposition. The elec- potential, EZneq, of the Zn deposition (ZnO22– + 2H2O + 2e–
trolytic solutions were prepared by dissolving reagent-grade →Zn + 4OH–) was –1.27 V, assuming pure Zn deposition.24)
ZnO (0.15 mol·dm − 3), NiSO4·6H2O (0.016 mol·dm − 3), The total polarization curve (Fig. 1(a)) rose in the nobler
N (CH2CH2OH)3 (0.34 mol·dm − 3), and NaOH (2.5 mol·dm − 3) potential region compared with the equilibrium potential of
in distilled and deionized water at room temperature. In Zn ( − 1.27 V), regardless of the solution temperature. Fur-
some experiments, the deposition behavior was investigated thermore, it significantly shifted to the less-noble potential
using a solution containing only Ni or Zn, eliminating the region when the current density exceeded 50–100 A·m − 2,
ZnO (0.15 mol·dm − 3) or NiSO4·6H2O (0.016 mol·dm − 3) and rose again when the potential reached the equilibrium
from the solution noted above. Electrodeposition was car- potential of Zn. At all the potential region nobler and less
ried out by the constant-current electrolysis method, without noble than the equilibrium potential of Zn, comparing the
stirring, at current densities of 10–500 A·m − 2, an amount of potential at the constant total current density, the potential
charge of 5 × 104 C·m–2, and solution temperatures of 293, shifted to noble direction with increasing solution tempera-
313, and 333 K. The amount of charge of 5 × 104 C·m–2 ture. At solution temperatures of 293 and 313 K, the current
corresponded to a film thickness of 2.37 μm, assuming the density range in which the cathode potential shifted signifi-
deposition of pure Zn at a current efficiency of 100%. A Cu cantly from the region nobler than the equilibrium potential
plate (1 × 2 cm) was used as the cathode and a Pt plate (1 × of Zn to the equilibrium potential was 50–100 A·m − 2. At
2 cm) as the anode, respectively. However, when preparing 333 K, it was as high as 100–200 A·m − 2.
samples for scanning electron microscopy (SEM) observa- The partial polarization curve of the Zn deposition (Fig.
tion and X-ray diffraction (XRD) analysis, an Fe plate (1 × 1(b)) rose in the nobler potential region than the equilib-
2 cm) was used as the cathode. The obtained electrodeposits rium potential of Zn, as with the total polarization curve,
were dissolved in HNO3, and Zn and Ni were quantified by regardless of the solution temperature. It then shifted to the
inductively coupled plasma-optical emission spectroscopy less-noble potential region, before sharply rising when it
(ICP-OES) to determine the composition of the deposited reached a potential less-noble region than the equilibrium
alloy and the current efficiency of the Zn and Ni depositions. potential of Zn ( − 1.27 V). In both potential regions, the
The current efficiency of the H2 evolution was calculated by partial polarization curve of the Zn deposition shifted to
subtracting the current efficiencies (%) of Zn and Ni from the noble direction as the solution temperature increased.
100, and the partial current densities of Zn and Ni deposi- For the Zn–Ni alloy deposition, the current density for Zn
tions and H2 evolution were calculated by multiplying the deposition was only slightly detected, even at approximately
total current density by the current efficiency (%)/100. The − 0.9 V, a value nobler than its equilibrium potential. Com-
partial current densities for Zn and Ni depositions and H2 paring the current density at a constant potential of –0.9 V,
evolution were calculated by multiplying the total current the current density of Zn deposition increased with increas-
density by their respective current efficiencies (%)/100. ing solution temperature.
The current efficiencies for Ni and Zn depositions from The equilibrium potential, ENieq for Ni deposition
the solution with only Ni or Zn were calculated using the (Ni(TEA)22 + +2e − →Ni + 2TEA) was –0.41 V. This was cal-
same method as for alloy deposition. An Ag/AgCl electrode culated by assuming that pure Ni had been deposited, based
(saturated KCl, 0.199 V vs. NHE, 298 K) was used as a on the complex stabilization constant K = 104.74,25) which
reference electrode to measure the polarization curve, but was formed by the coordination of two triethanolamine
the potential was converted to a standard hydrogen electrode molecules toward Ni2 + ions. Similar to the total polariza-
and displayed. The surface morphology of the deposited tion curve, the partial polarization curve of the Ni deposi-
tion (Fig. 1(c)) also rose in the potentially nobler region
compared with the equilibrium potential of Zn, regardless
Table 1. Solution compositions and electrolysis conditions.
of the solution temperature. It then shifted to the less-noble
ZnO (mol∙dm − 3) 0.15
Current density
10–500
potential region and rose again at potentials less noble than
(A∙m − 2) the equilibrium potential of Zn ( − 1.27 V). In both potential
NiSO4∙6H 2O (mol∙dm − 3) 0.016 Temperature (K) 293, 313, 333 regions, the partial polarization curve of the Ni deposition
Amount of charge shifted to nobler potential direction as the solution tempera-
N(CH2CH 2OH)3 (mol∙dm − 3) 0.34 5 × 104 ture increased.
(C∙m − 2)
NaOH (mol∙dm − 3) 2.5 Cathode Cu (1 × 2 cm 2) The H2 evolution in the Zn–Ni alloy solution (Fig. 1(d))
rose in the region nobler than the equilibrium potential of
Quiescent bath Anode Pt (1 × 2 cm 2)
Zn, decreased once (despite the shift in the potential to the

