ISIJ International, Vol. 48 (2008), No. 4, pp.

506–511

Electrodeposition of Composites of Zinc with Vanadium Oxide

from Sulfate Solutions

Hiroaki NAKANO,1) Satoshi OUE,1) Daisuke KOZAKI,2) Shigeo KOBAYASHI3) and Hisaaki FUKUSHIMA1)

1) Faculty of Engineering, Kyushu University, 744, Motooka, Nishi-ku, Fukuoka 819-0395 Japan.
2) Formerly Graduate School of Engineering, Kyushu University. Now Kawasaki Heavy Industries, Ltd., 3-1-1, Higashi-
kawasaki-cho, Chuo-ku, Kobe 105-6116 Japan. 3) Faculty of Engineering, Kyushu Sangyo University, 2-3-1,
Matsukadai, Higashi-ku, Fukuoka 813-8503 Japan.
(Received on November 14, 2007; accepted on January 8, 2008; originally published in Tetsu-to-
Hagané, 93, 2007, pp. 703–708 )

Electrodeposition of Zn with V was examined from optionally agitated sulfate solutions containing Zn2
and VO2 at pH 0–3 and 40°C under galvanostatic conditions. XPS spectra of the deposits showed that V
was present in the deposited Zn in the form of its oxide, formed by hydrolysis of V ions. The V content of
the deposits increased with increasing pH of the solution and increasing current density. These conditions
appear to accelerate the hydrolysis of V ions by means of an increase in hydrogen evolution in the cathode
layer. SEM and EPMA studies of the deposits showed that the V in the deposits was segregated at the
edges of layered platelet crystals of Zn. Agitation of the electrolyte decreased the V content of the deposits
but reduced the segregation of V oxide. Anodic polarization curves for dissolution of Zn in 3 % NaCl solution
were polarized by codeposition of V oxide with Zn for V contents of 5 mass%. The corrosion current den-
sities of deposits obtained from agitated solutions were smaller than those from un-agitated solutions.
KEY WORDS: electrodeposition; Zn with V; hydrolysis; polarization curve.

VO2, which hydrolyzes at a lower pH than Zn2, was

1. Introduction
added to the electrolyte to investigate the deposition behav-
Steel sheets are coated with zinc by hot-dip galvanization ior of the composite of Zn and V oxide, and the effect of
or electroplating processes. The electroplating technique the current density, pH, agitation, and addition of a quater-
has been used to produce coatings of pure Zn and Zn–Ni nary ammonium salt surfactant on the codeposition behav-
alloy on steel sheets, and plating with Zn–Cr alloy1–3) has ior of V was examined. The chemical state of each element
also been studied because of its high resistance to corro- codeposited with Zn and the structure and polarization
sion. In the future, when designing highly corrosion-resist- properties of the composite of Zn and V oxide were also
ant Zn alloy films, it will be necessary to avoid substances studied.
that are harmful to the environment and metals that are
more noble than Fe, which are difficult to recycle. Investi-
2. Experimental
gations of Zn alloy films produced by hot-dip galvanization
and dry-process coating have shown that the alloying ele- Table 1 shows the solution composition and electroly-
ments less noble than Zn, such as Mg, Al, or Ti, improve sis conditions. The electrolytic solution was prepared by
the corrosion resistance of Zn alloy films.4–13) These less- dissolving fixed amounts of high-grade ZnSO4 · 7H2O
noble metals are naturally present in rocks and cannot (0.52 mol/L) and VOSO4 · 5H2O (0.79 mol/L) in distilled,
therefore be regarded as environmental pollutants. V (the deionized water. In some experiments, Benzyl(dimethyl)-
standard single-electrode potential E 0
1.186 V vs. NHE) (stearyl)ammonium chloride [C6H5CH2N(CH3)2C18H37Cl;
is a considerably less noble metal than Zn (E 0
0.76 V),
Table 1. Electrolysis conditions.
and therefore expected to improve the corrosion resistance
of Zn alloy films. There have, however, been very few stud-
ies so far on the codeposition of V with Zn.
In electrodeposition of a less-noble metal such as Zn, the
pH in the cathode layer generally increases as a result of the
evolution of hydrogen. Therefore, when metal ions that hy-
drolyze at low pH values are added to the electrolyte as a
secondary element, these metal ions could codeposit with
Zn in an oxidized state as a result of the hydrolysis
reaction.14)

