ISIJ International, Vol. 33 993), No.

(1 9, pp.
I 009-101 5

Electrode position Behavior of Zn-lron-grou

Sulf ate and Chloride Baths
p Metal Alloys from

Hisaaki FUKUSHIMA.
Tetsuya AKIYAMA.Masaaki YAN0.1) Tatsuo ISHIKAWA2)and Roland
M
KAM EL3)

Faculty of Engineering, Kyushu University. Hakozaki. Higashi-ku, Fukuoka. Fukuoka-ken, 81

Japan. 2
)
1 Graduate School, Kyushu University, Hakozaki. Higashi-ku. Fukuoka, Fukuoka-ken, 81 Japan.
2) Formerly Graduate School, Kyushu University.
2
Nowat Fuji Film Corporation. Ogi-machi. Odawara-shi. Kanagawa-ken,
250Japan 3) Instltute of Metallurgy. Technical University of Berlin, Str. des 7. Juni 35,
'

1 1 I
.
OOOBerlin 2, Germany. 1
(Received on February l9. l993, accepted in final form on May2l. 1993)

Electrodeposition of Zn-iron-group metal binary alloys, which has been applied in the
production of
highly corrosion-resistant alloy plated steel sheet,
was conducted from sulfate and chloride baths and the
alloy deposition behavior
was comparedbetween two types of baths. The current density-dependence of
alloy composition showed typical feature of
a an anomalouscodeposition in the sulfate baths. In the chloride
baths, the deposition behavior shifted gradually from an anomalousto a regular type with increasing
was
chloride ion concentration. On the basis of the factors determining the characteristic
current density at
which Zn deposition began, the alloy deposition behavior discussed with the particular reference to
was
the effect of catalytic chloride ions for iron-group metal deposition.

KEYWORDS:
electrodeposition; Zn alloys; iron-group metals; anomaloustype; transition current density;
catalytic chloride ions,

l. Introduction formed and adsorbed on the cathode. Therefore, the

presence of certain catalyst which promotes the
Electrodeposition of Zn-iron-group metal alloys has deposition will bring about a great change in the alloy
been applied to the production of highly corrosion- deposition. In this study, the alloys were electrodeposited
resistant alloy plated steel sheet mainly for automotive from catalyst-free sulfate baths and from chloride baths
body panels.1~3) Zn-iron-group metal alloys can be containing a large amount of chloride ion which is
electrodeposited from various types of baths such as catalytic for iron-group metal deposition,20,21) and the
sulfate, chloride, cyanide, ammoniacal, alkaline zincate, alloy deposition behavior
was compared between the
pyrophosphate and fiuoborate baths.4~9) The sulfate baths.
type baths have been mainly adopted in the high speed
alloy plating on a simple shapedsteel strip at high current 2. Experimental
densities. In
a batch plating of small componentshaving
a complicated shape, on the other hand, chloride baths The baths of five different chloride ion concentrations

have been preferred because of their better throwing were prepared by dissolving metal sulfate and/or chlo-
ride in distilled and ion exchanged water. The bath
power, I
o)

The electrodeposition of Zn-iron-group metal alloys composition wasshownin Table 1. The pHwasadjusted
in sulfate baths is
one of the best-known examples of
Table 1. Composition of baths used. (mol/1)
anomalouscodeposition, in which electrochemically less
noble Zn deposits preferentially under most plating
conditions.4'9)
Bath No. l 2 3 4 5
Although many hypotheses have been
proposed to explain this anomaly, the hydroxide ZnS0+ 0.5
suppression mechanismiI ~ 15) is at present considered to ZnC12 0.5 0.5 0.5 0.5
be most plausible.9' 16 19) According to this mechanism, MS04 o.5 0.5
MC12 o.5 0.5 0.5
the deposition rates of both hydrogen and iron-group
NaCl 2,0 4.0
metals were kinetically suppressed greatly at potentials
where they can deposit thermodynamically. This in- Cl conc. o 1.O 2,0 4.0 6.0
hibition was caused by the inherent minimumover-
potential for the initiation of their depositions and by M: Iron-group metal.

the extra-overpotential
pH of
the solution was adjusted to l,
3or 5with H2S04or HCI in
due to inhibitory Zn hydroxide each bath.

