Electrochimica Acta 46 (2001) 3743 3754

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Study of the initial stage of white rust formation on zinc

single crystal by EIS, STM/AFM and SEM/EDS techniques
L. Sziraki a,*, E. Szo3 cs b, Zs. Pilbath a, K. Papp b, E. Kalman b
a
Department of Physical Chemistry, Eot6os Uni6ersity, P.O.B. 32, H-1518 Budapest, Hungary
b
HAS Central Research Institute for Chemistry, Pusztaszeri u. 59, H-1025 Budapest, Hungary

Received 21 June 2000; received in revised form 12 September 2000

Abstract

The kinetic consequences of morphological changes due to the zinc exchange process have been related to the
corrosion performance and a further understanding of the initial stage of the white rust formation occurring
preferentially in a thin layer of moisture in the absence of oxygen. Electrochemical impedance diagrams for a
uniformly covered Zn corrosion product layer can be interpreted by a one-step dissolution mechanism, while on a
non-uniform, partially active surface a consecutive dissolution occurs via adsorbed Zn(I) and Zn(II) species. The in
situ EC-STM and EC-AFM observations revealed oriented Zn dissolution, deposition along the atomic steps and
oriented oxide formation on the redeposited crystal planes in the early stages of each process. 2001 Elsevier Science
Ltd. All rights reserved.

Keywords: Zinc corrosion; Zinc exchange reaction; EIS; STM; AFM; SEM EDS

1. Introduction Electrochemical impedance spectroscopy (EIS) is a

The structure and protective properties of oxidehy-
droxidehydroxycarbonate films formed on Zn under
atmospheric environments are greatly determined by
the specific conditions under which the corrosion pro-
cess initiates, i.e. relative humidity, dissolved O2, anion
content, pH, temperature.
Zinc exposed to well-aerated environment with low
moisture corrodes with the formation of thin adherent
corrosion products known as patina. Under humid and
poorly aerated conditions, porous non-adherent white
rust forms under which local damage of the zinc surface
often occurs. However, another important parameter to
be considered in the white rust formation is that the
corrosion rate being commensurable with the Zn2 + /Zn
exchange rate from about 10 5 to 10 4 mol dm 3 zinc
ion concentration in near neutral sulfate solutions [1].
* Corresponding author. Fax: + 36-1-2090602.
E-mail address: sziraki@ludens.elte.hu (L. Sziraki).
useful method to provide data for identifying occur-
rence of multistep charge transfer, coupling of the
interfacial reactions, type of diffusion, various interme-
diate adsorption steps and different growing mode of a
new phase.
Direct structural information on the surface changes
due to dissolution and deposition can be obtained by in
situ surface sensitive techniques, such as scanning tun-
neling microscopy (STM) and atomic force microscopy
(AFM). Recently, morphological changes during disso-
lution/deposition at the nanoscale were observed by in
situ STM AFM [2,3] methods.
In this work we point out with the application of
EIS, AFM/STM techniques and scanning electron mi-
croscopy (SEM) with energy dispersive X-ray spec-
trometry (SEM EDS) that Zn redeposition due to
Zn2 + /Zn exchange reaction results in an activated,
roughened zinc/oxide/hydroxide surface which en-
hances further corrosion.

0013-4686/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 1 ) 0 0 6 5 6 - 9
3744 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754