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 ISIJ International, Vol. 48 (2008), No. 4

hereafter simply referred to as C18-Benzyl] was added

to the solution as an organic additive in amounts of
0.5–50 mmol/L. The pH was adjusted to 0–3 (standard: 2)
with sulfuric acid. The electrodeposition was conducted in
un-agitated solutions under coulostatic (5105 C/m2) and
galvanostatic conditions of 100–8 000 A/m2 at 40°C. In
some experiments, the electrodeposition was performed in
solutions agitated at 400 rpm by stirrer to examine the ef-
fects of agitation on the codeposition of V with Zn. Sheets
of copper and platinum measuring 12 cm2 were used as
cathodes and anodes, respectively. Because VO2 is oxi-
dized to V2O5 on a platinum anode during electrolysis, the
electrolysis was performed in a H-section cell in which the
catholyte was separated from the anolyte by sintered glass.
The deposits were dissolved from the cathode by nitric
acid. Both Zn and V were quantitatively analyzed by induc-
tively coupled plasma spectroscopy (ICP), and the V con- Fig. 1. Potential–pH diagram for V–H2O system at 25°C
(aV
0.8).
tent of the deposit, the cathode current efficiency and the
partial current density for Zn deposition were calculated.
The cathode potentials during deposition were measured
against a saturated Ag/AgCl reference electrode (0.199 V
vs. NHE, 25°C). In the presentation of the polarization
curves, the potentials are plotted with reference to the
NHE.
The chemical state of Zn and V in the deposits was in-
vestigated by X-ray photoelectron spectroscopy (XPS) after
sputtering for 2–9 min with Ar gas. The morphology of the
deposits was observed by SEM, and the distribution of Zn
and V was visualized by EPMA. The crystal orientation of Fig. 2. Effect of current density and pH on the V content in de-
the deposited Zn was determined by applying the method of posit and the current efficiency for Zn deposition.
Willson and Rogers15) to the X-ray diffraction intensity of
the (0002) to (112̄2) planes. The polarization curves from activity coefficient of V ion becomes less than 1.0 due to
the less-noble to the more-noble direction were obtained by the high concentration of the electrolyte; consequently, the
using a potential sweep rate of 1.0 mV s1 in an oxygen-sat- critical pH values for hydrolysis of VO2 and V3 increase
urated 3% NaCl solution at 40°C. The corrosion current to above 3.0.
density and the corrosion potential of deposits were calcu-
lated by a Tafel plot extrapolation method. 3.2. Codeposition Behavior of Vanadium
Figure 2 shows the effects of current density and pH on
the V content in deposits and the current efficiency for Zn
3. Results and Discussion
deposition. The V content in deposits in this study was cal-
3.1. Chemical State and Equilibrium Potential of culated from the masses of V and Zn in the deposits by
Vanadium using the following equation.
Figure 1 shows the potential vs. pH diagram for the
V content
[mass V/total mass (ZnV)]100
V–H2O system. The concentration of V in the solution and
the activity coefficient of V ion are assumed to be 0.8 mol/L The V content in the deposits increased with increasing
and 1, respectively. The thermodynamic data are quoted current density and pH in solutions of pH 1–3. However, no
from Paurbaix.16) As can be seen from Fig. 1, V exists in elemental V codeposited with Zn in the solution of pH 0,
the form of VO2 in the electrolyte of pH 2. When the elec- despite an increase in the current density to 3 000 A/m2.
trode potential is shifted to the less-noble direction, V3 The current efficiency for Zn deposition increased with in-
and V2 become stable. On further polarizing the electrode creasing current density, and became maximal at about
potential, the most stable chemical state becomes metallic 1 000 A/m2 in solutions of pH 1–3.
V at potentials less noble than 1.178 V. On the other hand, Figure 3 shows the XPS spectra of V and Zn in the de-
at pH values above 2.38 and 2.50, V2O4 and V2O3 are posit with V content 20 mass%, obtained at 3 000 A/m2
formed as a result of hydrolytic reactions of VO2 and V3, from a solution containing Zn2 and VO2 of pH 1. The
respectively. In the electrodeposition of Zn from aqueous peak (a) resulting from V in the XPS profile corresponds
solution, the pH in the cathode layer increases as a result of with that of V2O3, showing that the V is present in the de-
the evolution of hydrogen. When the pH in the cathode posits in its oxidic form. It can be presumed that the VO2
layer reaches the critical pH value for the hydrolysis of V in the solution is initially electrochemically reduced to V3,
ions, V ions are expected to be converted into oxides such which subsequently undergoes hydrolysis to form V2O3. On
as V2O4 and V2O3. However, no precipitation was observed the other hand, the XPS peaks (b) resulting from Zn corre-
in electrolytes of pH 3 in this study. It is assumed that the sponds with those of Zn and ZnO, showing that Zn is pres-