1009 C 1993 ISIJ


to l,
3or 5with sulfuric acid for sulfate baths and with
hydrochloric acid for chloride baths. small amountof
citric acid (2 g/1)
was added to Zn-Fe alloy plating baths
to prevent ferric hydroxide formation. The alloys were
obtained from un-agitated baths on a Cu cathode of
l x 2cm2 using a Pt anode at 40'C under coulostatic
(1.0 x 105C/m2) and galvanostatic conditions. The
current density was varied from 1.0 to 5.0 x 104A/m2.
A beaker type cell was used for Zn-Ni and Zn-Co alloy
depositions while Zn-Fe alloy deposition was conducted
in an H-section cell where catholyte was separated from
anolyte by a sintered glass. The deposited alloys were
dissolved from the cathode with nitric acid. Alloys were
quantitatively analyzed by atomic absorption spectrom-
etry to determine the composition, the current efficiency
and the partial current density of each metal. In some
cases, cathode potential was measuredduring the alloy
deposition using an AglAgCl reference electrode to
obtain the polarization curve. In the presentation of
polarization curves, the potentials were plotted with
reference to NHE.
ISIJ International, Vol. 33 (1993), No. 9
of the bath.4) The iron-group metal content of the alloy
A below the CRLindicates the anomalous codeposition
because the alloys contain a larger ratio of less noble Zn
than the baths.
As shown in Figs. I (1)(3) and 2(lO) and (13), the
alloy deposition in the sulfate baths was obviously
divided into the following four segments with respect to
the current density: region I where the electrochemically
most noble hydrogen evolved preferentially and the
normal type alloy deposition occurred with a very poor
current efficiency; region 11 where the preferential
deposition of less noble Zn proceeded with high current
efficiency and the alloy composition hardly changed;
region 111 where the content of iron-group metal of the
alloys steadily increased while considerably high current
efficiency was still maintained; and region IV where the
alloy composition approximately reached the CRLof
the baths and the current efficiency decreased greatly.
Thealloy deposition in the sulfate baths mentioned above
was already reported by the present authors.13 ~ 15)
As can be seen from Figs. I (4)(9) and 2(ll), (12),
(1 4) and (1 5), the partial current efficiency for iron-group

3. Results and Discussion metal deposition in region I was greatly improved in the
chloride baths. When the chloride ion concentration was
3.1. Comparison of the Alloy Deposition between the increased, the boundary current density between regions
Sulfate and the Chloride Baths
I and 11 becamelarger to reduce the width of region II.
Figures I and 2 show examples of the current In Zn-Co and Zn-Fe alloy deposition from the high
density-dependence of alloy composition and current chloride ion concentration baths, the region 11 almost
efficiency for Zn alloy deposition with iron-group metals. disappeared as shown in Figs. 2(12) and (15), showing
The CRL in the figures stands for the composition the typical feature of regular type alloy deposition.4)
reference line which shows whenthe weight-percentage The alloy deposition behavior was thus considerably
composition of the alloy just equals the metal-percentage different between the sulfate and chloride baths.

Sulfate bath Cl~ 2mol/L Cl~ 6 mol/L

1OO (1)
o (4) (7)

80
e Ni content
~~oo
o c.C.E.
60
O
~,
-CRL - ' -CRL -CRL -
e =cL
C
- -

,(p_ 40

~
UJ 20
SO
o (2) (5) (8)

8O 80
~
,
60 ,,,

=a.
'~,El

- CRL-- CRL-- -CRL•-

O 40
~~oo

2o
'QO

CL O (3) (6) (9)

O o
Q 80
ld
C 60
,p bD
'~
i -CRL-- CRL -CRL-- =cL
O - - -

O 40
Z 20
e
o 102 103 104 100
100 IO 10 10 10 100 10 10 10 10 IO
Current Density (Nm2)
Fig. l. Effect of current density on the alloy composition and the current efficiency for Zn-Ni alloy deposition
from the baths of various pH and chloride ion concentrations.