2. Experimental tials of the electrode and tip were independently

Zinc single crystal slices (triple distilled, crystal
grown by the modified Bridgman method) cleaved at
the (0001) plane under liquid nitrogen were used as the
working electrode. The Zn single crystal slice of 0.1 0.5
cm2 area was connected by conducting paste to a zinc
rod embedded in a Teflon holder.
The corrosion measurements were carried out in
aerated/deaerated 0.5 mol dm 3 Na2SO4 and deaerated
0.1 mol dm 3 ZnSO4 +0.4 mol dm 3 Na2SO4
solutions. The pH was adjusted to 5.
In electrochemical measurements the disc electrodes
were rotated using a Tacussel EDI 101T assembly. The
electrode potential was measured against a saturated
calomel electrode (SCE). To reduce the high-frequency
impedance distortion the reference electrode was
shunted by a platinum wire with a capacitance of 1 mF.
The small amplitude EIS measurements were carried
out using a Solartron 1250 Frequency Response Ana-
lyzer coupled to a 1286 Electrochemical Interface. The
impedance spectra were recorded in the frequency range
between 50 kHz and 10 mHz. The evaluation of the
impedance spectra was made using the EQUIVCRT soft-
ware written by Boukamp [4].
AFM and in situ STM investigations were carried
out using a Nanoscope III apparatus (Digital
Instruments).
STM measurements were carried out in a three-elec-
trode electrochemical cell. The electrochemical poten-
controlled by means of a potentiostat. The working
electrode was Zn single crystal. The tunneling tips were
made of Pt and were covered with an epoxy layer up to
the operational tip to decrease the faradic current. The
AFM tip was made of Si3N4. The measurements were
taken either under solution or in air. SEM investiga-
tions used to study the surface morphology were per-
formed using a HITACHI S-570 apparatus, and the
element/chemical compositions were measured by a
RO8 NTEC EDR 288 X-ray spectrometer.
3. Results
3.1. Electrochemical impedance results of clea6ed and
redeposited Zn single crystal at the open-circuit
potentials
Generally, during Zn corrosion a dissolution precip-
itation and direct oxide formation may proceed simul-
taneously depending on several circumstances. The
nature of a corrosion process can often be revealed
using EIS [5,6].
Curve 1 of Figs. 1 and 2 indicates a uniform oxide
layer growing on cleaved Zn single crystals. The corro-
sion layer is more porous if it forms in a deaerated
solution with Na2SO4 concentration higher than 0.1
mol dm 3 than in an aerated solution. Accordingly, the
rate-determining steps of the corrosion reaction are the

Fig. 1. Complex plane plots of impedance diagrams of cleaved Zn single crystal electrodes measured at the open circuit potentials
in: (1) deaerated 0.5 mol dm 3 Na2SO4 solution after 2 h corrosion; (2) 0.1 mol dm 3 ZnSO4 +0.4 mol dm 3 Na2SO4 solution
after 3 h immersion; (3) 3 h corrosion in deaerated 0.5 mol dm 3 Na2SO4 following a 3 h immersion in solution 2. Electrode
rotation rate, f= 1000 rpm.
 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754 3745

Fig. 2. Complex plane plots of impedance diagrams of cleaved Zn single crystal electrodes measured at the open circuit potentials
in: (1) aerated 0.5 mol dm 3 Na2SO4 after 5 h corrosion; (2) deaerated 0.1 mol dm 3 ZnSO4 +0.4 mol dm 3 Na2SO4 solution after
3 h immersion; (3) aerated Na2SO4 solution after 3 h corrosion following a 6 h immersion in solution 2; (4) aerated 0.5 mol dm 3
Na2SO4 solution after 66 h corrosion following a 6 h immersion in solution 2. Electrode rotation rate, f =1000 rpm.