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 ISIJ International, Vol. 48 (2008), No. 4
Fig. 3. XPS spectra of V and Zn in deposit obtained at
3 000 A/m2 from the solution of pH 1 (V content in de-
posit: 20 mass%).
Fig. 4. Total polarization curves measured in the Zn–V plating
solutions of various pH.
ent mainly in its metallic form, except at the surface of the
deposits. In electrodeposition of Zn from aqueous solution,
the pH in the cathode layer rises as a result of the evolution
of hydrogen. The increase in the V content in deposits with
increasing current density and pH, as shown in Fig. 2, is as-
cribed to an increase in the hydrolysis reaction of V ions
due to the pH in the cathode layer with increased current
density and pH.
Figure 4 shows the total polarization curves measured in
solutions containing Zn2 and VO2 at various pH values.
The total polarization curve in the VO2-free solution was
also measured to elucidate the effect of VO2 on the depo-
sition behavior of composites of Zn and V oxide. The total
polarization curve was shifted to the more-noble direction
in the solution of pH 0, but there was little difference in the
polarization curves for solutions of pH 1–3. The depolar-
ization in the solution of pH 0 seems to be due to evolution
of hydrogen or, possibly, to reduction of VO2 to V3 and
V2. The total polarization curve was more polarized in the
VO2-contaning solution than in the VO2-free solution.
This polarization in the presence of VO2 appears to result
from an increase in resistance overpotential caused by V
oxide films formed by hydrolysis of V ions on the cathode.
Figure 5 shows the partial polarization curves for depo-
sition of Zn from solutions of various pH values containing
Zn2 and VO2. The partial polarization curve of Zn was
more polarized in the solution containing VO2 than in the
VO2-free solution, as was the case for the total polariza-
tion curve shown in Fig. 4. The pH had little effect on the
partial polarization curve for Zn deposition.
© 2008 ISIJ
Fig. 5. Partial polarization curves for Zn deposition in the Zn–V
plating solutions of various pH.
Fig. 6. Effect of additive surfactant on the V content in deposit
and the current efficiency for Zn deposition.
Zn deposited partially in the form of ZnO, as shown in
Fig. 3. In Zn electrodeposition, Zn(OH)2 is formed on the
cathode by hydrolysis of Zn2 due to the increase in pH in
the cathode layer caused by evolution of hydrogen. Zn dep-
osition is reported to proceed through Zn(OH)2 adsorbed
on the cathode.17,18) It was assume that the reduction of
Zn(OH)2 to Zn was suppressed by the resistance of the V
oxide films formed on the cathode in the solution contain-
ing VO2. Consequently, un-reduced Zn(OH)2 seems to re-
main on the cathode, resulting in the presence of Zn oxide
in the deposits.
It has been reported that Mg and Al codeposit with Zn
during the electrodeposition of composites of Zn with Mg
oxide or Al oxide from sulfate solutions containing C18-
Benzyl.14,19) Therefore electrodeposition was conducted in
solutions containing Zn2, VO2, and C18-Benzyl. Figure
6 shows the current density dependence of the V content in
deposits and the cathode current efficiency for deposition of
Zn from the solutions containing C18-Benzyl. The V con-
tent in deposits increased by addition of C18-Benzyl. The
V content in deposits was high, even at a low current den-
sity of 100 A/m2, particularly at concentrations of C18-Ben-
zyl of more than 5 mmol/L. The V content in deposits in-
creased with increasing current density, except for the solu-
tion containing 50 mmol/L of C18-Benzyl. On the other
hand, the current efficiency for Zn deposition decreased
with increasing concentration of C18-Benzyl in solution.
The current efficiency of Zn increased with increasing cur-
rent density in the solution containing 0.5 mmol/L of C18-
Benzyl, whereas the current efficiency was maximal at
300 A/m2 and decreased with increasing current density in
solutions containing C18-Benzyl in concentrations of more
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 ISIJ International, Vol. 48 (2008), No. 4

