Electrodeposition of Ni-Zn Alloy

II. Electrocrystallization of Zn, Ni, and Ni-Zn alloy

Yu-Po Lin* and J. Robert Selman**

Department of Chemical Engineering, Illinois Institute of Technology, Chicago, Illinois 60616

ABSTRACT
The initial stages of the electrodeposition of nickel, zinc, and nickel-zinc alloy were investigated by nucleation analy-
sis. A novel deconvolution technique was applied to obtain the individual chronoamperometry of each species and eluci-
date the nucleation and growth mechanism of nickel-zinc alloy deposition. In agreement with earlier conclusions (part I of
this study), codeposition of hydrogen and nickel occurs in the initial stage of deposition. Adsorption and evolution of
hydrogen are significant and cause the enhancement of nickel content. From the deconvoluted chronoamperograms of
nickel-zinc deposition, we see that the nucleation and growth mechanism of the alloy is similar to that of the pure metals
(i.e., nickel or zinc). This similarity implies a weak interaction between nickel and zinc nuclei in the initial stages of
deposition.

Literature reports show that different electrodeposition Experimental Selup

conditions cause different phase structures even if the
chemical composition of the deposited alloys is similar. 1'2
The orientation of deposits and their phase composition are
influenced not only by the electrodeposition rate but also,
sometimes strongly, by the substrate. This is not surprising
because different substrates have different distributions of
the surface free-energy distributions and the crystallogra-
phy of the initial deposit is determined by the surface free
energy of the substrate. In alloy electrodeposition the phase
composition, which is frequently associated with preferen-
tially oriented deposition, is substrate related. The concept
of substrate-dependent deposition can imply that changing
the surface free-energy distribution of a surface changes
the properties of the initial deposit layer, such as the mor-
phology and the oriented-growth direction. The growth of
a multilayer deposit is a historical process. In alloy deposi-
tion, uniformity of deposit properties (such as the local
composition) across the layer thickness is an indicator that
its structure was determined in the initial stage of deposi-
tion. The phase composition of such an alloy is determined
by the interaction of the initial deposit layers with the sub-
strafe. Changing the deposition mechanism in the initial
stages influences the properties of later layer growth.
In part I of this paper (p. 1299), hydrogen codeposition
with nickel during Ni-Zn electrodeposition was shown to
be an important determinant of structure. In this sequel,
the influence of initial deposition of hydrogen, as well as
nickel and zinc, on the electrocrystallization of Ni-~n alloy
is investigated by a nucleation study.
The formation of alloy phase structure depends on the
nucleation rate and on the competition between nucleation
and growth, i.e., on the nucleation mechanism. Although
the details of phase formation are not yet clear, there are
several main pathways by which phase structures can be
formed. For example, one pathway is individual nucleation
of each species, without interaction between the nuclei.
This may cause either an alloy phase, which is a solid solu-
tion, or a phase which has a small amount of one species
inserted in the matrix of the other major species. Which of
these two cases occurs depends on the type of nucleation;
instantaneous nucleation tends to lead to the former, and
progressive nucleation to the latter. The final phase struc-
ture also depends on the mass-transfer and kinetic limita-
tions of the reactions. A second pathway is that an interme-
diate phase forms by direct interaction between two types
of nuclei.
Here, the interactions of components during the initial
stages of deposition were investigated by nucleation analy-
sis using a potential step technique.
* Electrochemical Society Student Member.
** Electrochemical Society Active Member.
1304 d. EIoctrochoro. Soc., Vol. 140, No. 5, May 1993 @ The Electrochemical Society, Inc.
A three-electrode cell was used to generate the Ni-Zn
alloy. A glassy carbon rotating disk electrode (RDE) was
used as the working electrode. A smooth platinum foil and
a standard calomel electrode were used as the counter and
reference electrodes, respectively.
The plating solution was prepared to have the composi-
tion (0.92M ZnC12 + 0.58M NiC12) with p H 1.6 adjusted by
adding acetic acid. A fitted tube near the edge of the RDE
working electrode sparged nitrogen to prevent formation of
an oxide layer and to remove bubbles adhering to the elec-
trode surface. The reference electrode was situated close to
the edge of the working electrode so as not to interfere with
the current distribution.
The working electrode potential was controlled by a po-
tentiostat (PAR 273) via the controller, an IBM PC-AT per-
sonal computer. The pulse function was generated by a
function generator (PAR 175). The chronoamperometry and
the chronopotentiometry were recorded by a Nicolet 310
oscilloscope.
Experimental technique.--Even though chronoampero-
metric (potential-step) study of an electrodeposition pro-
cess is a powerful techique and is widely used to explore the
nucleation mechanism of pure metal deposition, there are
several difficulties in applying this technique to study the
nucleation mechanisms of alloys. One problem is that one
obtains a mixed-current response, determined by the ki-
netics of two or more reacting species involved. This
mixed-current response must be separated from the chron-
oamperometric response due to the growth of either zinc or
nickel nuclei. Because the initial nucleation layer is in a
transient state, an in situ analysis technique is needed to
explore the current response of each species. Furthermore,
the very short time necessary to form the transient layer
compounds the difficulties of studying the nucleation
mechanisms involved in alloy deposition.
To solve these problems, a deconvolution technique was
designed to gain kinetic information about Ni-Zn elec-
trodeposition from the mixed-current chronoamperomet-
tic response. This technique is based on computer-con-
trolled instrumentation applied to the chronoamperometry
and galvanic stripping analysis of the deposit.
The transient of the overall depositioin current, meas-
ured experimentally, can be translated into the coulombic
charge transient as shown in Fig. 1. The coulombic charge
in this figure is obtained from Eq. 1
Qn(tn) = i(t)dt [1]
Here Qn is the overall eoulombie charge forming the deposit
upon applying a potential step during deposition time to.