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negative direction), and increased again in the region that maximum at 250 A·m − 2. The current efficiency rarely
was less noble than the equilibrium potential of Zn. The decreased, even when the current density was increased to
partial polarization curve of the H2 evolution did not differ 500 A·m − 2. At solution temperatures of 293 and 313 K, the
significantly at solution temperatures of 293 and 313 K. In current efficiency of Zn deposition during alloy deposition
contrast, at 333 K, it was clearly depolarized (i.e., the elec- (Fig. 2(b)) was very low in the low-current density range
trode potential shifted to a nobler value when comparing of 10–50 A·m–2, and it was also very low in the range of
the electrode potential at a constant-current density), and 10–100 A·m–2 at 333 K. However, it increased sharply when
the current density at which the potential sharply shifted to the current density exceeded 50 and 100 A·m–2, respec-
the less-noble direction was higher than those measured at tively. The current efficiency of Ni deposition during alloy
293 and 313 K. deposition (Fig. 2(c)) also decreased with increasing current
Figure 2 shows the correlation between the current effi- density, regardless of the solution temperature. Furthermore,
ciency and current density for Zn–Ni, Zn, and Ni deposi- the current efficiency of Ni deposition was higher at higher
tions and H2 evolution during Zn–Ni alloy deposition at solution temperature. In the low-current density range of
different temperatures. The current efficiency of Zn–Ni alloy 10–50 A·m–2 at solution temperatures of 293 and 313 K,
deposition is the sum of the current efficiencies of Zn and and in the range of 10–100 A·m–2 at 333 K, H2 evolution
Ni depositions. As shown in Fig. 2(a), the current efficiency had the highest current efficiency (Fig. 2(d)), followed by
of the alloy deposition at a solution temperature of 293 K Ni deposition. However, in the high-current density range
was low, ranging from 14% to 26% in the low-current den- above 50–100 A·m–2, the current efficiency of Zn deposition
sity range of 10–50 A·m − 2. However, it sharply increased was the highest. Thus, the current efficiency of Zn–Ni alloy
when the current density exceeded 50 A·m − 2 and reached deposition reflected the current efficiency of Ni deposition
a maximum at 100 A·m − 2. It then decreased as the current in the low-current density region and that of Zn deposition
density further increased. A similar trend was observed at in the high-current density region.
313 K, although the current efficiency was slightly higher The current efficiency of Zn deposition (Fig. 2(b)) was
in the low and high-current density ranges of 10–50 A·m − 2 also compared with the total polarization curve shown in
and 500 A·m − 2, respectively. Contrastingly, at a solution Fig. 1(a). The range of 10–50 A·m–2 was nobler than the
temperature of 333 K, the current efficiency was low, rang- equilibrium potential of Zn at solution temperatures of 293
ing from 18% to 52% in the low-current density range of and 313 K, and the current efficiency of Zn deposition was
10–100 A·m − 2, although it significantly increased when thus considered as being low. When the current density
the current density exceeded 100 A·m − 2 and reached a exceeded 50 A·m − 2, the potential shifted to the less-noble