C 1993 ISIJ 1ol o

 ISIJ international, Vol. 33 (1993), No. 9

Sulfate bath 2mol/L 6 mol/L

1oo (10)
80 o (11) (12)

o
~~eo
O
60 O e
-o~
~~=,D ---- CRL-- -----CRL-- cRL-----
40
So
'0~E
OaLU 20 iLO
c'c'E'
a' 1~S
Qg,
,:LL
o
(13) (i4) (15)
.-
1.,: = 80
(~) o
~~'D

O
,:
O 8 6o
J:1-

.-
,~,
--CRL ---- -CRL---- ---CRL----
ZO 40
20

o =- J
1Oo 10 10 10 10 10 10 10 103 104 100 10 102 I03 Io
Current Density (Nm2 )
Fig. 2. Effectof current density on the alloy composition and the current efi~lciency for Zn-Co or ZnFealloy
deposition from pH 3baths of various chloride ion concentrations

104
The cathode potentials were more noble than the
tii equilibrium potential of Zn at these lower current
densities. Therefore, the fact that the iron-group metal
content of barely depositing alloys was not identical to
~
~~
103
lOOo/o indicates an appreciable amountof underpotential
deposition of Zn. The underpotential deposition of Zn
~
:gC'o
102 occurred only in thc presence of iron-group metals and

O
Q)
was never observed in other Zn alloy systems.15) The
~
':
[] mechanismwhich permits this anomaly still remains
10
~ unknown.The current for underpotential deposition was
8 100 neglected in the partial polarization curve for Zn
~ l *~
E~Z~
deposition in Fig. 3. A
substantial amountof alloy began
I to deposit at the transition current density at which
I overpotential deposition of massive Zn began. The
l
10-1 present authors have reported that the transition current
*0.25 -0.50 -0.75
-1 .OO *1 .25 -1 50
density dependedon the pHbuffering capacity of sulfate
Cathode Potential (V vs. NHE)
baths. i 3)
Frg. 3. Partial polarization curves for Zn, Ni and hydrogen In pure Zn deposition in highly acidified Zn sulfate
deposition from the sulfate bath of pH 3.
solutions for electrowinning,22) the partial polarization
curves for hydrogen and Zn are identical to those in the
3.2. Factors Determining the Current Density at which alloy deposition shown in Fig. 3. There also existed a
Zn begins to Deposit in the Sulfate Baths characteristic current density at which the cathode was
The boundary current density between regions I and discontinuously polarlzed to the equilibrium potential of
II has been referred to as the transition current density Zn. This minimumcurrent density required for initiating
in the field of alloy plating. It
was originally defined by Zn deposition has been called the critical current density
Brenner4) as the current density at which the alloy in the field of Zn hydrometallurgy. 22,23) It was reported
composition becameidentical to the CRLduring the that the magnitude of critical current density depended
abrupt transition of alloy deposition from a normal to material22) and
on cathode on the species or amountof
an anomaloustype. Figure showsthe galvanostatically 3 impurity metal ions in electrowinning baths.22,24)
measured polarization
partial curves for hydrogen In sulfate baths, the transition from predominant
evolution and each metal deposition from the sulfate hydrogen evolution to substantial overpotential deposi-
bath of pH 3. The corresponding alloy deposltion be- tion of Zn was observed at the transition current density
havior was shown in Fig, (2). The transition
I
current for alloy deposition or at the critical current density for
density is given as the sumof each partial current density pure Zn deposition. This indicates that the transition or
at which the cathode potential shifts from
- 0.4 to
the V the critical current density appears owing to the same
equilibrium potential for Zn deposition. In the sulfate mechanism. Figure 3
revealed that the suppressed
baths, predominant hydrogen evolution occurred at hydrogen current began to increase at the transition
lower current densities than the transition current current density. In pure Zn deposition, the hydrog~n
density, as shownin Figs, I (1)-(3) and 2(lO) and (13). current changes around the cntrcal current denslty

1ol 1 ,c"J
1993 ISIJ
 ISIJ International, Vol, 33 (1993), No. 9
exactly in a similar manner.22) Whenthe rising part of
the partial polarization curve of hydrogen in Fig. was 3 EeHq_E~~ c l?
o q, d
extrapolated to current zero at potentials less noble than - ~* \•
the equilibrium potentiai of Zn, the hydrogen evolution
was found to apparently begin at the equilibrium L:: o f
nH(Zn)->
potential of Zn. This Indicated that the deposition ~
overpotential nH for hydrogen must satisfy the following + Tl~(Cu)
o:: (r---
equation in order to inltlate the overpotential deposition F a b g
of Zn.

