2886 Journal of The Electrochemical Society, 146 (8) 2886-2891 (1999)

S0013-4651(98)10-079-4 CCC: $7.00 © The Electrochemical Society, Inc.

Anomalous Codeposition of Iron Group Metals

I. Experimental Results
N. Zech,* E. J. Podlaha,**,a and D. Landolt**,z
Laboratoire de Métallurgie Chimique, Département des Matériaux, Ecole Polytechnique Fédérale de Lausanne (EPFL)
CH-1015 Lausanne, Switzerland

The codeposition behavior of three alloy systems, FeNi, FeCo, and CoNi, was studied in acid sulfate electrolytes using rotating
cylinder electrodes to control mass transport conditions. The partial current densities of the codepositing metals and of the side
reaction were determined from an analysis of the deposit and were compared with those measured for the pure metals deposited
under identical conditions. Results confirmed that Ni is inhibited by the presence of Fe21 and Co21 ions. Fe deposition rate is
enhanced by the presence of Co21 and Ni21 ions. The ion of the less noble metal has a stronger influence on the deposition behav-
ior of the partner ion. Co is inhibited by codeposition of Ni21 ions and enhanced by Fe21 ions. The present data demonstrate that
anomalous codeposition of iron group metals involves both inhibiting and accelerating effects.
© 1999 The Electrochemical Society. S0013-4651(98)10-079-4. All rights reserved.

Manuscript submitted October 21, 1998; revised manuscript received June 23, 1999.

The iron group metals Fe, Co, and Ni exhibit a so-called anom-
alous codeposition behavior, i.e., the less noble metal is deposited
preferentially to the more noble one.1 The phenomenon has been ex-
plained in the literature as an inhibition of the deposition of the more
noble metal by the codepositing less noble metal.1-6 The inhibiting
effect is generally strongest when the reaction rate of the less noble
metal is kinetically controlled and it diminishes as the limiting cur-
rent is reached.4-6 In an earlier study in our laboratory,7 the codepo-
sition behavior of iron group metals was studied using the rotating
cylinder Hull (RCH) cell. This cell permits one to perform alloy
deposition over a wide range of current densities in a single experi-
ment while maintaining well controlled mass transport conditions.8,9
On the other hand, the potential scale used is a calculated one and
therefore its validity depends on the accuracy of the numerical sim-
ulation of the potential distribution.7,8,10 The data of the study in
Ref. 7 confirmed the inhibition of the more noble metal by the less
noble one. It also suggested that deposition of the less noble metal is
enhanced by the codepositing more noble iron group metal.7 Such an
effect cannot be accounted for by present theories. Therefore, it was
considered necessary to verify the observed enhancing effect and
study in more detail the mutual interactions between codepositing
species using an electrode with a uniform primary current distribu-
tion and controlled mass transport conditions. The experimental re-
sults of such a study are given in the present paper. A theoretical
model for simulating the codeposition behavior of iron group metals
will be presented in a subsequent publication.11
The different models on anomalous codeposition published in the
literature explicitly or implicitly assume that during codeposition the
reaction rate of the less noble metal is the same as in single metal
deposition.5,6,12,13 However, there are some indications in the litera-
ture of the existence of enhancing effects. Notably, there is a slight in-
crease in the deposition rate of iron when deposited from an FeNi
alloy plating electrolyte compared to the single metal deposition rate
is apparent in Fig. 1 of the classical paper of Dahms and Croll14 and
a similar result is suggested by earlier data of Croll and Romankiw.15
Very recently, Sasaki and Talbot16,17 studying anomalous codeposi-
tion of iron group metals with a rotating disk electrode also observed
that the deposition of iron is enhanced by the codepositing nickel and
cobalt. Inhibiting and enhancing effects in alloy deposition were dis-
cussed previously by the present authors18,19 who proposed a com-
mon theoretical approach to the description of the anomalous and in-
duced codeposition phenomena. Deposition was carried from acid
** Electrochemical Society Student Member.
** Electrochemical Society Active Member.
* a Present address: Department of Chemical Engineering, Louisiana State Universi-
ty, Baton Rouge, Louisiana 70803, USA.
*z E-mail: dieter.landolt@epfl.ch
sulfate electrolytes under well-defined mass transport and current dis-
tribution conditions, using a recessed rotating cylinder electrode
(RCE). The concentrations of the reacting species were chosen to
facilitate the observation of expected interaction phenomena rather
than to achieve specific alloy compositions of technological interest.
The purpose of this paper is to investigate in more detail the inter-
actions between codepositing iron group metals and to provide ex-
perimental data suitable for testing theoretical models.
Experimental
Electrochemical cell.—A two-compartment cell with a mercury
sulfate reference electrode (MSE) was used. The anolyte and
catholyte were separated by an anion selective membrane (type
PCAcid 100, Polymerchemie Altmeier), supported on a cylindrical
holder. A dimensionally stable anode (DSA type A, Eltech Systems
Corporation) in the form of a cylindrical mesh was used as the
counter electrode. It was placed concentric to the working electrode,
on the opposing side of the membrane. The working electrode was a
copper RCE having a diam of 1.5 cm. The rotation rate was con-
trolled by a Pine Instrument rotator. The cylindrical electrodes were
recessed 0.25 cm from the insulating shaft to provide a more uni-
form primary current distribution. The height of the working elec-
trode was 2 cm. Current densities between 1 and 100 mA cm22 were
applied, producing a deposit thickness of 2-4 mm. Unless otherwise
stated, all experiments were performed at a rotation rate of 800 rpm.
Instrumentation.—A potentiostat (Autolab PGSTAT20, Eco
Chemie BV) interfaced to a 486-80 MHz PC was used for galvano-
static experiments. The MSE was fixed several millimeters away
from the surface of the electrode (no Luggin capillary). The ohmic
drop was determined by impedance spectroscopy (Zahner Instru-
ment) using a frequency range of 10-110 kHz and amplitude of 10
mV. The ohmic resistance was readily measured from the intercept
with the real-axis in a Nyquist plot. All applied potentials reported
here are corrected for ohmic drop.
Solutions.—An acid sulfate solution was chosen for this study,
containing metal sulfates (NiSO4·6H2O, CoSO4·7H2O, and/or
FeSO4·7H2O), boric acid, sodium sulfate, and double distilled water.
The water was sparged 1 h with nitrogen before solution preparation.
When preparing metal salt solutions of different concentrations, the
amount of sulfate ions was kept constant by the addition of sodium
sulfate. The pH was adjusted to a value of 3 with sulfuric acid. The
compositions of the different solutions used are listed in Table I. The
prepared solutions were sparged before the experiments, and a nitro-
gen flux was maintained above the solution during experiments. The
bulk pH was measured before and after every deposition (Jenway pH
meter 3010). In the event of a pH change, the value was corrected by