Fig. 1. Polarization curves for Zn–Ni alloy deposition at 293, 313 and 333 K [(a) Total polarization curves, partial polar-
ization curves of (b) Zn, (c) Ni and (d) H 2].

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Fig. 2. Current efficiencies for Zn–Ni alloy deposition at 293, 313 and 333 K [(a) Zn–Ni, (b) Zn, (c) Ni and (d) H 2].

Fig. 3. Ni contents in the Zn–Ni alloys deposited at various current densities from different temperatures. (b) Magnified
view of the area of 0–10 mass% of the Ni content.

region compared with the equilibrium potential of Zn rium potential of Zn to that of the equilibrium potential of
(Fig. 1(a)), therefore, the current efficiency of Zn seems to Zn in the total polarization curve. The decrease in the cur-
increase sharply. At a solution temperature of 333 K, the rent efficiency at 500 A·m − 2 at solution temperatures of 293
potential was nobler than the equilibrium potential of Zn and 313 K appeared to have been caused by the fact that the
in the range of 10–100 A·m − 2. However, when the cur- Zn deposition approached the diffusion limit of the Zn ions.
rent density exceeded 100 A·m − 2, the potential shifted to a Figure 3 shows the effect of the current density on the Ni
potential range less noble than the equilibrium potential of content of the Zn–Ni alloy films. The broken line (the com-
Zn (Fig. 1(a)), resulting in a sharp increase in the current positional reference line [CRL] of Ni) represents the Ni con-
efficiency of Zn. Thus, the current densities at which the tent in the deposits predicted from the concentration ratio of
current efficiency sharply changed, at all measured tempera- Ni ions against the total metal ions in the solution. When
tures, corresponded to those at which the cathode potential the Ni content in the deposited films exceeded the CRL,
changed from the potential region nobler than the equilib- a normal co-deposition occurred, with electrochemically

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noble Ni being preferentially deposited over Zn. In contrast, above 250 A·m − 2 at which the anomalous co-deposition
when the Ni content in the deposited films was lower than occurred (Fig. 3(b)).
the CRL, an anomalous co-deposition occurred, with base
Zn being deposited preferentially over Ni. As shown in Fig. 3.2. Effect of Solution Temperature on the Microstruc-
3, the Ni content in the deposited films altered significantly ture of Deposited Films
in the range of 50–100 A·m − 2 at solution temperatures of Figure 4 shows the X-ray diffraction patterns of the films
293 and 313 K. At current densities below 50 A·m − 2, the Ni obtained at various current densities from the solutions at
content in the deposited films was approximately 90 mass% different temperatures. Three main peaks were observed in
above the CRL, indicating the normal co-deposition, while the films obtained at 10 A·m–2 (Figs. 4(a)–4(c)). The dif-
at current densities above 100 A·m − 2, the Ni content in the fraction angles of the substrate Fe and α-Ni phases (solid
deposited films was below the CRL, indicating the anoma- solution of Zn in the Ni) overlapped at 44.7°, making it
lous co-deposition. In contrast, at 333 K, the Ni content in difficult to identify the α-phase. Therefore, we investigated
the deposited films was significantly altered in the region the XRD pattern of the substrate Fe only and confirmed
from 100 to 250 A·m − 2. Below 100 A·m − 2, the Ni content that the peak intensity at a diffraction angle of 44.7° was
in the deposited films was above the CRL, indicating the smaller than that at 65.0°. However, it was larger than that
normal co-deposition. Above 250 A·m − 2, the Ni content at 65.0° for the deposited film obtained at 10 A·m–2, regard-
in the deposited films was below the CRL, indicating the less of the solution temperature; it was thus concluded that
anomalous co-deposition. The current density at which the the α-phase existed in all the deposited films. Weak peaks
deposition behavior shifts from normal to anomalous is indicating the presence of the α-phase were also detected
called the transition current density.26–28) At all the solution at diffraction angles other than 44.7° in the deposited films
temperatures, the transition current density corresponded obtained at 333 K. The deposition at 10 A·m − 2 exhibited the
to the current density at which the potential of the total normal co-deposition, regardless of the solution tempera-
polarization curve shown in Fig. 1(a) abruptly shifted to ture, and the Ni content in the deposited films was above
the less-noble potential region, or to the current density 90 mass%. As a result, only the α-phase was thought to
at which the current efficiency significantly changed (Fig. be detected. No peaks related to Zn, obtained by underpo-
2(b)). As described above, the transition current density at tential co-deposition, were detected. In the deposited films
293 K was almost identical to that at 313 K, although it was obtained at 100 A·m − 2, the η-phase (solid solution of Ni in
higher at 333 K. The Ni content in the films increased with the Zn) and γ-phase (intermetallic compound Ni2Zn11), were
increasing solution temperature in the low-current density detected at solution temperatures of 293 and 313 K (Figs.
range, where the normal co-deposition was observed. The 4(d) and 4(e)), whereas only peaks of the α-phase and Fe
Ni content in the deposited films also increased slightly with were detected at 333 K (Fig. 4(f)). At 100 A·m − 2, the depo-
increasing solution temperature in the current density range sition behavior differed significantly, based on the solution