than 5 mmol/L. C18-Benzyl is reported to greatly polarize

the cathode potential for Zn deposition.14,19) The evolution
of hydrogen is promoted as a result of the electrolysis of the
solvent H2O at potentials less noble than 1.0 V vs.
NHE.19) Consequently, the hydrolysis of V ions appears to
be accelerated, resulting in an increase in the V content of
the deposits.

3.3. Structure of the Deposits

Figure 7 shows SEM images of deposits with V contents
of 4.8 and 19.9 mass% obtained at 300 and 2 000 A/m2 Fig. 7. SEM images of deposits obtained at 300 A/m2 (a) and
from a solution of pH 2. The deposit with a V content of 2 000 A/m2 (b) from the solution of pH 2.
4.8 mass% (a) consisted of layered hexagonal Zn platelet
crystals with white deposits on their edges, whereas the de-
posit with a V content of 19.9 mass% (b) showed blocks of
granular crystals at the boundaries of the Zn platelet crys-
tals.
Figure 8 shows the EPMA images of the deposit with a
V content of 4.8 mass%. The back-electron image (a) and
the characteristic X-ray image of V (c) show that V is seg-
regated at the boundaries of Zn platelet crystals. Segrega-
tion of oxygen (d) was also observed, and its position coin-
cided with the position of segregated V, showing that V
codeposited in its oxide form with Zn. Accordingly, the
white deposits on the edges of Zn platelet crystals shown in
Fig. 7(a) consist of V oxide.
Figure 9 shows the EPMA images of the deposit with a
V content of 19.9 mass%. The characteristic X-ray images
of Zn (b) and V (c) show that the V concentration was high
in areas of low Zn concentration: in other words, the V and Fig. 8. EPMA images of Zn–4.8mass%V obtained at 300 A/m2
Zn concentrations were inverted. The concentration of oxy- from the solution of pH 2.
gen (d) corresponded to that of V. Therefore, the granular
crystals at the boundaries of Zn platelet crystals shown in
Fig. 7(b) appear to consist of V oxide.
Because the distribution of V in deposits obtained from
un-agitated solutions was heterogeneous, as can be seen
from Figs. 8 and 9, the electrodeposition was also con-
ducted in agitated solutions. Figure 10 shows EPMA im-
ages of deposits obtained from agitated solutions. The V
content in the deposit from the un-agitated solution was
4.9 mass%, but this decreased to 1.0 mass% in case of the
agitated solution. Despite the evolution of hydrogen in the
cathode layer during electrolysis, the hydrolysis of V ions
was retarded as a result of an increase in the diffusion of
H into the cathode layer in agitated solutions, resulting in
a decrease in the V content of the deposits. The V element
in deposits obtained from agitated solutions also segregated
at the boundary of Zn platelet crystals, as shown in Fig. 10,
but the area of V oxide was smaller as a result of a decrease Fig. 9. EPMA images of Zn–19.9mass%V obtained at 2 000 A/
in the V content of the deposits compared with the case of m2 from the solution of pH 2.
the un-agitated solutions. Consequently, the distribution of
Zn in the deposits obtained from agitated solutions was At current densities of more than 1 000 A/m2, however, the
more homogeneous. In deposits obtained from un-agitated orientation of the (0001) plane decreased and that of (112̄2)
solutions, the characteristic X-ray of S was also detected: S increased in solutions containing VO2. Since the V content
was concentrated at the boundaries of Zn platelet crystals, in deposits increased with increasing current density, as
suggesting the involvement of the electrolyte in the deposit. shown in Fig. 2, V oxide codeposited with Zn appears to in-
Figure 11 shows the crystal orientation of Zn deposited hibit the lateral growth of Zn along the (0001) plane.
from VO2-containing (a) and VO2-free solutions (b). At
low current densities (below 1 000 A/m2), the preferred ori- 3.4. Polarization Properties of Deposits
entation of deposited Zn was the (0001) basal plane of the Figure 12 shows the polarization curves of deposits in
hcp structure, regardless whether or not it contained VO2. 3% NaCl solution. The polarization curve of the deposit