P~--
T]~(Ni)
E~q-nH
= E~~ (1) ~
••••••••• m n

Whenthe equilibrium potentiai is different too much

between the competitive components, as just in the case Current Density -~
of hydrogen and Zn, the deposltion overpotential should Fig. 4. Schematic representation of the dependence of
be normally resulted from the diffusion control for more nlol nl,h the current density.
+ on
noble component. In the codeposition of Zn with
hydrogen, however, the limiting current for more noble
deposition on a Cu cathode used in this study. The
hydrogen was not attalned yet because the hydrogen
current began to increase when the transition current
hydrolysis of Zn ions begins at point in the figure and b
hereafter the nlH~h goes on increasing due to the steadily
density was exceeded. increasing rate of hydrogen evolution. Whenn~ + nlH~h js
On the basis of hydrogen's inherent property of not increased to reach EH*q-E~~ at point c, the Eq. (2) is
beglnning to deposit at its equilibrium potential but
satisfied to permit Zn deposition. Consequently, it can
requiring an extra-overpotential, the present authorsl9)
be concluded that the critical or transition current density
have already studied the critical or transition current Is the hydrogen deposition current density which brings
density appearing in pure Zn or Zn-iron-group metal
about the nlH~h
which is identical to EH'q Ez'~ -n~-
alloy deposition from the sulfate type baths, and reported
Therefore, the magnitude of the critical or transition
-
that the nH was composedof n~ and nlH~h. Consequently,
current density depends essentially on the n~ and any
the electrochemical requirement for initiating the
other factors affecting the depletion rate of hydrogen
overpotential deposition of Zn can be modified and
ions at the cathode layer. In the case of Zn deposition
described by following equation.
on the Ni cathode with smaller nfi than Cu, for example,
n~ + [~h E~~ •••••••••(2) the current density-dependence of nfi + nlH"h js given by
nH = E'Hq the segmentm-n-o. Therefore, the critical current density
Whenthe Eq. (2) is satisfied at the transition current is predlcted to increase from point
density, Zn begins to deposit. In the equation, n~, c to o. It is reported
that the larger critical current density was observed on
so-called hydrogen overpotential, is the minimumover-
the cathode with smaller n~ in the electrowinning of Zn
potential for initiating the hydrogen evolution. It is
from highly acidified sulfate baths.23)
well knownthat the n~ depends mainly on the cathode
material. The n~ derives from the rate determining step 3.3. Effect of pHand Chloride lon Concentration on the
in the multi-step reduction of hydrogen ions. Therefore, Transition Current Density
the deposition sites for hydrogen should be substantially Figure 5
shows the relationship between the pH and
limited on the cathode. The limited numberof deposition the transition current density in the electrodeposition of
sites for hydrogen will easily give
an extra-overpotential Zn-Ni alloys on a Cu cathode in the baths of various
when the sites are occupied by adsorbed foreign species. chloride ion concentrations.
In hydrogen evolution in the presence of Zn ions, Zn The transition current density was increased with
hydroxide, formed by hydrolysis due to the predominant decreasing pHin the sulfate baths. The transition current
hydrogen evolution in region I in Figs. I (1)-(3), acts as density is thus remarkably dependenton the pHof sulfate
such an inhibitor. The increment of overpotential due to baths. Provided that the initial Cu surface could remain
adsorbed inhibitory Zn hydroxide wasexpressed as nlH"h I
unaltered in region because of a negligibly small current
The term (h~H'q Ez'~) in the Eq. (2) is unequivocally efficiency for alloy deposition as shownin Figs. (1)(3), I
-
determined whenthe bath composition and temperature the n~ of the cathode is kept at constant and no change
are fixed. The n~ is primarily determined by the cathode in the transition current density should be expected. In
material. The nlH"h is determined by the coverage of the case of simple sulfate type baths, the dissociation of
hydrogen deposition site by adsorbed Zn hydroxide. The HSO~to S0~~ (pK=2) is the major pH buffering
coverage is proportional to the difference between the reaction and therefore the buffering capacity changes
chemical formation and electrochemical consumption greatly around pH 2. Consequently, Iowering the bath
rates of Zn hydroxide and therefore the nlH"h should pHcauses the increase in the buffering capacity, resulting
depend on the current density. The current density- in the larger hydrogen evolution rate required to achieve
dependenceof nlH~h was already presented by the present the critical pHfor Zn hydroxide formation at the cathode.
authorsl9) and the dependenceof n~ nlH"h
+ on the current In this case, therefore, the transition current density
density was schematically illustrated in Fig. 4. The increases from point c to because the current density h
segment a-bH~-d~-f corresponds to the case of Zn for initiating the hydrolysis of Zn ions increases from