Fig. 4. X-ray diffraction patterns of the Zn–Ni alloy films deposited at various current densities from different tempera-
tures (▲ Ni[α] PDF # 87-0712, ○ Fe PDF # 65-4899, ● Zn[η] PDF # 87-0713, and ★ Ni2Zn11[γ] PDF # 65-5310).

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temperature. In particular, the depositions at 293 and 313 K to that of the deposited films obtained at 10 A·m − 2 (Fig.
exhibited the anomalous co-deposition, resulting in a high 5(f)). As noted above, for the deposition at 100 A·m − 2, an
Zn content (approximately 93 mass%) in the films, while anomalous co-deposition was observed at 293 and 313 K,
the deposition at 333 K exhibited the normal co-deposition, and the deposited films with approximately 7 mass% of Ni
resulting in a high Ni content (approximately 87.4 mass%; content in deposits comprised η and γ-phases, while a nor-
Fig. 3). The XRD patterns of the deposited films obtained mal co-deposition was observed at 333 K, and the deposited
at 100 A·m − 2 reflected this same deposition behavior. In films with 87.4 mass% of Ni content in deposits comprised
contrast, the η- and γ-phases were detected in the depos- an α-phase. The surface morphology of the films obtained
ited films obtained at 500 A·m − 2 (Figs. 4(g)–4(i)), and the at 100 A·m − 2 seems to reflect the phase structure noted
formation of the γ-phase was dominant at higher solution above. In contrast, that of the films obtained at 500 A·m − 2
temperatures. Since the Ni content in the deposited films where an anomalous co-deposition was observed at all the
increased with increasing solution temperature (Fig. 3(b)), temperatures, exhibited the plate-like crystal characteristics
the formation of the γ-phase seems to become easy with of the η-phase at a solution temperature of 293 K (Fig.
increasing temperature. At 100 A·m–2, the main peak of the 5(g)). However, this plate-like structure disappeared with
γ-phase was higher at 313 K than at 293 K, indicating that increasing solution temperatures (Fig. 5(i)), and a smooth
the γ-phase had increased with temperature. These results surface was observed. The films deposited at 500 A·m − 2
indicated that the γ-phase increased with increasing solution comprised η and γ-phases, and the γ-phase became domi-
temperature in the case of the anomalous co-deposition of nant with increasing solution temperature, as a result, the
deposited films with a high Zn content. surface morphology seems to change.
Figure 5 shows the SEM images of the deposited films
obtained from the solutions at different temperatures and
4. Discussion
current densities. The films deposited at 10 A·m − 2 were
smooth at 293 K (Fig. 5(a)) but became slightly coarse The effect of solution temperature on the deposition
at higher solution temperatures (Figs. 5(b) and 5(c)). The behavior of the Zn–Ni alloys from alkaline zincate solutions
films obtained at 10 A·m − 2 comprised the α-phase and was investigated. The transition current density at which
had an Ni content of greater than 90 mass% at all the solu- the deposition behavior shifted from the normal to anoma-
tion temperatures, while the grain size was thought to be lous, the current efficiency of the alloy deposition, and the
increased as the solution temperature increased, due to a composition of the deposited films changed depending on
decrease in the overpotential for deposition. In the films the solution temperature. The reasons for these effects are
deposited at 100 A·m–2, the agglomerations consisting of discussed as follows.
fine crystals were observed at 293 and 313 K (Figs. 5(d) The partial polarization curve of Ni deposition in the
and 5(e)), while at 333 K, the morphology was similar alloy deposition (Fig. 1(c)) is first explained. This partial