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 J. Electrochem. Soc., Vol. 140, No. 5, May 1993 9 The Electrochemical Society, Inc. 1305

For m species involved in the charge transfer reactions Galvanic Stripping

leading to the alloy deposition, Eq. 1 can be extended as
follows
Ni dissolving from
Qn(t.) = ~ Qk(tn) porous Ni layer Is ( iaaoaic)
k=l
[2] ...........................................

Zn dissolving I
= ik dt from r phase i
= Zn dissolving . T
from 11+'/ phases | J
Here Qk represents the coulombic charge of species k dur- E
ing deposition (t = t,) The partial current contributed by
each species may be obtained from Eq. 3

Q~(t.)
ik(t.) = ~ • i.(t.)
Here ik and in are, respectively, the partial current of spe-
cies k and the total mixed-current response, for deposition
time tn. Equation 3 can be used as long as the interval of
deposition time At is very small (Fig. 1). Experimentally,
the interval of deposition time can be controlled precisely,
i To obtain the partial current transient of each species,
g which provides an in situ analysis of the partial coulombic
[3]
1 ./
I Iml
0
time tA tB
Fig. 2. Anodic chronopotentiogram of Ni-Zn deposit by galvanic
stripping, deposition time t = tn.
via a computer-controlled potentiostat, to within a few
milliseconds. In the present case, At is set to 4 ms.
the variable that must be determined in Eq. 3 is the partial
coulombic charge transient contributed by each species.
This can be achieved by the galvanic stripping method,
charge of each species during alloy deposition by applying
an anodic current step (10 ~A - 1 mA) which dissolves the
alloy deposit. From the potential response during dissolu-
tion, it is possible to gain the coulombic charge information

4'
I I of each species in the alloy. Figure 2 shows the chronopo-
I I tentiogram of Ni-Zn alloy dissolution.
I I The interpretation of the dissolution mechanism of Ni-
Zn has been reported previouslyJ Three plateaus normally
Eo ', are found in the anodic chronopotentiogram of a Ni-Zn
alloy. These plateaus represent the dissolution of different
I I ..... I ...... I species from different alloy phases. Zinc is dissolved first
I I I from the ~ and 7-phases. The second plateau also is due to
zinc dissolution, but this time from the s-phase. After the
h dissolution of zinc, nickel starts to dissolve from the porous
structure left after stripping the zinc metal. By analyzing
the chronopotentiogram of the Ni-Zn deposit immediately
time after deposition the partial coulombic charge of a species
may be obtained using Eq. 4
Q
Q~ = i~nodicx tk [4]

,/ Here i,no~ is the dissolution current applied; tk is the time

during which species k dissolves from the alloy deposit.
Results and Discussion

,/
Nucleation of zinc from ZnCl2 + KCl solution.--The
0 chronoamperograms of electrodeposition of zinc at differ-
ent applied potentials on glassy carbon are shown in Fig 3.
The current density increases in the initial stages of nucle-
8 ation. Then, after reaching a maximum current, it de-
creases and finally reaches a steady state. In the literature,
& both mass-transfer control 5 and charge-transfer control*
during the nucleation and growth process lead to a peak
ci similar to that of Fig. 3. Therefore, to clarify the nature of
this peak, the effect of convection on nucleation and
4 growth was investigated.
II, I Figure 4 indicates that the nucleation of electrodeposited
zinc is controlled by mass transfer of zinc ion. If one in-
0 tlt2 ti tn creases the rate of convection (to e.g., 1000 rpm for the
time RDE) the current peak disappears and a steady-state cur-
rent plateau is reached. The electrodeposition of zinc is a
mass-transfer-controlled process. Convection can over-
come the mass-transfer limitation, in part, and the rate
At = t. - process then is controlled by both kinetics and mass trans-
fer. When the applied potential is very negative (cathodic),
Fig. I. Reconstructionof overall chronoamperogram of alloy depo- mass-transfer limitation at the same rate of convection is
sition. still very strong and influences the nucleation process.

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 1306 J. Electrochem. Soc., Vol. 140, No. 5, May 1993 9 The Electrochemical Society, Inc.

0.5 Table I. Kinetic information on zinc nucleation contained

in chronoamperograms at a stagnant and an RDE.
1 - Eap=-l.245 V
Eap 2 - Eap=-l.225 V
3 - Eap=-l.205 V P(C 2 9s -~ 9cm -3) 0.033 experimental
S(C. s -3/2 . cm -2) 7.610 experimental
,,_~0.4 -- 4 - Eap=-l.185 V t~(s) 0.005 experimental
e~ L 5 - Eap=-l.165 V C(M) 2 0.885 Eq. 6
D(cm . s -1) 6.85 x 10 -6 Eq. 7
N ( s i t e 9 cm -2) 3.113 x 10 § Eq. 8
N(site 9cm -2) 3.145 X 10+6 Eq. 9
0.3 Iss(A 9cm -2) 0.59 experimental
Iss(A 9cm -2) 0.52 Eq. A-7

4 Applied voltage = -1.40 V; v = 0.008973 cm 2 9s-l; and oJ(RDE) =

,~ 0.2 -5 16.67 s -1.

