J. Electrochem. Soc., Vol. 143, No. 12, December 1996 © The Electrochemical Society, Inc.

3895

throughput compared to serial nanofabrication processes. REFERENCES

The process is reproducible and reliable when openings
down to 60 nm diam have to be fabricated in films with a
thickness not exceeding half the diameter of the masking
nanoballs. Using titanium as an adhesion layer, the mech-
anical stability of the deposited gold structures is good
enough to withstand mechanical, chemical, and electro-
chemical treatments.
Nanostructuring has so far only been investigated in
detail using 60 nm particles, which is optimal considering
the dimensions of biomolecules and the restrictions of the
process. At much larger diameters, it is to be expected that
evaporated metal deposits underneath the masking parti-
cles leading to blurred edges. Furthermore, it is certainly
not reasonable to use the process in a range where litho-
graphic techniques allow a fast and easy fabrication of
regular structures. On the lower end of the scale, there is a
natural limit to the process when the diameter of the
nanoballs is of the same order of magnitude as the grain
size of the evaporated metal.
Acknowledgment
Thanks are due to Daniel Jeggle for the preparation of
the nanostructured samples. This work was supported by
the Swiss National Science Foundation, Priority Program
Biotechnology, Grant No. 5002-035137.
Manuscript submitted March 18, 1996; revised manu-
script received July 29, 1996.
Paul Scherrer Institut assisted in meeting the publica-
tion costs of this article.
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Oxidation of Zinc inAlkaline Solutions Studied by

Electrochemical Impedance Spectroscopy
Ming Cai* and Su-Moon Park*
Department of Chemistry, The University of New Mexico, Albuquerque, New Mexico 87131, USA

ABSTRACT
Electrochemical dissolution and passivation reactions of zinc have been studied in 1.0 M KOH solutions by electro-
chemical impedance spectroscopy. Equivalent circuits have been worked out by simulating the impedance data and using
the results to model the dissolution and passivation reactions. A Tafel plot constructed from the charge-transfer resis-
tances provides an exchange current of 0.11 A/cm 2 and an a value of 0.36 for zinc oxidation. The maximum rate of zinc
oxidation is observed at about -1.30 V vs. the Hg/HgO reference electrode as judged from the charge-tranfer resistance
minimum obtained from impedance measurements. A negative polarization resistance with a reverse semicircle on the
Nyquist plot illustrates the transition process from an active to passive potential region at -1.10 V. At high anodic over-
potentials, the zinc electrode behaved as a semiconductor electrode due to a compact ZnO passive film formed on the elec-
trode surface.

Introduction low anodic overpotentials in an active dissolution re-

gion.'- 3 This conclusion was first reported by Dirkse' from
Numerous investigations have been conducted on the
their electromotive force (EMF) measurements and sup-
dissolution and passivation of zinc electrodes in alkaline ported later by Fordyce and Baum 2 from Raman and IR
solutions of various concentrations in the past few
spectroscopic studies, and Newman and Blomgren 3 from
decades. '-5 As batteries employing zinc electrodes, includ-
nuclear magnetic resonance studies. However, the mech-
ing zinc/air and Zn/NiOOH cells, show a great deal of
anism of anodic dissolution is still not well understood,
promise for applications to electric vehicles, the electro-
and those proposed by Farr and Hampson, 4 Bockris, 9 and
chemistry of zinc oxidation has received considerable at-
others need to be further confirmed.
tention. Since the characteristics of dissolution and passi-
The electrochemical passivation reaction of zinc elec-
vation reactions of zinc electrodes in alkaline solutions
trodes and the properties of the passive films formed
determine the performance of the zinc electrode, a better on the electrodes have also been studied by many
understanding of these processes is crucial to improving
groups. 5 - 8 '0-'3 Most of the investigators in this area believe
cell performance such as minimizing capacity losses and
that the passive films are composed of ZnO. In situ spec-
lengthening shelf lifetimes.
troelectrochemical studies on the subject also showed that
A variety of techniques have been used to study the
the passive film consists of heavily doped semiconducting
kinetics and mechanism of dissolution of zinc elec-
ZnO.4 Three different models, i.e., a dissolution-precipita-
trodes.- 5 9' 3 -5 There is a general agreement that the pre-
tion model's an adsorption model, 5 and a nucleation and
dominant oxidation products are soluble zincate ions at
growth model,' 6 have been proposed to describe the mech-
* Electrochemical Society Active Member. anism of the passivation process. However, it has been