Fig. 5. SEM images of the surface of the Zn–Ni alloys deposited at various current densities from different tempera-
tures.

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polarization curve rose at approximately –0.9 V, regardless was Zn(OH)2, which was formed by the hydrolysis of Zn2 +
of the solution temperature, which was a nobler value than ions.34) However, no hydrolysis reaction of the Zn2 + ions
the equilibrium potential of Zn, and then sharply shifted to occurs in zincate solutions. Generally, Zn deposition from
a less noble potential region (Fig. 1(c)). The partial current a zincate solution has been reported to proceed by the mul-
density at which the cathode potential changed sharply to tistep reactions shown in Eqs. (3)–(5),35–37)
a less noble potential region was similar to the diffusion-
Zn ( OH )4 → Zn ( OH )3 + OH − ................ (3)
2− −
limiting current density of the Ni deposition. However, if
this current density was assumed as the diffusion-limiting
Zn ( OH )3 → Zn ( OH )2 + OH − .................. (4)
−
current density of Ni, the Ni content of the deposited films
would be above the CRL in the entire current density
Zn ( OH )2 + 2e → Zn + 2OH − ................... (5)
range,29–31) which would contradict the results of the present
study. In fact, it has been reported that in the normal type In Zn–Ni alloy deposition from a zincate solution, the
deposition, the deposition of the noble metal becomes the Zn(OH)2 formed during the multistep reactions is thought
diffusion-limiting current density, and the content of the to act as an inhibitor for the H2 evolution and Ni deposi-
noble metal in the films will be above the CRL in all the tion. In this study, the current density for H2 evolution
current density range.29–31) In the present study, the partial from the Zn–Ni alloy solution decreased once, despite
current density of Ni deposition at which the cathode poten- a shift in the potential to the less noble direction in the
tial changed sharply to a less noble potential region shown region that was nobler than the equilibrium potential of Zn
in Fig. 1(c) was not the diffusion-limiting current density (Fig. 1(d)); this was attributed to suppression by Zn(OH)2,
because the anomalous co-deposition was observed in the formed through the multistep reactions of Zn deposition.
high-current density region. The transition current densities at solution temperatures of
It was reported that the transition current density in Zn– 293 and 313 K were almost identical but they significantly
Ni alloy deposition from a sulfate solution corresponded increased at 333 K (Fig. 1(a)). Focusing on the effect of
to the current density that generated the overpotential for solution temperature on the partial current densities of Zn
the H2 evolution ηHInh; this is represented by Eq. (1) as and Ni depositions and H2 evolution in the transition current
follows:32–34) density region, it was found that the partial current densities
of the H2 evolution and Ni deposition were almost identi-
EH eq − ηH 0 − ηH Inh = EZn eq ...................... (1) cal at solution temperatures of 293 and 313 K but clearly
Here, EHeq and EZneq denote the equilibrium potentials increased at 333 K (Figs. 1(b)–1(d)). That is, because the
for H2 evolution and Zn deposition, respectively; ηH0 is H2 evolution and Ni deposition were promoted at 333 K,
the minimum overpotential for H2 evolution, and ηHInh is the current density that was required to complete Eqs. (1)
the overpotential for H2 evolution in the presence of its and (2), i.e., the transition current density, seems to increase
inhibitor. In the case of Zn deposition from an acidic solu- with solution temperature.
tion, the reaction intermediate Zn(OH)2 will be formed by In Zn–Ni alloy deposition, a competition reaction between
hydrolysis of the Zn2 + ions (Zn2 + +2H2O→Zn(OH)2 + 2H + ), the Zn and Ni depositions and H2 evolution occurs. Hence,
caused by the increase in pH due to H2 evolution reaction deposition was performed with solutions including only Ni
(2H + +2e − →H2) at the cathode layer. This Zn(OH)2 appears or Zn to compare the effect of the solution temperature on
to create the overpotential for H2 evolution, i.e., ηHInh.32–34) each reaction. Figure 6 shows the effect of solution tem-
In Zn–Ni alloy deposition from a sulfate solution, Ni deposi- perature on the partial polarization curve for Ni deposition
tion is suppressed by Zn(OH)2 and becomes almost zero in and H2 evolution for the Ni solution. Both Ni deposition
the normal co-deposition region, resulting in H2 evolution
only.26) Therefore, to complete Eq. (1), the transition cur-
rent density is defined as the H2 evolution current density
that is required to generate the overpotential, i.e., ηHInh.32–34)
However, in Zn–Ni alloy deposition from zincate solutions,
Zn and Ni are deposited in the region of the normal co-
deposition at potentials nobler than the equilibrium potential
of Zn (Figs. 1(b), 1(c)), and the potential of Ni deposition
shifts significantly to the equilibrium potential of Zn at the
transition current density. Therefore, the transition current
density in the zincate solution is considered to be the sum
of the current densities of the H2 evolution and Zn and Ni
depositions required to satisfy both Eqs. (1) and (2).
ENi eq − ηNi 0 − ηNi Inh = EZn eq ..................... (2)
Here, ENieq denotes the equilibrium potential for Ni deposi-
tion, ηNi0 is the minimum overpotential for Ni deposition,
and ηNiIn is the overpotential for Ni deposition in the pres-
ence of its inhibitor. Fig. 6. Partial polarization curves for Ni deposition and H2 evolu-
It was reported that the inhibitor of H2 evolution and Ni tion from the Ni only alkaline solutions at 293, 313 and
deposition in Zn–Ni alloy deposition from acidic solutions 333 K.