Zn2 + ion diffusion through the oxide layer and the
diffusion of the depolarizer to the electrode surface,
respectively [7,8]. Zinc dissolution on an active surface
proceeds via adsorbed Zn(I) and Zn(II) intermediates
[5,9]. This mechanism is ascertained by the inductively
intersecting loops that appear on the low-frequency
part of the impedance spectra similarly as shown by
curves 3 and 4 of Figs. 1 and 2. The presence of this
type of inductive behavior on the impedance diagram
of the corroding Zn is characteristic for the redeposited
Zn only. According to our measurements, in the case of
a smoother surface e.g. for single crystal, polycrystal
or bright electrodeposited Zn during prolonged cor-
rosion, the oxide layer provides a more uniform cover-
age and the shape of the impedance diagram becomes
purely capacitive at medium and low frequencies. To
explain the observed differences in the shapes of the
impedance diagrams on corroding Zn depending on the
quality of the surface state, the following corrosion
pathway is suggested.
When zinc is exposed to a Zn2 + ion containing
reaction gives rise to an active surface in two ways.
First, there are a large number of active sites for
dissolution and, second, there are probably many oxide
nuclei available for further grain growth. As a conse-
quence, the oxide hydroxide precipitation due to the
oversaturation and the local oxide growth become the
characterizing steps of the corrosion process. This leads
to fast and unevenly distributed white rust formation.
Comparing curves 1 and 3 of Fig. 1 and curves 1, 3 and
4 of Fig. 2 shows that the corrosion rate is higher if it
occurs on the redeposited surface.
During the corrosion process, the surface state may
continuously change either in kinetic or spatial sense. In
the case of non-stationarity a similar inductive capac-
itive impedance behavior can be obtained, as is depicted
in Figs. 1 and 2 [10]. Therefore, before modeling the
impedance spectra a quality assessment is needed.
The Kramers Kronig (K K) integral transforms
[11] are suitable to check the measured data, whether
the calculated real (imaginary) parts from the imagi-
nary (real) parts are equal or deviate from each other.
If the measured spectra are finitely valued at high and
solution two parallel reactions occur simultaneously [1].
The extent of the parallel reactions depends mainly on
the structure and electrical conductivity of the oxide
and Zn2 + concentration. As a consequence of the
corrosion and Zn2 + /Zn exchange reaction a microcrys-
talline Zn Zn oxidehydroxidesulfate containing
layer is deposited. The dissolution deposition exchange
low frequencies including =0 and = , then the
K K transformation could be carried out on real data
with a relatively little divergence [12 14]. When the
equality of the interrelation between the real and imag-
inary parts of the impedance function holds then the
conditions of linearity, causality and asymptotical sta-
bility obviously are maintained.
3746 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754

Fig. 3. Comparison of measured and K K transforms of the impedance spectra of single crystal Zn at the open circuit at various
conditions: (a) curve 1 in Fig. 2; (b) curve 2 in Fig. 1; (c) curve 4 in Fig. 2. Measured and transformed spectra are denoted with
,
or + symbols, respectively.

In order to render the data to be K K trans- position of crystal imperfection [16]. In simple salt
formable, expansion over two decades (to =0.01min solutions depending on current density and other
and =100max) using an extrapolation based on the parameters as a result of competition of the nucleation
partial fit modeled with a depressed semicircle circuit and growth rate the deposit becomes spongy, compact
was performed [15]. Between 30 kHz and 10 mHz some or dentritic [17,18]. In the case of leaving the Zn single
impedance spectra that were measured in steady state crystal in Zn2 + ion containing solution at the rest
condition were K K transformable with fairly good
relative error, as is displayed in Figs. 3 and 4. From
these results it may be concluded that the impedance
diagrams of the corroding Zn do obey the quasi-sta-
tionarity and are characteristic to the corrosion
kinetics.

3.2. AFM, STM and SEM results

A typical AFM image taken in air is shown in Fig. 5.

Steps of 1 3 atomic height (0.2 0.7 nm) are clearly
visible on the cleaved Zn surface.
The morphological changes studied by EC-STM,
AFM and SEM techniques support the conclusions
drawn from electrochemical results.
Fig. 6 shows the Zn surface in 0.01 mol dm 3
Na2SO4 solution at a potential of 100 mV above the
open circuit potential. The anodic dissolution of Zn in
this solution was followed. Atomic steps of 0.24 nm can
be seen on the surface at 75 nm scale. The dissolution
started at the step edges and proceeded along it.
It is known that during Zn deposition the adion
incorporation in the lattice at the growth site may occur Fig. 4. Plot of relative errors between K K transforms and
either directly on an active edge (kink) site or via measured impedance data of Fig. 3: (1) real part; (2) imaginary
surface diffusion in a proper nucleus existing at a part.
 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754 3747

Fig. 5. AFM image of a cleaved single crystal Zn taken in a dry cell.