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 3896 J. Electrochem. Soc., Vol. 143, No. 12, December 1996 © The Electrochemical Society, Inc.
concluded that no single mechanism is wholly satisfacto-
ry.5 This is because it is not easy to conduct the kinetic
studies in the passivation region by a conventional elec-
trochemical technique due to an extremely low current.
Cachet et al?. related the electrode kinetics with the mor-
phology of zinc electrodes in the active region by simulat-
ing the electrochemical impedance spectroscopy results.
Aurian-Blajeni and Tomkiewicz conducted a study on the
passivation of the zinc electrode using impedance meas-
urements and proposed a mechanism for the growth of the
passive layers on zinc electrodes. °
We have been studying electrochemical oxidation of
metals and alloys in aqueous media employing electro-
chemical and spectroelectrochemical techniques.14 17 -23 In
the present work, we use electrochemical impedance spec-
troscopy (EIS) to study the dissolution and passivation
reactions and the active to passive transition process of
zinc in 1.0 M KOH solutions. The data analyses were made
by simulating the impedance dispersion spectra. The reac-
tions involved in dissolution and passivation are modeled
using equivalent circuits, and interpretations are made
with the parameters used to fit the observed EIS behavior.
Modeling of electrode-electrolyte interfaces using equiva-
lent circuit components has been reported frequently in
the literature, but their interpretations in terms of chemi-
cal and electrochemical reactions have rarely been made.
In this work we demonstrate that physical and chemical
significances of the components in equivalent circuits can
be discussed in relation to electrochemical and chemical
reactions involved.
Experimental
The working electrode was a well polished disk made of
a 99.9999% zinc rod (Johnson-Matthey Ltd.) with a 5.0 mm
diam. The electrode was made by sealing the rod in a
shrinkable Teflon tubing with only the disk perpendicular
to the long axis exposed. The reference electrode was an
Hg/HgO (in 1.0 M KOH) electrode, and all the potentials
are referred to this electrode unless otherwise stated. A
platinum wire spiral was used as a counterelectrode. The
electrolyte used in all the experiments was a 1.0 M KOH
solution. J. T. Baker's reagent grade potassium hydroxide
was used to make up KOH solutions with doubly distilled
deionized water. The results obtained from this solution
was identical to those obtained using a solution prepared
with Alfa Chemical's extrapure KOH.
For each experiment, the working electrode was first
polished with 30 pm aluminum oxide coated paper, suc-
cessively down to 1 Lm alumina powder, and rinsed with
doubly distilled water. The cell was purged with N2 while
the working electrode was held at -1.5 V vs. Hg/HgO for
10 min before each experiment was started.
The impedance spectra were recorded at room tempera-
ture (22 1C) with an EG&G Princeton Applied Research
Model 273 potentiostat-galvanostat equipped with an
optional impedance measurement board plugged in. The
instrument was driven by EG&G 378/388 software. The
measurements were made at a rate of five points per
decade between 100 kHz and 5 Hz at stationary electrodes.
In the high frequency region of 10 - 5 Hz, single sine
measurements were made with an EG&G 5210 lock-in
amplifier, whereas multisine measurements were conduct-
ed at low frequencies down to 10 - 3 Hz. The measurements
took about 5 min between 100 kHz and 5 Hz and more
than 1 h when the measurements were made down to the
millihertz region; the measurement time depended on the
frequency range and how stable a system was. Some of the
spectra reported here were the ones merged from both sin-
gle and multisine measurements.
For analysis of the impedance data, a software program,
"Equivalent Circuit," provided through EG&G by Univer-
siteit Twente24 was used. The program used a variety of
electrical circuits to numerically fit the measured imped-
ance data. The program is capable of conducting analysis
of heavily convoluted frequency dispersion data by decon-
voluting the complex response into those of simple sub-
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components. This approach combined with the general
nonlinear least squares fit procedure allowed us to con-
struct equivalent circuits, whose simulated responses fit
actually measured data well.
In this work, a constant phase element (CPE or Q) and a
finite length diffusion element, 0, are used for equivalent
circuits. The CPE is a general diffusion-related element.
Its admittance representation, Y, has the form2 4
Y = YQw" cos (nrr/2) + jYQ"o sin (nar/2) [1]
where YQ is a constant containing the diffusion coeffecient,
w is 2rf where f is frequency, and n is a number between
-1 and 1 (see below). The CPE may be interpreted as a dif-
ferent electronic component depending on the n value. It
represents a resistor with its value of R = 1/YQ when n =
0, a capacitor with a capacitance of C = Y with n = 1, an
inductor with an inductance L = 1/YQ for n = -1, and a
Warburg response when n = 0.5. Note that with n = 0.5
Eq. 1 becomes
Y= yQjo)42 [2]
which is the admittance response of the Warburg element
that relates to Fick's second law for a semi-infinite diffu-
sion process.
The admittance representation of the finite diffusion
element, 0, is
Y = Yo(jo) "' 2 coth [B(jow). 2] [3]
This element deals with a finite-length diffusion where a
constant activity or concentration is a common boundary
condition for the interface removed from x = .25 The
parameters Y, and B contain the diffusion coefficient and
the thickness of the thin layer. Its explicit impedance
response is26
Z = R,,[1 + kf tanh {r(jow/DO)12/(/Do) 2}
+ k tanh {,N(jw/DR)l/U(jwDR))l}] [4]
where R is the charge-transfer resistance, k and k b are
forward and backward electron transfer rate constants, 8 s
is the thickness of the Nernst diffusion layer, and DO and
DR are diffusion coefficients of the oxidant and reductant,
respectively. At high frequencies, the impedance response
is dominated by the Warburg behavior while it can be
modeled by a parallel circuit of a resistance and a capaci-
tance at low frequencies. Obviously, we obtain the
Warburg impedance if N CC.
Results
The electrochemical impedance spectra for the oxida-
tion of the zinc electrode in 1.0 M KOH solutions were
recorded between -1.50 and -0.70 V vs. Hg/HgO at poten-
tials marked on the cyclic voltammogram shown in Fig. 1.
A potential was stepped anodically from -1.50 V (rest
potential) to a value of interest after the electrode is held
at -1.50 V for at least 10 min under a nitrogen atmos-
phere, and then an impedance spectrum was recorded.
While the measurements were made after currents de-
cayed to the steady-state values, we opted not to show the
steady-state voltammogram for two reasons. The first is
that currents observed in steady-state voltammograms
would not represent those after currents have decayed as
was the case in our study. The second is that they have
been published in the literature (see, for example, Ref. 5).
Equivalent circuits shown in the bottom of Fig. 2-8 were
derived from the simulation of the oberved data, and all
the parameters obtained from the simulation are listed in
Table I.
The complex impedance spectra recorded at -1.50 and
-1.45 V are shown in Fig. 2. At these potentials, almost
perfect fits of simulated curves to the measured data lead
to a simple equivalent circuit with different radii at dif-
ferent potentials as shown in Fig. 2. The Rs,component in
the circuit is the solution resistance with the value at a
high frequency intercept on the Z' (real reactance) axis.
 J. Electrochem. Soc., Vol. 143, No. 12, December 1996 © The Electrochemical Society, Inc. 3897