C 1993 ISIJ 1ol 2

 ISIJ International, Vol. 33 (1993), No. 9
ions were evldently catalytic for Ni deposition bLrt
contributed no depolarization for hydrogen evolution in
the presence of Ni ions. Thus, chloride lons act as a
E
~_ catalyst to reduce the minimumoverpotential of n~i for
102 initiating Ni deposltion. This explains well the fact that
>
'o
c,D Ni depositlon occurred in preference to hydrogen
a evolutlon even at low pH In the bath of high ch]oride
=a' ion concentration as shownin Fig. I (7).
:'
In the chloride baths, as evident from Figs. I (4)-(9)
o 10 Sulfate bath and 2(1 1), (1 2), (14) and (1 5), the catalytic chlorlde ions
=
o A Cl ; I mollL improved the partial current efficiency for iron-group
'o
=a'
CI
; 2 mol/L metal deposition remarkably in region l. As mentioned
Cl*;
4 mollL previously, the substantial amount of iron-group metal
H CI*;
6 mol/L begins to deposit in the sulfate baths when the
10o overpotential deposition of massive Zn begins at the
O 1 2 3 4 5 transition current density. Therefore, the current
pH efficiency for alloy deposition begins to increase abruptly
Fig. 5. Relationship between the transltion current density at the transition current density, and thus the transition
and pH of the Zn --Ni alloy plating baths of various current density can be determined clearly. In the chloride
chloride ion concentrations.
baths, on the other hand, the iron-group metal deposi-
tion with high current efficiency in region I induced
104
H2 -1 a pronounced underpotential deposition of Zn. This
prevented the clear determination of the current density
103
at which the overpotential deposition of Zn began in
102 Figs. I and 2. The transition current densities plotted in
Fig. 5were defined originally by Brenner4) as the current
E
~_ 10 I;;i';;;Lii~~:"~'=~'~
density at which the alloy composition becameidentical
~
.'
,~ 100 ~1 cr; 6 moVL
to the CRL. It becomespossible to discuss qualitatively
c:
a'
the current density at which Zn begins to deposit in the
o
~' 1o ~1
chloride baths whenthe underpotential deposition of Zn
= is ignored.
o Ni
103
:s
o
Figure 5
revealed clearly that the magnitude of
transition current density becameless dependent on the
102
~ 10 pH and much more dependent on the chloride ion
concentration when chloride ion concentratlon was
increased. The high partial current efficiency for I\;Ii
100 deposition in region I will affect the initiation of Zn
10~1 deposition in a following manner: the cathode surface is
-0.2 -O.4 -0.6 *0.8 -1 .O altered from initial Cu with higher n~ to deposited Ni
Cathode Potential (V vs. NHE) with lower n~; and larger current density is required to
Fig. 6. Effect of chloride ions on the partial polarization
inltiate the hydrolysis of Zn ions because the hydrogen
curves
for hydrogen and Ni deposition from the Ni single evolution rate decreases considerably. Therefore, the
bath. segmenta-b~ is shifted to -p-q, resulting in the higher
m
transition current density at point (Fig. 4). It can be
q
point b
to g in Fig. 4. seen from Figs, I
(5)-(9) that the partial current efficiency
In the chloride baths, on the other hand, the alloy for Ni deposition was little affected by the pHin region
deposltion behavior wasconsiderably different from that I and therefore the partial current efficiency for hydrogen
in the sulfate baths as shownin Figs,
I (1)--(3) and 2(lO) evolution is almost kept at constant in the higher chloride
and (13). It was reported that the electrodepositions ion concentration baths. Consequently, the transition
of iron-group metals, which had the inherent property current density becomes primarily dependent on the
of not beginning to deposit at their equilibrium poten- chloride ion concentration which governs the partial
tials, proceeded by a multi-step reduction mechanism current efficiency for Ni deposition in region I.
through a transient intermediate containing hydroxyl
groups25~27) and thus chloride ions catalyzed the iron- 3.4. Alloy Deposition Behavior at Higher Current Den-
group metal deposition by modifying the composition than the Transition Current Density
sities