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and H2 evolution were depolarized with increasing solution increase in solution temperature had a stronger effect on
temperature. At a partial current density of 3 A·m–2 for Ni H2 evolution. Comparing the effects of solution tempera-
deposition, the potential shifted to the noble direction by ture on the Zn and Ni depositions and H2 evolution (Figs.
approximately 0.2 V, when the solution temperature was 6–9), in the low-current density range, where the charge
raised from 293 to 333 K. At a partial current density of transfer process was rate-limiting, the degree of promotion
100 A·m–2 for H2 evolution, the potential shifted by approxi- with increasing solution temperature followed the order Ni
mately 0.06 V with increasing solution temperature, and the deposition > H2 evolution > Zn deposition. Zinc deposi-
degree of depolarization was greater for Ni deposition. Here tion from an aqueous solution is known to occur in the case
the overpotential for metal deposition, i.e., ηM, is defined by where there is a small overpotential for deposition, whereas
the following equation: Ni deposition and H2 evolution occur when there is a large
overpotential for deposition since they proceed in the mul-
ηM = EM eq − EM ............................. (6)
tistep reactions via adsorption intermediates NiOHad and
where EMeq is the equilibrium potential of metal deposi- Had, respectively and slow elementary process is present. As
tion, and EM is the electrode potential for metal deposition. shown in Figs. 6 and 8, the overpotential for Zn deposition
Comparing the overpotential for Ni deposition with that for was small, even from the zincate solution, while that for Ni
H2 evolution, the one for Ni deposition was larger. Figure deposition was large. Since Ni deposition and H2 evolution
7 shows the effect of solution temperature on the current had an inherently large overpotential, the promotional effect
efficiency of Ni deposition from the Ni solution. The cur- of increasing the solution temperature on the Ni deposi-
rent efficiency for Ni deposition increased with increasing tion and H2 evolution appeared to have been stronger than
solution temperature at all current densities. Particularly, in that on the Zn deposition. In the deposition from the Ni
the low-current-density region of 10–20 A·m–2, the current solution, the promotional effect of increasing the solution
efficiency for Ni deposition significantly increased with
solution temperature. Based on Figs. 6 and 7, it was found
that both Ni deposition and H2 evolution were promoted
with increasing solution temperature, while an increase in
solution temperature had a stronger promotional effect on
the Ni deposition.
Figure 8 shows the effect of solution temperature on the
partial polarization curve for Zn deposition from the Zn
solution. The partial polarization curves for Zn deposition
depolarized with increasing solution temperature. At 313
and 333 K, the Zn began to deposit near its equilibrium
potential, indicating that the deposition overpotential was
small. At a solution temperature of 293 K, the Zn depo-
sition approached the diffusion limitation of Zn ions at
approximately − 1.6 V. Figure 9 shows the effect of solution
temperature on the current efficiency of Zn deposition from
the Zn solution. In the low-current-density range of 10–20
A·m − 2, the current efficiency for Zn deposition decreased
with increasing solution temperature, indicating that an Fig. 8. Partial polarization curve for Zn deposition from Zn only
alkaline solutions at 293, 313 and 333 K.