. O nn
60

40

20 W

o
0
I

-20

-1.7 -1.5 -1 3 -11I 9 -0.7

Potential, V vs. AgjHgO

Z', ohms
Fig. 1. Cyclic voltammograms of a zinc disk electrode in a 1.0 M - -
8UL
KOH solution at a sweep rate of 50 mV/s for the first five cycles.
Impedance measurements were made at potentials marked with in-
verted triangles, and horizontal arrows indicate the scan direction.
60C
The response from the parallel charge-tranfer resistance,
Rp, and the CPE, Q1, makes up the semicircle. As men-
tioned, the n value close to 1.0 (-0.9; see Table I) for this E 400
CPE indicates that this is a double-layer capacitor. The
equivalent circuit shown here, which has a parallel RC
network, suggests that a faradaic reaction is taking place 200
at these potentials with an impedance for charge-transfer
of Rc,. The reaction taking place at these potentials, which
are about 140 - 90 mV more negative than the equilibri-
um potential, -1.36 V, for zinc dissolution under the ex- 0
perimental conditions used here, is most likely mixed re-
action of hydrogen evolution and zinc oxidation. As a
result, a small amount of anodic current is observed as the
zinc oxidation is slightly larger than that of hydrogen evo-
lution. Although the hydrogen evolution has a large over-
(C) Q1
potential at the zinc electrode, a small cathodic current
would flow at these potentials judging from the thermo-
dynamics of the reaction. Mathewson 27 reported that the
difference between the potential required to deposit zinc
on the zinc surface in sulfuric acid and the potential
required to deposit hydrogen under the same conditions is
only 0.05 V.
When the potential was stepped close to the equilibrium Fig. 2. Complex impedance spectra for a zinc disk electrode in
potential, -1.36 V vs. the Hg/HgO electrode, the oxidation 1.0 M KOH at (a) -1.50 V and (b) -1.45 V vs. Hg/HgO, and (c)
currents resulting from the dissolution of zinc increased an equivalent circuit for the data shown in (a) and b).
gradually. Figure 3 shows the complex impedance spectra
recorded at -1.40 and -1.37 V along with an equivalent
circuit fitting the data in the bottom. At these potentials, the dissolution process is limited by the diffusion of the
a Warburg component with an n value close to 0.5 (the ele- oxidation products. During the very beginning of the dis-
ment with a symbol, Q3, in the circuit) is observed in most solution process at less positive applied potentials, the
of the frequency range, which indicates that the kinetics of anodic dissolution current is very small and the diffusion

Table I. Parameters obtained for simulation of the elements in equivalent circuits.'