zinc electrodeposition. (First, the t i m e to reach a current

~ o.1
I I
0
0 0.5 1 1.5
Time (s)
Fig. 3. Chronoamperograms of zinc elec~'odeposition from ZnCI2
solution under different applied potential.
Hills 3 has p o i n t e d out t h a t in such a m a s s - t r a n s f e r - c o n -
trolled nucleation, the occurrence of a current p e a k is due
to the coalescence of the diffusion zone of the h e m i s p h e r i -
cal g r o w t h nuclei. Based on this hypothesis, it m a y be as-
s u m e d t h a t a h e m i s p h e r i c a l diffusion zone develops from
each nucleus and grows o u t w a r d w i t h a r a d i a l velocity
given by 3
St = ( k D t ) u2
Here 3t is the diffusion zone; k is a constant; and D is the
diffusivity of the reacting species. However, as the radius of
the g r o w t h center increases and the h e m i s p h e r i c a l diffu-
sion zones of various nuclei begin to overlap, the supply of
m a t e r i a l from the planes close to the electrode surface be-
comes restricted. E v e n t u a l l y the only source of reacting
species is the diffusion t o w a r d the surface in the direction
n o r m a l to the electrode surface. The diffusion p a t h be-
comes t h a t of linear diffusion t o w a r d a f r a c t i o n of the elec-
trode surface. This hypothesis can e x p l a i n the current
peaks in Fig. 4.
In the initial stages, the current t r a n s i e n t is the same in
the convected and c o n v e n t i o n - f r e e c h r o n o a m p e r o g r a m s of
0.8
-- with c o n v e c t i o n
without convection
k
p e a k is the same in each case and, second, the p e a k current
changes little w i t h m o d e r a t e applied convection.) A m a t h e -
m a t i c a l m o d e l of the initial stages of n u c l e a t i o n and g r o w t h
for a s t a g n a n t and an R D E is given in the A p p e n d i x .
The key e x p e r i m e n t a l p a r a m e t e r s in this m o d e l are as
2 follows:
S, the slope of the I vs. t ~ curve (n equal to 89here), w h e r e
the v a l u e of n depends on w h e t h e r the n u c l e a t i o n m e c h a -
nism is i n s t a n t a n e o u s or progressive; and
P, the p r o d u c t of m a x i m u m current squared and t i m e at
the current m a x i m u m in a current transient. This is a po-
t e n t i a l - i n d e p e n d e n t c o n s t a n t and can be used to character-
ize the n u c l e a t i o n mechanism.
The m o d e l relates these macroscopic p a r a m e t e r s to the
m o l e c u l a r parameters, the nuclei density N, the diffusivity
of the reacting species D, and the c o n c e n t r a t i o n difference
b e t w e e n b u l k and electrode surface C. U s i n g this model,
the values of C, D, and N can be o b t a i n e d s i m u l t a n e o u s l y
from the convecteti and convection-free c h r o n o a m p e r o -
[5] g r a m s of zinc deposition, as shown in Eq. 6-8.
C=26.32(zF) 4/~(M)I/3.ps-2/3.N2/3 [6]
M)-2/3
D = 0.00886 ( Z F ) 2/3 9 P 1S4/~ 9 N -4/3 [7]
M -i/2
N = 0.199 ( z F ) 1/2 . p3/2S-7/2tog/4t[9/4 v 3/4 [8]
The i n d e p e n d e n t variables P, S, and t~ are o b t a i n e d from the
current t r a n s i e n t of a s t a g n a n t electrode. The value of t~ is
o b t a i n e d from the intersection of the dip current following
the current p e a k w i t h the initial slope in a log-log plot (see
the u p p e r transients in Fig. 4). D and C t h e n can be ob-
t a i n e d simultaneously, once the value of N is known.
Table I shows the kinetic i n f o r m a t i o n o b t a i n e d w i t h
Eq. 6-8 from the c h r o n o a m p e r o g r a m s of Fig. 4, u n d e r con-
ditions of high applied cathodic potential.

~ 0.6
The steady-state current calculated from the values of D
and C in Table I is less t h a n the e x p e r i m e n t a l current at an
RDE. This is becasue the convected current transients in
Fig. 4 do not reach steady state. The e x p e r i m e n t a l diffusiv-
ity is close to the v a l u e r e p o r t e d in the literature (about 3 %
0.4 lower). The surface c o n c e n t r a t i o n is almost e q u a l to zero,
w h i c h indicates that m a s s - t r a n s f e r resistance controls the

0.2
S F~p = - 1.40 V
rate process.
E q u a t i o n A-12 is an a p p r o x i m a t e solution w h i c h yields
the ~/alue of the p a r a m e t e r p.3 A t high cathodic potentials,
it fits the e x p e r i m e n t a l data well. At low cathodic p o t e n -
- 1.30 V tial, Eq. A-12 is not e x a c t and therefore Eq. 8 is not a p p r o -
- 1.245 V
priate. An a l t e r n a t i v e is to treat the diffusivity as an inde-
p e n d e n t v a r i a b l e (i.e., as a k n o w n value). Then, Eq. 8 can be
0 I I I I r e p l a c e d by
0 0.2 0.4 0.6 0.8 1
N = O.O549 (zF)l/2(M)-I/2 . S-1/2 . D-1/2~3/4t:~/%-l/4 [9]
Time (second)
Fig. 4. Chronoamperograms of zinc electrodeposition with/with- and D can be o b t a i n e d from c h r o n o a m p e r o g r a m s at high
out convection; rotating rate, 1000 rpm. cathodic potential.