potential both characteristic steps of the deposition can average grain size is about 7 mm (see Figs. 10(b) and
be observed. Fig. 7(a) shows an AFM image of Zn 11(b)). However, the composition of the corrosion films
single crystal immersed in Zn2 + containing solution for detected by EDS analysis was similar. The oxygen
30 min. The image clearly illustrates the oriented prop- content varied between 20 and 89 wt.%, while that of
agating crystal planes of 1 4 nm height. After changing embedded S was 3 9 wt.% in average.
the solution to 0.1 mol dm 3 Na2SO4, one can observe,
on the section analysis of Fig. 7(b) the oxide growth
occurring on the terrace (of 10 15 nm height) whereas 4. Discussion
the oxide propagation is blocked at the terrace ledge.
On top of the crystal planes in the Zn2 + containing The models proposed to understand the elemental
solution many small randomly distributed globular nu- processes in zinc dissolution and deposition are based
mainly on the analysis of the shapes of the EIS
clei were formed (as shown in Fig. 8(a)). Similar Zn
diagrams.
cathodic deposition on HOPG substrate was detected
The characteristic feature of Zn dissolution is that it
by in situ STM investigations and numerical simula-
involves consecutive and parallel paths coupled to
tions were carried out [2]. A hemisphere-shaped nucle-
chemical and catalytic steps.
ation mode was dominant at low current density.
The anodic reaction paths for Zn dissolution in Cl
Lateral size and distribution of small crystallites do
or SO24 containing solution of pH between 3 and 10
not alter with deposition time. Fig. 8(b) shows the
[5,6,9,19] can be summarized as follows:
topography of a thick, irregular, spongy deposit grown
during a longer redeposition time. ZnUZn(I)ads + e (1)
Fig. 9 illustrates that on a freshly deposited Zn ZnZn(I)ads Zn2 + (aq) + Zn(I)ads + e (2)
surface, oxidation in air leads to an uneven surface 2
SO 4 /Cl
covered with zinc/oxide/hydroxide crystals of different Zn(I)ads Zn(II)ads + e 
Zn2 + (aq) ZnO(s)
shape and, locally, dendritic oxide is growing. (3)
2 2
SO 4 SO 4 /H2O
Outstanding differences in the morphology of oxide Zn(II) ads ZnO(s) 
ZnSO4(s)
Zn 2+
(aq)
layers formed on different substrates can be seen by the (4)
SEM observation (magnification: 1000) in Fig. 10.
The oxide layer grown on Zn single crystal is com- ZnOHadsUZnOH (aq) + e
+
(5)
pact but the surface is covered unevenly by its subse- The first step is Zn(I)ads adion formation, which at an
quent layers (see Fig. 10(a)). Inhomogeneity of the active kink position invokes the consecutive catalytic
crystal grains is well illustrated by the scatter of the size renewal of the kink adion sites (reaction (2)), and as a
of the main and small axes (see Fig. 11(a)). The size of consequence the dissolution pattern becomes oriented
most oxide crystallites exceeds 15 mm. The microtexture along the atomic steps (cf. Fig. 6).
of the oxide grown on the redeposited Zn single crystal The parallel reaction path (3) shows the Zn(II)ads
surface is more inhomogeneous in the sense that the formation and that Zn(II)ads is consumed in a chemical
oxide does not cover the whole surface. Small oxide step that is influenced strongly by the presence of
grains are distributed in a rather uniform manner. The anions [5,9].
3748 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754

The parallel reaction path (4) describes the direct
solid state formation of the oxide or mixed salts and
their chemical dissolution occurs also with the partici-
pation of anions [6].
The parallel reaction (5) is the electrochemical disso-
lution of ZnOHads formed in chemical steps due to
cathodic corrosion reactions. This path is evidently
hindered in the case of progressive hydroxide/oxide
formation.
Derivation of the electrode impedance transfer func-
tions for anodic dissolution close to the corrosion po-
tential were given by Cachet et al. [9] and Deslouis et
al. [5] with assumption of several simplifying conditions
for reactions (1) (3) and (5). The calculated impedance
transfer function consists of three low-frequency time
constants: two inductive and one capacitive in between.
In aerated sulfate containing solutions at the corrosion
potential, two characteristic inductively intersecting ca-