Q1 Q2 Q3
YQ X 10- 6
Y X 10 YQ X 103 B (s/2 )
T
Eapp,,e (V) RCT (fl) R (1) R2 () R () n n Y n L, H YO

-1.50 1257 - - - 17.8 0.89 - - - - - - -

-1.45 1119 - - - 18.2 0.91 - - - -
-1.40 177 - - - 40.1 0.89 - - 0.358 0.59 - - -
-1.37 157 - - - 34.4 0.89 - - 0.386 0.56 - - -
b
-1.30 10.5 8.9 1.6 17.9 314 0.74 1.8 x 106 0.85 - - 6.3 x 102 - -
-1.25 9.1 9.1 2.1 - 245 0.73 1067 1.0 42.2 0.62 - - -
-1.20 12.8 12.8 16.9 - 86.6 0.78 608 1.0 1.90 0.82 - - -
d
-1.10 64.6 - - - 3665 0.94 - - - - - 1.38 0.976
-0.90 75.4 75.4 103 - 10.45 0.94 25.6 1.0 4.64 0.43 - - -
-0.70 115 - - - 11.7 0.92 - - 5.17 0.48

aRs values are not listed as they are almost constant at 3.7 0.3 1 for measurements made between -1.50 and -0.70 V.
bRC is R + R2 in this circuit. See Fig. 4.
CRCT here is R,. See Fig. 5.
dThe R value is -172 l. The RCT value was obtained from the high frequency arc. See Fig. 6.

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 3898 J. Electrochem. Soc., Vol. 143, No. 12, December 1996 The Electrochemical Society, Inc.

process of the oxidation products from the electrode sur-
face to the bulk of the solution is slow due to small con-
centration gradients. With increasing anodic polarization,
more zincate ions are generated and the diffusion process
becomes faster. As a result, the electrochemical dissolution
of the zinc electrode becomes easier. A sharp rise in values
of l/RCT, which indicates a sharp increase in dissolution
currents with the increasing anodic polarization, is noted
in this potential region (more on this below; see also
Fig. 9a).
The complex impedance spectrum at —1.30 V is shown
in Fig 4. A reasonably small Ra value (=R1 + R2) of 10.5 11
is observed at this potential. The inductive loop shown in
the medum frequency range indicates that the rapid in-
crease in the oxidation current is impeded at the elec-
trode/electrolyte interface by the inductive current flow-
ing in the opposite direction. This might have been caused
by the intermediate species generated during zinc dissolu-
tion. The low frequency capacitive response (Q2) may be
related to the adsorbed intermediate species generated
during the active dissolution process and subsequently
adsorbed on the electrode surface. Thus, the dissolution
reaction may be limited by the diffusion process due to
350
o Measured 5 Hz —o
300 — Simulated
250
200
this adsorption, and the CPE has an intermediate charac-
ter (a = 0.85) between a capacitor (n = 1) and a Warburg
impedance (a = 0.5). These adsorbed intermediate species
are believed to be the cause of the prepassivation. A simi-
lar phenomenon has been observed during the dissolution
process of the iron electrode.26 At this point the increase in
current slows down dramatically, and the films formed on
the electrode surface gradually become compact. The cur-
rent is close to a limiting value at this potential. A large
drop in current (or in the l/RCT value) is noted at potentials
more positive than —1.30 V (see Fig. 9 below).
The complex impedance spectra recorded at —1.25 and
—1.20 V are shown in Fig. 5. Two continuous semicircles
are convoluted into what appears to be one. The semicir-
cle at high frequencies (the R — Q1 parallel network in the
left of the equivalent circuit) is attributed to the faradaic
charge-transfer process while the second at the intermedi-
ate frequencies is to an adsorbed species that contributes
to the prepassivation of the electrode. Three CPEs (Q1 —
Q3) are included in the equivalent circuits. From Table I,
we can see that Q1 is basically the double-layer capacitor
with ann value of 0.73 at high frequencies and Q2 at medi-
um frequencies shows the capacitive property of the film
with large capacitances. This probably indicates that a
large capacitive film blocks the charge-transfer in the
lower frequency region. The Q3 at very low frequencies
changes from Warburg (a = 0.62) in Fig. 5a to a more
capacitive response (n = 0.82) at more positive potentials
(a) as indicated by an increase in the a value from 0.62 at
—1.25 V to 0.82 at —1.20 V. The Warburg-like behavior
shown here indicates that the mass transport is blocked
accross the film as pointed out above. At —1.10 V (Fig. 6),
a reverse semicircle is observed in the complex impedance