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 J. Electrochem. Soc., Vol. 140, No. 5, May 1993 9 The ElectrochemicalSociety,Inc. 1307
Table II. Nucleation parameters of Zn deposition from 0.6
a ZnCI2 solution at different applied potentials
(assuming instantaneous nucleation).
0.5
E~ S C D N t,
(c 9 s - m . cm -2) (M) (em 2 - s -1) (site 9 -2) (s)

-1,245 4.392 1.095 6.85 x 10 -8 1.32 • 106 0.022 ~ 0.4

-1.225 3.776 1.059 6.85 • 10 -6 1.19 • 106 0.028
-1.205 2.962 0.941 6.85 • 10 -6 1.12 • 106 0.0357
-1.185 1.822 0.657 6.85 • 10 -~ 1.18 • 10~ 0.0485 "~
0.3
e~

U s i n g a c o m b i n a t i o n of c o n v e c t i o n a n d n o n c o n v e c t i o n 6 0.2 s // c E" -1.3o~v vs.

c u r r e n t t r a n s i e n t s , t h e n u c l e a t i o n c h a r a c t e r i s t i c s of zinc // 4.245 v vs. scE
e l e c t r o d e p o s i t i o n a n d t h e d i f f u s i v i t y of zinc i o n are found. [ -1.225 Vvs. SCE
The d i f f u s i v i t y of t h e zinc ion w a s o b t a i n e d f r o m t h e h i g h 0.1
c a t h o d i c p o t e n t i a l r a n g e d a t a , as s h o w n i n T a b l e I. T h e
nucleation characteristics at different applied cathodic po-
t e n t i a l a r e s h o w n i n T a b l e II. P r o g r e s s i v e n u c l e a t i o n a p - 0 I I I
p e a r s w h e n t h e a p p l i e d p o t e n t i a l is b e l o w - 1 . 1 8 5 V. T h i s is 0.5 1 1.5
i n d i c a t e d b y t h e a b r u p t d r o p i n ion c o n c e n t r a t i o n a n d b y Time (second)
i n c o n s i s t e n c y of t h e d e c r e a s e of n u c l e i d e n s i t y w i t h de-
crease of a p p l i e d c a t h o d i c p o t e n t i a l . T h i s i n c o n s i s t e n c y is Fig. 6. Chronoamperograms of nickel from chloride solution.
d u e to t h e i m p r o p e r a s s u m p t i o n of i n s t a n t a n e o u s n u c l e -
a t i o n a t t h e a p p l i e d p o t e n t i a l , - 1 . 1 8 5 V.
Nucleation of nickel from NiC4 + KCl solution.--Fig- Similarly, the first peak occurring in convection-free
u r e 5 i l l u s t r a t e s t h e c u r r e n t t r a n s i e n t s of n i c k e l e l e c t r o d e - chronoamperograms of Ni deposition (Fig. 7) corresponds
position from a NiCI2 + KCI solution at different applied to the codeposition of [~-Ni as well as a small amount of
potentials. The chronoamperograms obtained are peak- a-Ni nucleation. The second peak apparently corresponds
current transients similar to those of zinc electrodeposi- to the dominant nucleation of a-Ni. When convection is
tion. However, in nickel deposition, the chronoamperogram applied the formation of ~-Ni is increased. This causes the
shows two overlapping peaks: a small peak followed by a current transient to have a single peak (by combination
larger current peak. If the applied potential is made more with the second peak), similar to the case described by
cathodic (Fig. 6), the first peak becomes larger than the Fleischmann et al. Other evidence which matches the con-
second. clusions of Fleischmann is the increase of codeposition of
Further investigations show that convection increases ~-Ni when the applied cathodic potential is increased. At
the peak current (Fig. 7). These results indicate that within low applied cathodic potential (Fig. 5 or 7) the kinetics
the range of potentials applied in this experiment, the nu- become sluggish, and therefore the second peak also starts
cleation of nickel is controlled by mass transfer. to decay, (i.e., the rate of nucleation is controlled increas-
Fleischmann et al. 7 have reported that in charge-trans- ingly by a mixture of mass transfer and kinetics).
fer-controlled nucleation of nickel from acidic solutions at
a glassy carbon electrode, the current transient initially is Nucleation of Ni-Zn from chloride solution.--The p a r t i a l
due to the eodeposition of H-Ni solid-solution, mostly as c u r r e n t t r a n s i e n t s of zinc, nickel, a n d h y d r o g e n ion i n a
-Ni. This codeposition is made possible by the supply of chronoamperometric study can be deconvoluted by anodic
H + ions. In the later stages, the supply of H § ions becomes s t r i p p i n g analysis. F i g u r e 8 s h o w s t h e d e c o n v o l u t e d cur-
the rate-limiting factor, as the hemispherical diffusion r e n t t r a n s i e n t s of e a c h species for d e p o s i t i o n a t - 1 . 2 0 5 V
fields surrounding the growth centers overlap and deple- potential. The two major electrode reactions during the
tion occurs. Eventually, the partial current transients of deposition are zinc deposition and hydrogen evolution.
~-Ni pass through a maximum and become fully mass-
transfer controlled~while the growth of c~-Ni continues.
0.6
-- with convection
"'" ~-- -- without convection
0.5
0.4
0.4
i 0.3
9~ 0.3
o
~ 0.2 F / i f / / -1.245 V vs. SCE 4.1
I///// ol.225 Vvs. SCE = 0.2
[//// -1.2o5 v vs. s c E /' F~p = - 1.40 V
- . .

[ - - 1.30 V
0.1 0.1 - 1.205 V

0 I I I
0 0 0.5 I 1.5 2
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
T i m e (s)
Time (s)
Fig. 7. Chronoamperograms of nickel from chloride solution with/
Fig. 5. Chronoamperograms of nickel from chloride solution. without convection at different applied potentials.

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 1308 J. Electrochem. Soc., Vol. 140, No. 5, May 1993 9 The Electrochemical Society, Inc.