Fig. 7. Current efficiencies for Ni deposition from Ni only alka- Fig. 9. Current efficiencies for Zn deposition from Zn only alka-
line solutions at 293, 313 and 333 K. line solutions at 293, 313 and 333 K.

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 ISIJ International, Vol. 62 (2022), No. 7

temperature on the Ni deposition was larger than that on perature in the region where the charge transfer process was
the H2 evolution, which was attributed to the fact that the rate-limiting, the Ni content in the deposited films seems to
overpotential for Ni deposition was larger than that for H2 increase with solution temperature in both the normal and
evolution on Ni. Contrastingly, in the high-current density anomalous co-deposition regions.
region of 500 A·m − 2, the current efficiency for Zn deposi- As shown in Fig. 1(b), in the Zn–Ni alloy deposition,
tion increased with increasing solution temperature (Fig. 9). the Zn appeared to have been deposited in a potential
Since the diffusion of Zn ions became the rate-limiting step region nobler than its equilibrium potential, whereas this
of the Zn deposition in the high-current density region, the phenomenon was not observed in the deposition from a
current efficiency for Zn deposition seems to increase with single Zn solution (Fig. 8). It was reported that Zn–Ni alloy
increasing solution temperature due to the promotion of Zn deposition in the potential range nobler than the equilibrium
ion diffusion. potential of Zn had been caused by the formation of a stable
The effect of solution temperature on the current effi- intermetallic compound, Ni5Zn21, through deposition, which
ciency for alloy deposition and the composition of the considerably reduced the activity coefficient of the Zn in
deposited films will be discussed next, based on the results the deposited films.42–44) That is, the co-deposition of Ni is
for the solutions that included only Ni or Zn noted above. essential for the Zn apparently depositing in the potential
First, the current efficiency for alloy deposition increased region nobler than its equilibrium potential. In the present
with increasing solution temperature in both the normal study, the deposition of Zn in the noble potential region is
(10–50 A·m − 2) and anomalous (500 A·m − 2) co-deposition thought to be increased with temperature because the depo-
regions (Fig. 2(a)). In the normal co-deposition region, the sition of Ni was accelerated at a higher solution temperature.
Ni content of the deposited films was approximately 90 Finally, we discuss the difference between the deposition
mass%, revealing that the competition reaction between Ni behavior of the Zn–Ni alloy from the zincate solution in this
deposition and H2 evolution mainly occurred in this region. study and that from a sulfate solution previously reported.
Ni deposition and H2 evolution were both promoted with The most important difference between the deposition from
increasing solution temperature, but the promotional effect zincate and sulfate solutions was the cause of Zn(OH)2
on the Ni deposition was stronger, as determined from formation, which is an inhibitor of Ni deposition and H2
the results for the Ni solution (Figs. 6 and 7). As a result, evolution. In sulfate solutions, Zn(OH)2 is formed by the
the current efficiency for alloy deposition increased with hydrolysis of Zn2 + due to the increase of solution pH by the
increasing solution temperature. In the normal co-deposition reduction of H + at the cathode. In contrast, in the zincate
region of 10–50 A·m − 2, the current efficiency for alloy solution, it is thought to be formed in the intermediate stage