71
spectrum with a negative polarization resistance, R. This
is a typical indication of the active-to-passive transition
1 50 which was also seen at the iron2° and chromium24 elec-
trodes. Here, the presence of Y0 indicates that the reactant
100 or product transport across the prepassivation film follows
the finite diffusion model and the large Q1 indicates a
50 capacitance of the film. The charge-transfer, albeit inef-
100 soI
0C I

100 200 300 400

Z', ohms 12
350 o Measured
10 (a)
300 - Simulated
8
250
200
1 50
2
100
0
50 100 KHz
—2
0 400 0 5 10 15 20
2', ohms
Z'. ohms

(c) QI (b) Qi

Fig. 3. Complex impedance spectra for a zinc disk electrode in

1.0 M KOH at (a) —1.40 V ond (b) —1.37 V, and (c) an equivalent Fig. 4. (a) Complex impedance spectra for a zinc disk electrode
circuit. in 1.0 M KOH at —1.30 and (b) an equivalent circuit.

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 J. Electrochem. Soc., Vol. 143, No. 12, December 1996 © The Electrochemical Society, Inc. 3899

fective, takes place as the RC and RP_ are parallel to each
other, bypassing the latter at high frequencies. The RT
value of 64.4 Q was estimated from the semicircle observed
in the high frequency region.
Figures 7 and 8 show the complex impedance spectra
recorded in the passive region at -0.90 and -0.70 V, re-
spectively. Warburg responses (Q3 s with their n values
close to 0.5) are observed in both cases due to the forma-
tion of the passive films on the electrode surface, which
shows a shielding effect on mass transport of reactants and
as the i vs. E curve. A plot of In (1/Rc,) vs. E, which is
equivalent to the Tafel plot, is constructed from the same
set of data and shown in Fig. 9b. A linear regression of the
linear portion in the active dissolution region of the
in (1/RT) vs. E plot was used to determine the transfer
coefficient, a, of 0.36 (see Eq. 11 below) for the rate limit-
. c
.
I. /

products. The Warburg behavior indicates that the film is

thick compared to the diffusion layer thickness and the 1 50
mass transport across it mimics the semi-infinite model
rather than that of the finite diffusion as shown at -1.10 V 125
(Fig. 6). Thus, the kinetics of the reaction is controlled by
the diffusion of OH- ions toward, and the oxidation prod- E100
ucts away from, the reaction sites through pores in the
passive films.
c- 75
The charge-transfer resistances, RCTs, were taken from
the semicircles in the high frequency region of the imped- 50
ance curves.30 Since the dissolution current is inversely
proportional to the charge-transfer resistance, the plot of
1/RCT vs. potential (E) shown in Fig. 9a has the same shape 25

0
-1

16 Z',ohms
(b)
o Measured (a) Q
12 - Simulated

M
I 5 mHz
8
Ii-

4
10 KHz

5 Hz
Fig. 6. (a)Complex impedance spectra for a zinc disk electrode
n I . I i I in 1.0 M KOH at -1.10 V and (b)an equivalent circuit.
0 4 8 12 16 20
Z', ohms
--
32 300

250
24
200
E
016 1 50
I
100
8
50

0 8 16 24 32 40 0
0 100 200 300
Z', ohms Z', ohms
(c) QI a2
(b)
Q2

Fig. 5. Complex impedance spectra for a zinc disk electrode in

1.0 M KOH at (a) -1.25 V and (b) -1.20 V, and (c)an equivalent Fig. 7. (a)Complex impedance spectra for a zinc disk electrode
circuit. in 1.0 M KOH at -0.90 V and (b)an equivalent circuit.

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 3900 J. Electrochem. Soc., Vol. 143, No. 12, December 1996 © The Electrochemical Society, Inc.

. _ _
ing one-electron charge-transfer step (see reaction 6 be-
175 low). The exchange current, i,, was determined to be
0.11 A/cm2 from the charge-transfer resistance, Rc, at lq=
150 0 or -1.36 V, from

125 io = RT/(nFR,) [5]