0.14 0~18
-2.4 '

0.12 "" ~ ~ 9 -26

slope = 2.5
9 o~l "N
-2.8

-3
~. 0.08 /- 9 "{Ni
0 -3.2
0.06 ca)
-3.4
~0.04
-3.6

0.02 -3.8
@ 9 9 9 9 9 9 9

0 I I l
0.02 0.04 0.06
Time (s)
Fig. 8. Deconvolution of the chronoamperogram of Ni-Zn deposi-
tion; Eap = - 1.205 V vs. SCE.
However, the HER decays quickly from the initial stages Of
deposition.
In Fig. 10, the cathodic coulombic charge of zinc shows a
linear relationship with t ~/2in the initial stages. This indi-
cates that mass-transfer-controlled progressive nucleation
of zinc occurs at -1.205 V which is similar to the nucle-
ation and growth mechanism of pure zinc. The decay of the
HER (Fig. 8) is understandable because the n u m b e r of hy-
drogen nuclei is reduced as they are crowded out by the
progressive nucleation of zinc; hydrogen nucleation is lim-
ited by mass transfer and by the kinetics of dissociation of
low activity H + ions from acetic acid. This results in the
abrupt increase of cathodic efficiency shown in Fig. 11.
The current transient of the nickel partial current shows
the two-peak type of current-transient described earlier
(Fig. 9). In the case of nickel this two-peak transient is, as
mentioned in the discussion of Fig. 5, due to the formation
of ~-Ni and ~-Ni. The nickel content in the alloy decreases
sharply from 55 weight percent (w/o) to 6 w/o within 50 ms,
then reaches a plateau. The Ni content at the plateau is
close to the average nickel content in a thick Ni-Zn alloy
deposit (7-8 w/o Ni). This low nickel content has been inter-
preted as the result of unfavorable kinetics of nickel depo-
sition on the electrode surface?
~ I l -4
0.08 0.1
-4.2 I I I I
-1.8 -1.6 -1.4 -1.2 -i -0.8
log t
Fig. 10. The coulombic charge transient of zinc in the nucleation of
Ni-Zn alloys; Eop = -1.205 V vs. SCE.
However, as demonstrated above, in the initial stages of
alloy deposition, high nickel content is observed due to the
codeposition of hydrogen atom and nickel nuclei (as ~- or
~-Ni). This enhanced nickel deposition due to hydrogen
codeposition also agrees with two observations,(/) the very
low cathodic efficiency in the initial stages increases
steeply Within 60 ms. Apparently, the nucleation of hydro-
gen is more 'favorable than the nucleation of zinc in the
first 60 ms of the deposition process (Fig. 11). (ii) The de-
crease of ~-Ni formation is accompanied by a decrease in
nickel content of the deposit during the initial stages of
deposition.
Thus, comparison of the nucleation mechanism of nickel
in pure nickel deposition and in Ni-Zn alloy deposition
shows that the nucleation mechanism is similar in various
stages of the deposition process. This may be concluded
from Fig. 12, where the two nickel charge transients have
the same slope in the initial stages of nucleation. The simi-
larity of the slope indicates that the pure nickel nucleation
mechanism mentioned above may be used to fit the partial
current transient of nickel nucleation during Ni-Zn depo-
sition. Thus, the surface concentration and nucleation
parameters may be obtained from the fitting.

0.018 . . . . 1

0.016
0.8

~ 0.014
o t
~0.6
._~
0.012

/
0.4
0.01
6
0.2
0.008

0.006 I I I I I 0 I I I I I
0.02 0.04 0.06 0.08 0.1 0 0.02 0.04 0.06 0.08 0.1 0.12
Time (s) Time (s)
Fig. 9. The chronoamperogram of the nickel partial current in Fig. 11. Nickel content of the Ni-Zn deposit and the cathodic cur-
Ni-Zn electrodeposition, Eop= - 1.205 V vs. SCE (two-peak transient). rent efficiency of Ni-Zn deposition; Eop = - !.205 V vs. SCE.

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 J. Electrochem. Soc., Vol. 140, No. 5, May 1993 9 The Electrochemical Society, Inc. 1309

(A) slo - ,
-1.8 i i i
0.02
-2 9 ~l~rimeat
curve fit
-2.2 e,i
~ 0.015
-2.4

~-2.6
Q
-2.8 "~" 0.01

-3
-3.2
0.005
I It" i I If I I -- ~
-3.42. 2 -2 -1.8 -1.6 -1.4 -1.2 -1 -0.S -0.6
log t
I | I I
-3.2 . . . . . . 00 0.02 0.04 0.05 0.08 0.1
slope = 1 . 4 5 / Time (second)
-3.4
Fig. 13. Simulation of nickel nucleation in the initial stages of Ni-Zn
-3.6 (B) deposition.

-4.2
-4"4-2 -1.8 -1.6
Fig. 12. The coulombic charge transient of:. (A) pure nickel nucle-
ation; and (B) nickel nucleation of Ni-Zn alloy.
An instantaneous mass-control nucleation mechanism
with hemispherical growth yields the best fit of the experi-
mental data. The total nickel current transient is obtained
by adding the partial H-Ni currents. The set of equations in
this simulation is as follows
as high as 97% (Fig. 13). The low SCF of [3-Ni indicates that
the formation of ~-Ni solid solution has been inhibited by
the decrease of the surface available for hydrogen atom
adsorption. This reduction of the surface covered by hydro-
gen adsorption may be due to the existence of zinc nuclei
which block the surface. Some evidence of the competing
I ! ! nucleation of zinc deposition and hydrogen adsorption/
-1.4 -1.2 -1 -0.8 evolution can be found in Ref. 10. That an instantaneous
log t nucleation mechanism is observed for both ~-Ni and ~-Ni
during Ni-Zn deposition, qompared with a progressive nu-
cleation mechanism for pure nickel deposition (Table IV), is
not surprising because the available nucleation sites of
nickel have been occupied by zinc nuclei.
From a plot on extended time scale, we see that the fit-
ting equations no longer represent the actual current tran-
sient. This result implies that interaction between zinc and
nickel nuclei may occur after the growth centers on the
electrode surface coalesce.