of intermediate. 21) Figure 4 can also explain the deposition behavior of

Figure 6
shows the partial polarlzation curves for pure Zn and Zn alloys with iron-group metals at higher
hydrogen and Ni depositions from Zn ion-free Ni single current densities than the critical or transition current
bath prepared by substituting Zn sulfate or chloride for density. Whenthe current density is increased along the
corresponding Na salt in the Zn-Ni alloy plating bath segment c-d-e-f from point c at which Zn begins to
of pH 3. It was found from this figure that the chloride deposit, hydrogen evolution is greatly suppressed to cause

1ol 3 (O 1993 ISIJ

 ISIJ International,
predominant Zn deposition with preceding Zn hydroxide
formation in the presence of constant nlH"h resulted from
well balanced rates of chemical formation and elec-
trochemical consumption of Znhydroxide. When the cur-
rent density is increased to reach point d at which the
supply of Zn ions to the cathode begins to be controlled
by diffusion, the nlH~hbegins to be decreased because of
the larger rate of consumption than the formation of Zn
hydroxide. The nlH~h disappears at point e where the
depositions of both metals reach their limiting currents.
At higher current densities than point d, the requirement
for Zn deposition cannot be satisfied because n~ nlH"h
+
becomessmaller than E*Hq E~~. In this case, however,
-
Zn deposition proceeds under diffusion control and thus
resulting diffusion overpotential maintains the cathode
at potentials less noble enough than the equilibrium
potential of Zn.
According to Fig. 4, it is expected in pure Zn deposition
on a Cu cathode in the sulfate bath that the current
efficiency is maintained at high level in the region between
d d
c and and it begins to decrease at point and that the
current efficiency decreased to negligibly small at point
e. Thus. Fig. 4explains well the actual current density-
dependenceof current efficiency for Zn deposition.
In Zn-Ni alloy deposition from the sulfate baths, as
shown in Fig. 3, the partial polarization curve for Ni
began to increase again after the cathode potential shift-
ed abruptly to the equilibrium potential of Zn at the
transition current density. Whenthe rising part of the
partial polarization curve of Ni was extrapolated to the
current zero at less noble potentials than the equilibrium
potential of Zn, it was revealed that the Ni deposition
would apparently begin at the equilibrium potential of
Zn. This indicates that the electrodepositiQns of iron-
group metals tended to be suppressed in the presence of
inhibitory Zn hydroxide just as in the case of hydrogen.
The anomaly that the electrochemically less noble Zn
deposited in preference to the more noble iron-group
metals has been explained by the inhibitory action of
adsorbed Zn hydroxide. This explanation was called the
hydroxide suppression mechanism.9'17,18) Figure
indicated that the Zn hydroxide exerted an inhibitory
action more effectively for the deposition of hydrogen
which was originally more noble than Ni. Therefore, as
shown in Figs. I (1)(3) and 2(10) and (13), the alloy
deposition behavior in regions II, 111 and IV in the sul-
fate bath showed the typical feature of regular type
codeposition4) whenZn behavedas the most noble metal.
d
The current density region between c and corresponds
to region 11 where the anomaloustype alloy deposition
occurs at high current efficiency because the deposition
of hydrogen, as well as iron-group metals, is suppressed
greatly in the presence of adsorbed Zn hydroxide. When
the apparently most noble Zn deposition begins to reach
its limiting current at point d, the depositions of less
inhibited iron-group metals are promoted in preference
to hydrogen. Therefore, the iron-group metal content of
the alloy increases without significantly decreasing the