The a and i values are in good agreement with those ob-
E100 tained by Farr and Hampson, 4 who reported an exchange
current of 0.092 A/cm 2 and an oavalue of 0.50 from simple
- 75 Tafel experiments under similar experimental conditions.
Discussion
50
Active dissolution.-In the electrodissolution process of
the zinc electrode in 1.0 M KOH, a Tafel behavior is ob-
25 served in the lower anodic overpotential region as can be
seen from Fig. 9b. The predominant oxidation products
OO O : generated
_ at
_ the lower
__ anodic
___1__ 1 _ __ overpotentials
1-3T____ _ are 1known
__ to_ O X
be zincate complex ions.' -- However, the mechanism of the
Z', ohms active dissolution is not well understood. For the poly-
crystalline zinc electrode used in this study, at least one
(b) adsorbed intermediate species is observed in the complex
impedance spectra in Fig. 3 as shown by the presence of
Qai the Warburg component. The dissolution process is slow at
]the, nfn''ille --1 AN tn -- 1 P47 VW nA hor-il limit+,d h,
ll-;> JuL-l-a-l \ -. tt -<U- - I - C, I-J IIIU- J
the diffusion of the oxidation products away from the elec-
trode surface or OH- into the reaction sites; this would
lead to the observed Warburg behavior. Farr and Hampson
proposed that the intermediate species was (ZnOH)a-d
based on their impedance and transient electrochemical
measurements using the double potential pulse tech-
niques.' Cachet et atl. ' used the impedance measurements
Fig. 8. (a) Complex impedance spectra for a zinc disk electrode to conclude that the zinc dissolution took place essential-
in 1.0 M KOH at -0.70 V and (b)an equivalent circuit.
¢ ly at the base of pores in a conductive layer of oxidation
products mainly composed of ZnO. Our in situ spectro-
electrochemical studies also showed the absorption bands
characteristic of a semiconducting ZnO with heavily
doped Zn atoms in the film at the beginning of the disso-
lution process."
niff-ren fnrmo nf
JlIlUJLIIL lUg lia U lb
h. ltx in+nt
zIIIC:LC.
nmnl-s i-ny
.UIIIlt
hno
IUllo IzVt
hn
U~xll
0.12
proposed both as intermediate species such as Zn(OH)+ ,
Zn(OH),, and Zn(OH), , and Zn(OH)2- as a final product in
0.1
concentrated alkaline solutions by Bockris et al.9 However,
Zn(OH)3 could also be one of the final products along with
I' 0.08 Zn(OH)4 2-
, depending on the concentration of OH-. In a
E
chemically prepared zincate solution in 1.0 M KOH, the
O 0.06 ratio of Zn(OH)3 to Zn(OH)2- is about 1:9. 31 The ratio
could be higher at some local area near the electrode sur-
a: 0.04 face due to the depletion of OH- ions. The Zn(OH)3
species was confirmed during zinc oxidation with cyclic
0.02 voltammetric and spectroelectrochemical studies.' 4 Thus,
it is reasonable to conclude that Zn(OH)3 produced during
0
the oxidation o zinc - ue to the depletion o nydroxide
-1.6 -1.4 -1.2 -1 -0.8 -0.6 ions becomes Zn(OH)4 after combining with one more
E(V) vs. Hg/HgO OH-, leading to the active dissolution in nonconcentrated
alkaline solutions.
The formation of the zincate ions could result from var-
-1 ious intermediate species. Since ZnO is found in a very
early stage of the dissolution process,' 4 " it should be one
-2
-3
/_0 (b) of the intermediates in the porous film initially formed on
the electrode surface and is then dissolved gradually when
the potential is stepped to a further anodic value. By con-
sidering our impedance measurements along with the elec-
U.l *
trochemical and spectroelectrochemical studies,' 4 we pro-
-65 i 7/ pose the following mechanism for the active dissolution of
zinc in 1.0 M KOH solution
-6
Zn + OH- - ZnOHd, + e- [6]
-7
ZnOH,, + OH- (ZnO)d + H2 0 + e [7]
-8 -~~l l + l l
(ZnO)ads + H2 0O+ OH- Zn(OH)- [8]
-1.6 -1.4 -1.2 -1 -0.8 -0.6
E(V), vs. Hg/HgO Zn(OH)- + OH- -* Zn(OH)2- [9]
The impedance dispersions shown in Fig. 3 indicate that
Fig. 9. (a) The 1/R vs. E and (b) In (1/RT) vs. E plots. The least the oxidation of zinc at a low anodic overpotential is
squares line has been drawn for the data obtained between -1.45 almost entirely controlled by the diffusion of OH-. The
and -1.25 V. electron-transfer process is faster in comparison to the