I~ = ~ [1 - exp (-B~,~. t)] [10]

I~ - ~ -t~/2
~ r L1 - exp (-B2, 9 9 t)]
where B~ and B2 are constant, and ? is the surface concen-
tration factor (SCF) which indicates the degree of concen-
tration difference between the bulk concentration and the
concentration at the electrode surface.
The diffusivity of nickel ion is assumed to be identical in
the formation of ~-Ni and ~-Ni. The value of B~ is known
from the values of bulk concentration and diffusivity (7.1 •
10 -~ cm 2 - s -~ obtained from the paper by Chapman et al. 9)
of the nickel ion. (Comparing Eq. 10 and A - l ) The values of
SCF, % which indicates the approach to zero surface con-
centration, and of B2 are obtained from a least squares fit.
The number of available nucleation sits (N) is calculated
from the values of "y and B2 using Eq. A-1 (Appendix).
Table III shows the simulation results. The low SCF of
B-Ni indicates that less nickel ion is needed to form the
high-hydrogen-content B-Ni. The correlation coefficient is
Conclusion
This study of the nucleation mechanism indicates that
the deposition of N i - Zn in the initial stages involves com-
[11] peting reactions of zinc and nickel, as well as hydrogen
adsorption/evolution. The phase formation in the Ni-Zn
alloy deposit is determined to a significant extent by the
growth pattern in the initial stages. The interaction be-
tween zinc and nickel nuclei or growth centers decides
which Ni-Zn phase is formed. This interaction between
zinc and nickel growth centers does not exist (or only very
weakly) in the initial stages of the nucleation and growth
process. This noninteraction is shown by the similarity of
the nickel nucleation mechanism in pure nickel deposition
and in Ni-Zn deposition.
In the initial stages of deposition, nickel and zinc nucle-
ation and growth are influenced by the kinetics of the re-
acting ion reduction process at the interface of substrate
and solution, and also by the character of hydrogen adsorp-
tion/desorption on the substrate. Weak adsorption of hy-
drogen atoms (H) on the substrate enhances nickel nucle-
ation through the formation of H-Ni solid solution (the ~-

Table IIh Resultsof optimal curve fitting of the Table IV. Curve fitting results for the chronoamperogram
chronoamperagram of nickel deposition in the of nickel deposition in the initial stages of deposition.
initial stages of Ni-Zn deposition.
ANo ~ ANo
N~ N~ Convection ~ % (s. crn-~) (s - cra -4)
-y~ ~o (s. cm 4) (s 9 c m - 4 )
No 0.713 0.97 4.19 • 10§ 2.74 • 10§
0.012 0.85 4.056 • 10+v 2.295 • 10+4 Yes 0.850 0.97 2.67 • 10+6 2.74 • 10§

D = 7.1 • 10-6 crn2 - s '; C = 0.58M. D = 7.1 • 10-6 cm2 - s-l; C = 0.58M.

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 1310 J. Electrochem. Soc., Vol. 140, No. 5, May 1993 9 The Electrochemical Society, Inc.