current efficiency at region 111. After the limiting currents
for the depositions of both metals are reached at point
e, the alloys whose compositions are approximately
C 1993 ISIJ
Vol. 33 (1993), No. 9
identical to those of the baths are obtained with extremely
poor current efficiency in region IV. In the chloride baths,
on the other hand, the transition current density increased
to reduce the width of region 11 which finally disappeared
in
somecases as shown in Figs. 2(12) and (15). When
the inherent overpotential no disappears, the iron-group
metals should behave as a normal metal such as Cu or
Zn during the alloy deposition. Therefore, the original
nobility of each metal is reflected in the codeposition to
permit a regular type alloy deposition in the presence of
a large amount of catalytic chloride ion.
As mentioned previously, the boundary current density
between regions 11 and 111, which was observed in most
cases except Figs. 2(12) and (15), corresponds to the
total current density at which Zn deposition begins to
reach limiting current. The limiting current density of
its
Zn is given by the product of this boundary current
density and the partial current efficiency of Zn at
corresponding current density. Therefore, the boundary
current density should be identical in the baths of
constant Zn ion concentration when the baths yield
equivalent partial current efficiency of Zn in region II.
In the case that the al]oys deposit with high current
efficiency in region II, above condition is nearly satisfied.
Thus the approxirnately constant boundary current
density of I OOO A/m2 was observed for ZnNi, and
600 A/m2 for Zn-Co and Zn-Fe alloy depositions, as
shownin Figs. I and 2.
At the boundary current density between regions 111
and IV, the deposition of iron-group metal, as well as
Zn, reaches its limiting current, resulting in a pronounced
decrease in the current efficiency for alloy deposition. In
this case, the alloy composition should be identical to
the limiting current ratio of each metal. The limiting
current is described as nFDC*/~• The F stands for the
Faraday constant, and n and C* indicate the valence
and the concentration of metal ions in the bulk solution
~
of the baths. The D and are the diffusion coefficient
and thickness of diffusion layer for each metal ion,
respectively. The fact that the alloy composition in region
3 IV becamealmost identical to the CRL, as shown in
Figs. I and 2, indicated that both metal ions had
approximately the samevalues of D and 8. The limiting
current density for alloy deposition is given by the
product of this boundary current density and the current
efficiency for alloy deposition. Therefore, the current
efficiency began to decrease
almost constant current
at
density of more or less than 2x 104 A/m2 as shown in
Figs. I and 2, because the total metal ion concentration
was kept constant at I mol/1 in the baths used.
In the sulfate baths, generally, the alloys can be
obtained with practically acceptable high current
efficiency in the anomalous regions 11 and 111, and the
maximumiron-group metal content of the alloy is
determined by the metal-percentage of iron-group metal
in the baths. Onthe other hand, in the chloride baths,
the alloys of high iron-group metal content are obtained
with high current efficiency in region I. In the baths of
high chloride ion concentration, the minimumiron-group
metal content of the alloys is almost identical to the
metal-percentage of iron-group metal in the baths.
1ol 4
 ISIJ Internationai. Vol. 33 (1993), No. 9

4. Summary REFERENCES
Zniron-group metal alloys were electrodeposited l) S.
A Watson: Internal
Report of Inco Europe Ltd., London,
England, Jan.. (1982).
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behavior in the sulfate baths was divided into following 3) T. Asamura: Te!su-to-Hagan~, 77 (1991), 861 .