Fig. 6. (a) (c) The sequence in time of the in situ EC-STM images of single crystal Zn in 0.01 mol dm 3 Na2SO4 solution (pH 3)
at an anodic potential DE= 0.1 V from the open circuit potential.
 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754
Fig. 7. (a) AFM image and section analysis of terraced planes of redeposited Zn taken under 0.1 mol dm 3 Zn2SO4 after 30 min
immersion. (b) AFM image after changing the solution to 0.1 mol dm 3 Na2SO4.
pacitive loops appear with an additional low-frequency
inductive arc. The four time constants belong to the
charge transfer process and relaxation of the coverage
of Zn(I)ads, Zn(II)ads and Zn(OH)ads, respectively.
Similar behavior is observable in the case of rede-
posited Zn surface (see Figs. 1(b) and 2(b)) with the
exception that at the lowest frequency the inductive arc
is absent. The inductive loop, although less pronounced
than at short immersion, is still present for longer
immersion time. The corrosion system exists in steady
state as can be concluded from K K transformable
impedance diagrams. Therefore, the active dissolution
mechanism on a partially covered surface may be appli-
cable. In the case of a cleaved single crystal at short
corrosion time the capacitive inductivecapacitivein-
ductive loops are still present in the impedance dia-
grams, but this trend disappears when uniform oxide
coverage is attained and the impedance diagram is
represented with two capacitive loops (Curve 1 in Figs.
1 and 2). Under passivation reactions (1), (2) and (5)
3749
are obviously hindered, a one-step dissolution with
activation and/or diffusion control is ascertained de-
pending on the porosity of the corrosion layer
[7,8,19,20].
The kinetic models for the cathodic electrodeposition
of Zn are based on an understanding of the low-fre-
quency inductive behavior of the impedance diagrams
developed by various electrochemical schools. Multi-
step discharge via adsorbed intermediates, the autocata-
lytic step induced by the adsorbed H atoms [17,18],
inhibition by the oxide, nucleation and growth mecha-
nism [18,21 23], identification of the surface, bulk and
hemisphere diffusion [16,24] are taken into consider-
ation. The concept of the chemical coupling of the
hydrogen evolution and zinc deposition via autocata-
lytic steps was first introduced by Epelboin et al. [17,18]
and was modified by Lee et al. [25].
The reaction scheme can be summarized as follows:
H+ + e H(ads) (6)
H(ads) + H + e H2
+
(7)
3750 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754

Fig. 8. (a) AFM image of the deposition pattern on a terrace

of Zn taken under 0.1 mol dm 3 Zn2SO4 after 30 min immer-
sion. (b) Morphology after 1 day immersion in the same Fig. 10. SEM observations of the Zn corrosion layers: (a) after
solution. immersion of a slice of single crystal Zn for 1 day in 0.1
mol dm 3 Na2SO4; (b) after 1 day immersion in 0.1
Zn2 + +Zn(I)ads +eU2Zn(I)ads (8) mol dm 3 Na2SO4 solution followed by a redeposition treat-
ment leaving the sample for 1 day in 0.1 mol dm 3 Zn2SO4.
Zn(I)ads +e Zn (9)

Zn2 + + Hads H+ + Zn(I)ads (10)

Zn(I)ads + Hads H+ + Zn (11)