and ~-Ni phases). This strong codeposition of H-Ni solid and the other symbols are the same as in previous equa-
solution is the reason for the high nickel content of the tions.
Ni-Zn alloy deposit in the initial stage of deposition. The For linear diffusion normal to the electrode, the current
transient following an applied potential step at an RDE
formation of H-Ni solid solution decreases later9 There is an follows that of a stationary electrode (i.e., the items outside
insufficient supply of adsorbed hydrogen atoms on the sub- the bracket of Eq. A-1 and A-3) 8 when the diffusion layer
strate (due to mass-transfer limitations) and many hydro- thickness is much thinner than 80, i.e., at very short times9
gen atoms become active enough to form hydrogen gas Based on the hypothesis of hemispherical nucleation and
bubbles (H2). These bubbles cover the nickel growth centers growth, a similar situation may be assumed to exist, before
and do not form H-I~i solid solution. In the later stages of the dominant process shifts from surface diffusion to linear
this process, zinc deposition is favored, therefore, the sub- ionic diffusion to the surface, so that the current transient
strate is covered increasingly by zinc deposits. Since hy- at an RDE is identical with that of a stationary electrode.
drogen adsorption is much weaker on zinc than on nickel, This situation explains the identical current transients in
the hydrogen adsorption/evolution reaction is reduced fur- the initial stages of deposition (i.e., before the current
reaches a maximum) for both convected and nonconvected
ther. Both the increase of hydrogen evolution and the cover-
chronoamperometries (Fig. 4).
age of the surface by zinc deposits reduce the nickel content It is possible to use Eq. A-1 and A-3 to obtain the nuclei
of the alloy. density, N, as well as the surface concentation and diffusiv-
Once the nickel and zinc growth centers start to interact ity, simultaneously. As mentioned above, at very short times
with each other, the nickel content of the alloy gradually the current transient follows Eq. A-6
becomes constant due to the redistribution of the deposit
surface free energy. Under this energy rearrangement the lira I~DE(t ) = lim Ist~g~t(t) = ~rzF(2DC) 3/2 t ~/2
t-+0 t-~0
hydrogen evolution is reduced to m i n i m u m on the new sur-
face (i.e., on the alloy layer with a steady-state composi- At sufficiently long times, the current reaches a steady state
tion). Thus, for example, cathodic efficiency reaches 90% at and becomes independent of time
steady-state in this case. The ratio of the deposition rates of
lim IRD~(t) = 0.62zFDmCoJ1/2v 1/6 [A-7]
zinc and nickel then becomes a constant.
Manuscript submitted Sept. 11, 1992; revised manuscript Therefore, two straight lines correspond to Eq. A-6 and A-7
received Jan. 8, 1993. in a log-to-log plot of I vs. t. These can be extrapolated and
intersect at time t~ (Eq. A-9)
T h e I l l i n o i s I n s t i t u t e o f T e c h n o l o g y a s s i s t e d in m e e t i n g
t h e p u b l i c a t i o n c o s t s o f t h i s article 9 lim IRDE(ts)= lim I~DE(t~) [A-8]
APPENDIX
Simulation of the Chronoamperomeh'yof Nucleation ~rzF(2DC) m N . t~/2 = 0.62zFD2/SCcd/2v -I'6 [A-9]
with Convection
In a mass-transfer-controlled nucleation and hemispher- After rearrangement, Eq. A-9 becomes
ical growth process, the current transient, due to nucle-
ation and growth following a potential step, can be ex-
pressed as follows
0~1/2 V1/6 9 D 5 / 6 C 1/2 9 Nts [A-10]
z F D 1/2C - 0.62
/stagnant- Tfl/2tl/2 [ l -- exp ( - N w k D t ) ] [A-l]
D and C can be obtained from the linear slope of I vs. t 1/2
for instantaneous nucleation; and in Eq. A-6 and the peak current 5 of Eq. A-1 with Eq. A-11
and A-12
zFDll2C[1-exp(~ - A N ~ r k 'Dt 2)] [A-2]
/stagnant-- Tfl/2t 1/2 S = ~ f 8 ~ z F ( M ) 1/2 9 (DC)3/2 [A-11]
for progressive nucleation. Here N is the number density of
nuclei; N~ is the n u m b e r of preferential sites for nuclei; A is P = I~maxtm~ = 0.163(zF) 2. D C 2 [A-12]
the nucleation rate constant; D is the diffusivity of the n u - Hence C and D can be expressed in terms of P and S (Eq. A-
cleating species; C is the concentration difference between 13 and A-14)
species at the electrode surface and in the bulk solution; M
is the molecular weight; p is the density of the species; z is
the n u m b e r of electrons transferred; and F is Faraday con- C = 26.32(zF) ,,3 (_M/'S 9 P S -2/3 . N2~ [A-13]
\p/
stant.
The terms inside the brackets in Eq. A-1 and A-2 repre-
sent the effective ratio of surface area coverage when the D = O.OO886(zF)2/3 ( ~ ) 2/3 . p - l s 4 / 3 . N -4/3 [A-14]
coalescence of the diffusion zones of the nuclei is consid-
ered. The rest terms (outside the bracket in Eq. A-1 and Substitute Eq. A-13 and A-14 into Eq. A-11, A-12 and rear-
A-2) represent the linear diffusion of the reacting species range, then
toward the stagnant electrode9 With applied convection,
based on the same procedure of derivation as Eq. A-1 and N = O.199(zF)1/2 (M)-l/2 . P312S-7/2~og/4t[9/% -3/' [A-15]
A-2 ~, the current transients of a RDE 8can be represented as
follows Once the value of N is obtained from experiment (i.e., P and
[1 + (- S), the diffusivity, D, and concentration difference of sur-
face and bulk concentration, C, can be obtained simulta-
neously.
9 [1 - exp ( - ~ k D N t ) ] [A-S]
REFERENCES
for instantaneous nucleation; and 1. M.H. Gelchinski, L. Gal-Or, and J. Yahalom, T h i s J o u r -
nal, 129, 2433 (1982).
2. Electrodeposition of Alloy, N. T. Kudryavtsev, Editor,
IRDE(t) = 2 90.62zFD2/SCcd/2v -lj6 1 + 2 ~ exp 80 /J U.S. Dept. of Commerce, Washington, DC (1964).
m=l
3. S. Swathirajan, T h i s J o u r n a l , 133, 671 (1986).
4. M. Y. Abyaneh, E l e c t r o c h i m . A c t a , 27, 1329 (1982).
9 [1 - exp (- 2 /j [A-4] 5. G. Gunawardena, G. Hills, I. Montenegro, and B.
Scharifker, J. E I e c t r o a n a l . C h e m . I n t e r r a c i a l E l e c -
for progressive nucleation. t r o c h e m . , 138, 225 (1982).
Here co is therotation rate; v is the kinematic viscosity; 80 is 6. Y. R Lin, Ph.D. Thesis, Illinois Institute of Technology,
the steady-state diffusion layer thickness, i.e. Chicago, IL (1991).
7. M. Fleischmann and A. Saraby-Reintjes, E l e c t r o c h i m .
80 = 1.61D1/So~-l/2~1/6 [A-5] A c t a , 29, 69 (1984).

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 J. Electrochem. Soc., Vol. 140, No. 5, May 1993 9 The Electrochemical Society, Inc. 1311

8. A. J. Bard and L. R. Faulkner, Electrochemical Meth- 9. M. E Mathias and T. W. Chapman, This Journal, 34,
ods, Ch. 8, p. 305, John Wiley & Son, Inc., New York 1408 (1987).
(1980). 10. Y. P. Lin and J. R. Selman, ibid., 138, 3525 (1991).