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 J. Electrochem. Soc., Vol. 143, No. 12, December 1996 © The Electrochemical Society, Inc.
mass transport. The half life of the Zn(I) species postulat-
ed to be involved in reaction 6 is reported to be in the order
of ,1/2 = 10-5 S.32 Therefore, electron transfer steps 6 and 7
must be fast but limited by diffusion; this is supported by
the Warburg impedance (Q3 ) observed in Fig. 3. In other
words, reaction 6 must be the rate-limiting step due to the
slow diffusion of OH- into the reaction site through the
ZnOHads layer. This mechanism, in which the electron
transfer is postulated as a rate-limiting step, is consistent
with the results reported by Bockris et al.9 The rate of
reaction 9 depends on the concentration of OH-, potential
scan rate, and how the electrode is positioned.6 '4 It would
be faster in highly concentrated OH- solutions at a verti-
cally positioned electrode. Natural convection at such
electrodes reduces the possibility of the depletion of OH-.
Prepassivation.-Whilethe active dissolution is in pro-
gress with the increasing anodic current at -1.30 V, an
inductive element is observed as seen in the impedance
dispersion shown in Fig. 4. This element is generated in
the electrode/electrolyte interface and generates a current
in the opposite direction resulting in a reduction of the
dissolution rate. We believe this is caused by the supersat-
urated zincate ions which are produced at the electrode
surface very rapidly at higher anodic overpotentials. The
supersaturation would lead to nucleation and eventually
to precipitation as zinc oxide. The inductive loop might
have resulted also from the two-step charge transfer as
summarized by reactions 6 and 7, which are increasingly
limited by the depletion of the hydroxide concentration in
this potential region.26 Another element we see in the
equivalent circuit is the low frequency capacitance which
is attributed to the adsorbed species on the electrode sur-
face. Both elements contribute to a slowdown of the active
dissolution rate.
The saturation of zincate ions leads to a layer of
adsorbed species on the electrode. This layer is believed to
be very loose with a composition of ZnO1 x(OH)2x from
spectroelectrochemical results. 4 The reaction involved in
the formation of this precipitate might be
Zn(OH)42 - ZnO,_(OH) 2,, + (1 - x )H2 0 + 2 OH- [10]
Active to passive transition.-The Rc values are ob-
tained from the relatively high frequency region as is evi-
dent from circuit diagrams. For an i-E or 1/RcT-E curve
such as that shown in Fig. 9a, we have an expression26 '24
i = i exp [(1 - )nFE/RT]
neglecting the cathodic term. The slope of this curve,
di/dE, is Rcr at a given point on the E or i axis and, thus,
we have a relation
1/R, = di/dE (or RcT = dE/di)
A sharp drop in current is observed with a large negative
RcT value.
When the potential is stepped to -1.10 V,the impedance
dispersion shows a reverse semicircle, or a negative polar-
ization resistance. This is a typical characteristic of an
impedance plot in the active-to-passive transition re-
gion.2 5 The negative resistance as - 0 is consistent with
the negative slope of the polarization curve. The origin of
the negative Rp shown in Fig. 6 has been accounted for
theoretically in terms of an increasing coverage of the
electrode surface by an adsorbed intermediate as the po-
tential is increased 29 Macdonald 2 5 mentioned that it could
result from the adsorption of a monolayer of oxygen on the
electrode surface. A finite diffusion element is included in
the equivalent circuit as shown in Fig. 6, which is related
to a thin film formed on the electrode surface. This thin
film would shield the electrode and block the diffusion of
the oxidation products species from the reaction sites,
which causes the current drop, i.e., the passivation of the
electrode. It is probably the "type II" film,6 which devel-
ops to become a compact passive film with a further
increase in potential. Its composition might be Zn-doped
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3901
ZnO.'4 The formation of the thin film results from further
oxidation of the electrode
Zn + 2 OH- -ZnO + H2 0 + 2e [13]
Passivation.-When the potential is stepped to the pas-
sivation region at around -0.9 V, a Warburg impedance is
observed, as shown in the complex impedance spectrum in
Fig. 7. The Q3 element in the equivalent circuit represents
the Warburg response with an n value close to 0.5. At this
potential, the thin film developed during the active-to-
passive transition becomes more compact as the passiva-
tion process progresses. Thus, the system starts to show
diffusion-controlled kinetics. However, the passive film is
not too compact yet at this potential and is mixed with the
adsorbed species generated from the precipitation of satu-
rated zincate ions as indicated by two semicircles in the
impedance dispersion. When the potential is at -0.7 V, the
passive film becomes very compact so that only one semi-
circle is observed in the complex impedance spectrum as
shown in Fig. 8. A typical Randle circuit fits well to the
measured data, and the electrode behaves as a semicon-
ductive electrode. The oxidation of zinc electrode takes
place through the ZnO layer. The Warburg impedance
indicates that the process is controlled by the diffusion of
reactants and products through the compact passive ZnO
film. A relatively small charge-transfer resistance is also
noticed. This is because the electrode is now recovered
from the sharp current drop during the active-to-passive
transition.
Conclusions
The electrochemical dissolution of the zinc electrode in
1.0 M KOH solutions starts slightly below the equilibrium
potential of -1.36 V vs. the Hg/HgO electrode. The active
dissolution takes place in the potential region of -1.4 -
-1.3 V, and the Tafel behavior is observed. The oxidation
current reaches a maximum at about -1.30 V The passiva-
tion of the electrode starts at more positive potentials than
this. The active-to-passive transition was confirmed by the
presence of negative polarization resistance and a reverse
semicircle in the complex impedance spectrum. At this
point, a sharp drop in current is also seen in the 1/R,, vs.
E plot. This is consistent with the above interpretation
because 1/RC is proportional to the anodic current. The
species ZnO1 _(OH),,2 precipitated from the supersaturated
[11] zincate ions may contribute to the prepassivation of the
electrode during the active dissolution process, while the
Zn-doped oxide produced on the electrode surface under
the adsorbed species ZnO1 _(OH) ,,2 may possibly cause the
active-to-passive transition. The heavily doped oxide film
on the zinc electrode in the passivation potential region
[12] makes the electrode behave as a semiconductive ZnO elec-
trode.
Manuscript submitted July 11, 1995; revised manuscript
received Sept. 2, 1996.
The University of New Mexico, assisted in meeting the
publication costs of this article.
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Electrochemical Behavior of Thin Anodic Oxide