509 © 2008 ISIJ

 ISIJ International, Vol. 48 (2008), No. 4
Fig. 10. EPMA images of deposits obtained at 2 000 A/m2 from the agitated and un-agitated solutions of pH 2
(ZnSO4 · 7H2O 0.52 mol/L, VOSO4 · 5H2O 0.12 mol/L).
Fig. 11. Crystal orientation of Zn deposited from V-containing
and V-free solutions of pH 2.
Fig. 12. Polarization curves of Zn–V oxide composite in 3%
NaCl solution.
with a V content of 4.8 mass% was shifted to the more-
noble direction than that of a deposit of pure Zn, whereas
that of a deposit with a V content of 19.9 mass% was more
polarized than pure Zn. The shapes of the cathodic polar-
ization curves were almost identical, regardless of the pres-
ence or absence of codeposition of V oxide.
Figure 13 shows the corrosion potentials of deposits de-
termined from the polarization curves. The corrosion po-
tentials of deposits obtained from un-agitated solution were
shifted to the noble direction with increasing V content up
to 5 mass%, whereas they were shifted to the less-noble di-
© 2008 ISIJ
Fig. 13. Relationship between V content and the corrosion po-
tential of Zn–V oxide composite in 3% NaCl solution.
rection with increasing V content above 5 mass%. Since an-
odic polarization curves for Zn dissolution are shifted to the
noble direction with codeposition of V oxide in the range of
V contents below 5 mass%, the corrosion potentials of de-
posits seem to shift to the noble direction. This shift in the
anodic polarization curve is ascribed to a barrier effect of V
oxide, which has a low conductivity, on the dissolution of
Zn. The reason why the corrosion potentials were shifted
to the less-noble direction at V content above 5 mass% is
at present unknown. However, at V contents exceeding
5 mass%, deep cracks occurred in the deposit and the sur-
face became very rough, suggesting that the surface mor-
phology of the deposit may affect the corrosion potential.
Figure 14 shows the corrosion current densities of de-
posits, determined from the polarization curves. The corro-
sion current densities of deposits obtained from un-agitated
solution showed dispersion, and no relationship was ob-
served between the V content in deposits and the corrosion
current densities. On the other hand, the corrosion current
densities of deposits obtained from agitated solution were
smaller than those from non-agitated solution. Because the
distribution of V oxide in deposits became homogeneous
on agitation of the solution, the distribution of V appears to
affect the corrosion current density of the deposit.
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 ISIJ International, Vol. 48 (2008), No. 4
Fig. 14. Relationship between V content and the corrosion cur-
rent density of Zn–V oxide composite in 3 % NaCl solu-
tion.
4. Conclusion
Electrodeposition of Zn with V was tried in sulfate solu-
tions containing Zn2 and VO2 to investigate the structure
and polarization property of deposits. The following results
were obtained. XPS spectra of the deposits showed that V
was involved in the deposited Zn in the form of its oxide by
hydrolysis of V ions. The V content of the deposits in-
creased with increasing pH of the solution and increasing
current density. These conditions appear to accelerate the
hydrolysis of V ions as a result of an increase in hydrogen
evolution in cathode layer. SEM and EPMA images of the
deposits revealed that the V in the deposits was segregated
at the edges of layered platelet crystals of Zn. Agitation of
the electrolyte decreased the V content of the deposits, but
decreased the segregation of V oxide. Anodic polarization
curves for Zn dissolution in 3% NaCl solution were polar-
ized by codeposition of V oxide with Zn in the range of V
content less than 5 mass%. The corrosion current densities
of deposits obtained from agitated solutions were smaller
than those from un-agitated solutions.
Acknowledgements
This work was supported by a 15th ISIJ Research Pro-
511
motion Grant from The Iron and Steel Institute of Japan.
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