Electrochemical Coloration of Stainless Steel

and the Scanning Tunneling Microscopic Study
K. Ogura,* M. Tsujigo, K. Sakurai, a and J. Yano
Department of Applied Chemistry, Yamaguchi University, Ube 755, Japan

ABSTRACT
The generation and topography of interference films on stainless steel in a mixture of chromic and sulfuric acids have
been studied by electrochemical and scanning tunneling microscopic (STM) methods. The psychometric chroma coordi-
nates of the colored film were determined as a function of the extent of anodic polarization, and the results indicated that
red and green were susceptible to the change in potential. In other words, it is very difficult to reproduce a desired color
in a wide range by the chemical coloration. Using the electrochemical method, however, any color can be always reproduced
by regulating the extent of anodic polarization, and the coloration could be suspended at any stage if the colored specimen
was polarized to more negative potential. The STM measurement disclosed that the interference film on stainless steel
consists of small crystallites (5-10 n m in diameter) and pores (about 5 nm) and is uniform for the most part.

It is known that a film exhibiting interference colors is
formed on stainless steel when it is immersed in a hot solu-
tion with chromic and sulfuric acids. I-~ The interference
color depends on the duration of immersion, the concentra-
tion of acids, the temperature of solution, and the proper-
ties of steel. The film is considered to have a spinel struc-
ture, to be heavily hydrated, and to be porous. I During the
formation of the interference film on steel, the spontaneous
potential shifts to the positive direction, and the rise in
potential is almost proportional to time. ~ These facts are
very interesting from a fundamental as well as a practical
standpoint, but the nature of such phenomena is not fully
understood.
In this paper, the reaction of formation of the colored film
and its topography have been investigated by means of
electrochemical and scanning tunneling microscopic
methods.
Experimental
Specimens (0.5 mm thick and 20 cm ~ in apparent area)
were cut from annealed Type 304 stainless steel sheet
[Cr 18; Ni 8; Mn 0.8; Si 0.5; Cu 0.1; C 0.06; N 0.03; P 0.03; S
0.07; Sn 0.003 weight percent (w/o)]. Each specimen was
degreased in ethanol and then electroreduced at a current
density of 1 m A c m -2 for 15 min in 1M (mol dm -3) nitric acid
solution. Pretreated specimens were thoroughly rinsed
with distilled water prior to testing. The electrochemical
experiment was performed in a mixture of 2.5M chromic
and 5M sulfuric acids at 70~ This is a typical coloring
solution for stainless steel. I
Electrochemical measurements were made with a three-
electrode system composed of test, counter-, and reference
electrodes. The counterelectrode was a platinum plate. A
platinum wire was used as a pseudoreference electrode,
and the potential of this electrode in the coloring solution
was +0.87 V vs. a .saturated calomel electrode. This poten-
tial was maintained constant at least for 24 h, and the Pt
wire reference electrode is considered to be very stable in
the coloring solutions. The spontaneous potential of the
stainless steel in the coloring solution varied in the manner
shown in Fig. i. First, the potential ascended rapidly from
a value at immersion of about -0.22 V (vs. Pt) to a peak
value of -0.195 V, from which it dropped to a minimum
value (E*) of -0.215 V. The potential ascended again to
attain a second peak at -0.181 V. In the potential range
* Electrochemical Society Active Member.
a Present address: Shunan Works, Nisshin Steel Co., Ltd.
from -0.215 to -0.181 V (i.e., 34 mV), the film causing
various interference colors was formed on the surface of
the steel. Beyond the second peak, the potential again
dropped slightly, and the potential stayed steadily at a
value of -0.186 V.
In the present experiment, the specimen was anodically
polarized to a potential between -0.215 and -0.181 V
when the spontaneous potential reached to E*. As de-
scribed below, the external current changed from a positive
to a negative value. The specimens were removed when the
external current became zero, and they were used as spec-
trophotometric and scanning tunneling microscopic (STM)
samples after having been rinsed thoroughly with distilled
water and dried in vacuum. As another experiment, the test
electrode was polarized to more negative potential (e.g.,
-0.25 V vs. Pt) immediately after the external current
reached to zero, and maintained at that potential for a
given time.
The expression of color is given by the chromaticity dia-
gram, and the color is defined by one point in the color solid
with three elements of hue, brightness, and chroma as
shown in Fig. 2. The point is described as (L, a, b) in the
rectangular coordinates. In the chemical coloration o f
steel, the hue is the only parameter that can be controlled
by changing the treatment time and the aggressiveness of
the solution. The value of psychometric chroma coordi-
nates (a, b) and brightness (L) were measured by means of
a colorimeter (H-CT, Suga Test Instruments).
Spectral reflectance of the colored steel was measured
with a Shimadzu UV 2200 spectrophotometer for wave-
lengths between 190 and 900 nm. An integrating sphere
refiectometer was used to measure the hemispherical-di-
rectional reflectance. The topography of the specimens was
determined by STM to investigate the surface condition on
the colored steel. The STM apparatus used was a Nano-
scope II (Digital Instruments, Incorporated), and the tip
was a 125 ~m diam Pt-Ir (80/20) wire.
Results
Anodic polarization.-- The potential of the stainless steel
in the coloring solution was decayed at open circuit until it
reached to E*, and then various anodic polarizations (hE =
E - E*) were applied. The change in potential in this proce-
dure is shown in the inset of Fig. 3. The external current is
plotted vs. the time reckoned from the beginning of the
polarization, showing the current variation from positive
to negative value following a maximum (Ip). The deviation
(AI = Ip - I) of the positive current from Ip is plotted vs. time

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