deposition decreased with increasing current density at all of the multistep Zn deposition reactions. In the case of alloy
solution temperatures. This was attributed to increase in the deposition from sulfate solutions, it was reported that the Ni
formation rate of Zn(OH)2 in the multistep reactions of Zn content in the deposited films was approximately 10 mass%
deposition, caused by increasing the current density and the in the region where an anomalous-type co-deposition
suppression of Ni deposition by Zn(OH)2. Contrastingly, in occurred, which was much lower than the CRL (50 mass%
the anomalous co-deposition region at 500 A·m − 2, the Ni Ni2 + content in the solution).29) In the case of the present
content in the deposited films was approximately 5 mass%, study, the Ni content in the deposited films from the zincate
revealing that the competition reaction between Zn deposi- solution was approximately 5–8 mass% in the region where
tion and H2 evolution occurred mainly in this region. The the anomalous co-deposition occurred (Fig. 3), which was
Zn deposition in this region appeared to proceed under a below the CRL (8.7 mass%). However, the anomalies were
mixed rate-determining process that included the charge greater in the sulfate solution than in the zincate solution
transfer and diffusion of Zn ions (Fig. 1(b)). The diffusion of (Fig. 3), indicating that the suppression of Ni deposition
Zn ions was promoted with increasing solution temperature, by Zn(OH)2 was stronger. The difference in the degree of
resulting in an increase in the current efficiency of the alloy Ni deposition suppression between the sulfate and zinc-
deposition. Comparing the current efficiency of Ni deposi- ate solutions may have been due to difference in cause of
tion from the alloy solution and the single Ni solution, that Zn(OH)2 formation. In the sulfate solution, the Ni content in
from the alloy solution was observably higher (Figs. 2(c) the deposited films increased from approximately 10 mass%
and 7). This suggested that the formation of Zn(OH)2 in to approximately 25 mass% as the solution temperature
the alloy solution suppressed both the H2 evolution and increased from 303 to 333 K.39) However, the increase in
Ni deposition but that the H2 evolution was more strongly Ni content may be larger than that in the zincate solutions
suppressed. (Fig. 3) because the inhibitory effect of Zn(OH)2 on the Ni
The Ni content in the deposited films increased with deposition is stronger in the sulfate solution.
increasing solution temperature in both the normal (10–50
A·m − 2) and anomalous (250–500 A·m − 2) co-deposition
5. Conclusion
regions (Fig. 3). The Zn and Ni depositions in the alloy
deposition appeared to proceed under a rate-determining The effect of solution temperature on the deposition
process comprising the charge transfer in the normal co- behavior of Zn–Ni alloys from alkaline zincate solutions
deposition region, while they appeared to follow a mixed was investigated. The transition current density at which the
rate-determining process comprising the charge transfer deposition behavior shifted from the normal to anomalous
and diffusion of Zn2 + ions in the anomalous co-deposition co-deposition was almost identical at solution temperatures
region. Since Ni deposition was promoted to a greater of 293 and 313 K but clearly increased at 333 K. The transi-
degree than Zn deposition by increasing the solution tem- tion current density appeared to increase due to the enhance-

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 ISIJ International, Vol. 62 (2022), No. 7

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