four segments with respect to the current density: region 4) A. Brenner: Electrodeposition of Alloys, Vols, l, 2, Academic
I where predominant hydrogen evolution occurred and
5)
Press,
L.
NewYork and London, (1963).
Domnikov: Met. Finish., 16 (1963), 49.
the alloys hardly deposited; region 11 where the
6) D. V. Subrahmanyam
and RamaChar: Meta!loberftaeche, 21
anomalous type deposition of alloy of almost constant (1967), 200.
composition proceeded with high current efficiency; 7) L. Domnikov: Met. Finish., 64 (1966), 68.
region 111 where the iron-group metal content of alloys 8) A. F. Bogenschutz and U. George: Galvanische Legierungs-
increased while the current efficiency was still kept at abscheidung und Analytik, 2nd Ed., Eugen G. Leuze Verlag,
higher level; and region IV where the alloy composition Saulgau, (1982), 156.
9) T. Akiyama a~rd H. Fukushima: ISIJ Int., 32 (1992), 787.
becameapproximately identical to the CRLand
the
1O) H. Enomoto and T. Omi: Alloy Plating, Nikkan Kogyo
current efficiency decreased greatly. In the chloride baths, Shimbunsha, Tokyo, (1987), I 12.
the partial current efficiency for iron-group metal l l) K. Higashi, H. Fukushima, T. Urakawa, T. Adaniya and K.
deposition increased markedly in region I. This reduced Matsudo: J. E!ecn'ochem. Soc., 128 (1981), 2081.
the width of region 11 which disappeared finally at high l 2) H. Fukushima, T. Adaniya, J. Lee, M. Yamaguchi and K.
Higashi: T,'ans. Jpn. Insl. Me'., 24 (1983), 125.
chloride ion concentration. Thealloy deposition behavior
l 3) H. Fukushima, T. Akiyama, K. Higashi, R. Kammeland M.
thus changedgradually from anomalousto regular type Karimkhani: Meial!, 42 (1988), 242.
when chloride ion concentration was increased in the l4) H. Fukushima, T. Akiyama, K. Higashi, R. Kammeland M.
baths. Karimkhani: Metall, 44 (1990), 754.
At the boundary current density betweenregions I and l 5) K. Higashi, Y. Hayashi, H. Fukushima, T. Akiyamaand H. Hagi:
NiDI Technical Series No, 10036, Nickel Development Inst.,
II, which is referred to as the transition current density,
a substantial amountof alloy began to deposit from the
(H.1990) .

16) Fukushima, T. Adaniya and K. Higashi: J. Me!. Finish. Soc.

sulfate baths. The magnitude of the transition current Jpn., 34 (1983), 446.
density dependedpredominantly on the bath pH. When l 7) D. E. Hall: P!at. Surf. Finish., 70 (1983), 59.
chloride ion concentration was increased in the chlo- l 8) T. Akiyama, H. Fukushima and K. Higashi: Tetsu-to-Hagan~,
72 (1986), 918.
ride baths, on the other hand, the pH-dependenceof
I9) H. Fukushima and T. Akiyama: J. Surf. Finish. Soc, Jpn., 41
transition current density disappeared whereas the (1990), 888.
chloride ion concentration in the baths governed the 20) K. Higashi and H. Fukushima: J. Jpn. Insl, Mer, 40 (1976), 765.
transition current density. The Zn deposition began to 21) M. Yasuda, I. Ohnoand S. Haruyama:J. Surf Finish. Soc. Jpn.,
41 (1990), 312.
reach its limiting current at the boundary current density
22) S. Ohyama and S, Morioka: Proc. Int. Symp. Extr. Metallurgy
between regions 11 and 111, and the limiting currents for of Zinc, Min. Metall. Inst. Jpn., Tokyo, (1985), 219.
both metal depositions were attained at the boundary 23) U. C. Tainton: Trans. Am. E!ectrochem. Soc., 41 (1922), 389.
current density between regions 111 and= IV. The 24) T. Akiyama, H. Fukushima, H. Nakayama and K. Higashi: J.
magnitude of above two characteristic boundary current Min. Met. Insl. Jpn., 102 (1986), 317.
densities becamealmost identical in both sulfate and
25) K. F. Bonhoeffer and K. E. Heusler: Z. Elektrochem., 61 (1957),
chloride baths. l 22.
26) K. F. Heusler: Z. Elektrochem, 62 (1958), 582.
On the basis of the electrochemical requirement for 27) J. O'M. Bockris and H. Kita: J. E!ectrochem. Soc., 108 (1961),

the initiation of overpotential deposition of Zrf, the alloy 676.

deposition behavior presented above was discussed by
taking into account the catalytic action of chloride ions.

1ol 5 C 1993 ISIJ