According to this model, the codischarged adsorbed

Fig. 9. AFM image of Zn after half hour immersion in 0.1
mol dm 3 ZnSO4. Measurement was taken in air.
H atom (reaction (6)) reacts chemically with both the
Zn2 + ion and the adsorbed Zn(I) adion leading to
Zn(I) adion formation (reaction (10)) and Zn incorpo-
ration (reaction (11)). Besides this process, the autocat-
alytical Zn(I) adion formation also occurs (reaction
(8)). The electrochemical incorporation step (reaction
(9)) takes place preferentially at growth steps forming
oriented crystallites. The chemical incorporation step
(reaction (11)) forms disordered nuclei giving rise to a
spongy deposit. This model accounts well for the multi-
ple steady state at the cathodic Zn deposition manifest-
ing itself in a S-shaped galvanostatic polarization curve
and in LF inductive arcs in the impedance diagrams.
 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754
The impedance diagrams obtained during a steady
state redeposition stage (see curves 2 in Figs. 1(a) and
3(b)) were found to be K K transformable below 5
kHz with fairly good errors. Fig. 12(a) displays the
impedance diagrams measured at the rest potential as a
function of the electrode rotation rate during simulta-
neous corrosion and Zn deposition in a Zn2 + contain-
ing solution. These diagrams consist of high-frequency
distorted capacitive and medium-frequency inductive
loops and a capacitive arc belonging to the lowest
frequencies. The diagrams exhibit a rotation depen-
dence, which is obviously related to a convective diffu-
sion process. On the basis of the deposition model
outlined in Eqs. (6) (11), equilibrium reaction (8)
might account for the Zn2 + diffusion control at the
Zn/solution interface. The structural evaluation of the
impedance diagrams in Fig. 12(a) using complex non-
linear least-squares fitting calculation, however, pro-
vided only phenomenological elements, but revealed a
coupling of the bulk mass transport properties with the
interfacial reactions. The equivalent circuit model is as
l 2j/D) tanh
l 2j/D, where RD is
follows (cf. the equivalent circuit description code in
Fig. 11). The solution resistance is connected in series
with two subcircuits. The first of this is a parallel
Rct Cl circuit, which corresponds to the charge transfer
Fig. 11. Distribution of grain size on oxide layers as SEM pictures shown in Fig. 10: (a) after corrosion of a Zn single crystal; (b)
after corrosion of a redeposited Zn.
3751
process of the Zn2 + and Zn+ discharge and the capaci-
tance of the viscous part of the Zn/ZnO/Zn(OH)2 layer,
respectively. The second one consists of three parallel
branches. The double layer capacitance is connected in
parallel with a low-frequency adsorption type Ra Ca
element belonging probably to the Zn(II)ads species.
The second parallel branch admits a finite length diffu-
sion element being in series with a parallel Ri ZCPE,i
circuit. The ZCPE element as a frequency dependent
capacitance is given by the expression ZCPE =
A 1(j) h, where is the angular frequency. The
parameters Ri and A are negative and both are show
inductive behavior, probably in terms of the coverage
relaxation of the adsorbed species. It is interesting to
note that the value of the h exponent was close to
0.590.02, referring to a diffusion character. However,
the elucidation of the nature of a pseudoinductive
behavior requires further investigations at different
deposition potentials. The diffusion impedance of a
finite-length diffusion layer is given by the expression
WF(j ) = (RD /
the dc limit of the diffusion impedance, l is the thick-
ness of the diffusion layer, D is the diffusion coefficient
of the electroactive species, and ~ =l 2/D is the time
constant of diffusion. The parameters of the fit are
3752 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754

cm2 s 1 [7,26]), respectively. It is assumed that the

Fig. 12. (a) Measured (shaped symbols and lines) and fitted
impedance diagrams (crossed symbols) on Zn single crystal at
the rest potentials immersing in deaerated 0.1 mol dm 3
Zn2SO4 +0.4 mol dm 3 Na2SO4 for 3 h. Electrode rotation
rate: (1) 1000, (2) 2000, (3) 3000, (4) 4000 and (5) 5000 rpm.
Standard deviation of the CNLLS fitting for the given equiva-
lent circuit model varied between 0.004 and 0.011. (b) Charac-
teristic frequency of the finite length diffusion impedance
versus electrode rotation rate curve.
increase of chemical dissolution of the precipitated
oxidehydroxide-mixed salt with increasing rotation
rate changes markedly the composition of the interfa-
cial region and the surface coverage of the adsorbed
species. The decrease of the charge transfer resistance
Rct (see Table 1) clearly shows the increase in the active
sites for the deposition reaction with increasing elec-
trode rotation rate. Similar rotation rate dependence
was determined in the range of 0.001 0.1 mol dm 3
Zn2 + concentrations, the apparent diffusion coefficient
varied between 1 and 6 10 4 cm2 s 1. In this concen-
tration range the zinc exchange rate slightly depends on
the zinc concentration [1], obviously due to the oxide
hydroxide precipitation. In addition, the above struc-
tural analysis fits fairly well to the diagrams measured
during corrosion on redeposited surface (see curve 3 in
Fig. 1 and curves 3 and 4 in Fig. 2). Table 2 exemplifies
the fitted parameters for corrosion in aerated solution.
From the rotation rate dependence smaller apparent
diffusion coefficients were calculated whose values de-
pended highly on the corrosion exposure time, i.e. on
the solubility of the corrosion products. On corroding
zinc the h parameter of the negative CPE impedance
element is definitely 1, showing that the coverage relax-
ation of Zn(I)ads yields a negative capacitance. There-
fore, the negative capacitance being in parallel with the
negative Ri performs the inductive intersection of the
capacitive impedance loops.