Films on Zircaloy-4
Role of the Mobile Defects
R. Salot and F.Lefebvre-Joud
C.E.A. Grenoble DTP/SECC, 38054 Grenoble Cedex 9, France

B.Baroux*
INP Grenoble/LTPCM, 38402 Saint Martin d'Heres, and Centre de Recherches d'Ugine, 73400 Ugine, France

ABSTRACT
The first stages of the electrochemical oxidation of Zircaloy-4 are investigated using simple electrochemical tests and
modeling the passive film modifications occurring as a result of contact with the electrolyte. Variations in electrode
potential (open-circuit conditions) or current density (potentiodynamic scans) can be simply explained by a high field
(F - 106 V/cm) assisted passive film growth. Under open-circuit conditions, this field does not vary with exposure time
(in the 2 h to 48 h range). The minimum electric field for the onset of high-field behavior is also evaluated and found
smaller than the theoretical value which can be explained by a variation in the concentration of mobile defects through-
out the film. Measurements of the electrode potential decay after a potentiodynamic scan confirm this model, allowing
interpretation of the film modification as a combination of two separate phenomena: film growth under a high electric
field and point defect annihilation.

Introduction
The general context.-Zircaloy-4, which is a zirconium
alloy containing Sn, Fe, Cr, and 0, is mainly used in the
nuclear industry, especially in pressurized water reactors,
as fuel cladding material. For safety reasons, the cladding
integrity has to be ensured for its entire working life in the
reactor core. In such a case, the oxidation rate of Zircaloy
in 300°C pressurized water has to be carefully controlled to
make sure that the mechanical properties of the cladding
are maintained and that the hydrogen uptake by the
cladding is not too high.
The general oxidation reaction of Zr alloys in water is
written as
Zr + H2O - ZrO + H2
The oxidation process is usually described in two steps
with a transition between a cubic and a linear oxidation
rate.'- 4 The first part of the kinetics is classical; it is the
result of the oxygen diffusion through a growing oxide
layer. 5 7 It is generally accepted that after the transition,
*Electrochemical Society Active Member.
the barrier between the metal and the water consists of an
inner dense oxide layer with a constant thickness. 8
It has been shown that the microstructure of the oxide
layer formed at the very beginning of the oxidation process
has a clear influence on the subsequent behavior.9 More
precisely, the initial structure of the oxide (in terms of its
grain morphology and size, marked preferential orienta-
tion, impurity content, and allotropic form of the oxide) are
closely linked to the occurrence of the destabilization of
the dense inner layer into a porous nonprotective one with
a consequent increase in oxidation rate. 5 1'0'
On the other hand, several works have also highlighted
the influence of irradiation on the oxidation behavior of
Zircaloy-4 or Ti. ""23 In order to further analyze the mech-
anisms which are implicated in such conditions, and espe-
cially the role played by irradiation defects, we first study
the electrochemical behavior of Zircaloy-4 without irradi-
ation, as a reference to be used later for those experiments
under irradiation conditions.
In this work, we focus on these first stages of the oxida-
tion process of Zircaloy-4 from an electrochemical stand-
point. We first recall the classical electrochemical proper-
ties of thin Zircaloy oxide layers. We then intend to model
the beginning of uniform oxide growth using the results of

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