listed in Table 1. It is well known that for convective 5. Conclusions

diffusion the characteristic frequency is linearly related
to the rotation rate according to the equation fD =
0.016D 1/3w 1/6f [7]. Fig. 12(b) shows the correspond-
ing fD versus rotation rate curve. The positive intercept
of this curve may be referred to a contribution of sur-
face or non-linear diffusion as well [24]. The apparent
diffusion coefficient estimated from the slope of the
linear section belonging to medium rotation rates (using
for solution kinematic viscosity w=0.01 cm2 s 1) was
about 5 15 times higher than that of H+ or Zn2 +
(DH+ =7.310 5 cm2 s 1 and DZn2 + =7.610 6
The chemical, structural and electrical properties of
the passive layer of Zn formed by atmospheric corro-
sion may significantly vary with the corrosion circum-
stances leading to occurrence of non-uniform corrosion.
Under humid environment, besides the cathodic corro-
sion process, the redeposition of the dissolved Zn2 +
may affect profoundly the morphology and activity of
the Zn surface. The nano- and microscale morphologi-
cal observations together with the results of the EIS
provided the evidence that the occurrence of zinc ex-

Table 1
Parameters of the fitted impedance diagrams measured on Zn single crystal after 3 h exposure in deaerated 0.1 M ZnSO4+0.4 M
Na2SO4 solution

Erest f Rct Cl Cdl RD ~D Ri Ai (mho cm2) h ~a

(V) (rpm) (V cm2) (mF cm2) (mF cm2) (V cm2) (ms) (V cm2) (s)

1.047 1000 58 68 21 716 27 529 2.54104 0.48 20

1.045 2000 44 72 20 620 20 469 2.50104 0.49 13
1.043 3000 30 81 20 577 14 446 2.30104 0.49 10
1.041 4000 20 94 20 547 11 432 2.13104 0.51 8
1.037 5000 9 119 20 465 6 388 1.98104 0.52 5
 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754
Table 2
Parameters of the fitted impedance diagrams measured on a redeposit Zn in aerated 0.5 M Na2SO4 solution

Ecorr tcorr f Rct Cl Cdl RD ~D Ri Ai h ~a (s)

(V2) (h) (rpm) (V cm2) (mF cm2) (mF cm2) (V cm2) (ms) (V cm2) (mho cm2)

1.07 2.5 500 0.78 164 112 116 24 91 1.19104 1 2

1.069 3 1500 0.75 135 108 86 20 66 1.37104 1 2
1.075 66 1500 1 98 101 93 42 50 3.76104 1 17

3753
3754 L. Sziraki et al. / Electrochimica Acta 46 (2001) 37433754
change reaction under certain corrosion circumstances
does contribute to the local corrosion performance, and
enhances the white rust formation.
The EC-STM and AFM morphological images taken
under solution revealed the oriented dissolution depo-
sition of Zn along the atomic steps, confirming the
kinetic interpretation based on the active self-perpetuat-
ing and the diffusing incorporating Zn(I) adsorption
sites. At an early stage, Zn redeposition as well as oxide
growth on a redeposited surface was also oriented.
The microscale morphological observations with the
help of AFM and SEM techniques show that, after
longer exposure time, the oxide structure is determined
by the morphology of the substrate and the distribution
of the active sites. The dentritic oxide growth is typical
on a roughened spongy and active Zn surface.
The evaluation of the EIS diagrams on a uniformly
growing, porous corrosion layer can be modeled with a
one-step dissolution with the diffusion of Zn2 + cations
or oxidizer depending either on porosity or electrical
conductivity of the oxide.
On an active or inhomogeneous surface the consecu-
tive dissolution with precipitation of adsorbed Zn(I),
ZnOH, Zn(II) intermediates should be taken into
account.
Impedance diagrams revealed that spongy Zn/Zn
oxide/hydroxide layer deposition at the rest potential
can be ascribed to the chemical coupling of Zn deposi-
tion with hydrogen evolution via adsorbed H atoms
and Zn(I)ads adions and to the chemical dissolution of
the corrosion products influenced by the fluid motion.
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