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 Journal of The Electrochemical Society, 146 (8) 2886-2891 (1999) 2887
S0013-4651(98)10-079-4 CCC: $7.00 © The Electrochemical Society, Inc.

Table I. Electrolyte compositions.

NiSO4 CoSO4 FeSO4 H3BO3 Na2SO4

Solution (M) (M) (M) (M) (M)

FeNi 0.025 M/ 0.2 M 0.2 0.025 0.4 0.5

FeNi 0.05 M/ 0.05 M 0.05 0.05 0.4 0.625
FeNi 0.2 M/ 0.2 M 0.2 0.2 0.4 0.325
FeNi 0.2 M/ 0.05 M 0.05 0.2 0.4 0.475
FeCo 0.025 M/ 0.2 M 0.2 0.025 0.4 0.5
FeCo 0.05 M/ 0.05 M 0.05 0.05 0.4 0.625
FeCo 0.2 M/ 0.2 M 0.2 0.2 0.4 0.325
CoNi 0.025 M/ 0.2 M 0.2 0.025 0.4 0.5
CoNi 0.05 M/ 0.05 M 0.05 0.05 0.4 0.625
CoNi 0.2 M/ 0.2 M 0.2 0.2 0.4 0.325
Ni 0.2 M 0.2 0.4 0.525
Ni 0.05 M 0.05 0.4 0.675
Co 0.2 M 0.2 0.4 0.525
Co 0.025 M 0.025 0.4 0.7
Fe 0.2 M 0.2 0.4 0.525
Fe 0.05 M 0.05 0.4 0.675
Fe 0.025 M 0.025 0.4 0.7

adding sulfuric acid. All experiments were conducted at a tempera- Co results from codeposition with the less noble Fe and an increase
ture of 258C. from codeposition with the more noble Ni.

Deposit analysis.—An X-ray fluorescence (XRF) spectrometer
(Kevex Instruments) in connection with OMICRON software was
used for compositional analysis and the determination of thickness
of the deposits. Pure metals were used as standards. The calibration
of the XRF was verified by atomic absorption analysis. On every
cylinder, 11 points along the height were analyzed to calculate an
average value. The partial current densities of the alloy components
were calculated from the XRF data using Faraday’s law. The current
density of the side reaction was obtained by subtracting the sum of
the metal deposition partial current densities from the total current
density at the same potential.
Results
Effect of codepositing iron group metals on partial current den-
sities.—The results shown in Fig. 1 and 2, obtained with different
electrolyte compositions, demonstrate the effect of inhibition and
enhancement observed during codeposition of iron group metals.
Fig. 1a illustrates the codeposition behavior of Ni. In these experi-
ments, the Ni concentration in the electrolyte was always 0.2 M. The
concentrations of codepositing Co and Fe were 0.025 M. The results
show that codeposition of Fe or Co reduces the Ni partial current
densities in the potential range up to 21.5 V, the effect of Fe being
more pronounced than that of Co. These data are in qualitative
agreement with results obtained with the RCH cell.7 A transition in
the behavior of nickel occurs at approximately 21.5 V when the par-
tial current density of iron reaches the limiting current. The partial
reaction of Co is also inhibited by the codepositing Fe (Fig. 1b), but
the effect is smaller than that for nickel.
The partial current densities of Fe measured during single metal
deposition and during codeposition with Ni and Co from electrolytes
containing 0.025 M Fe21 are shown in Fig. 2a. Codeposition with Ni
or Co results in an enhancement of the reaction rate of Fe, the effect
of Co being larger than that of Ni. A limiting current plateau for Fe
deposition is reached at sufficiently cathodic potentials. Its height is
the same for single metal and for alloy deposition, indicating that no
significant differences in deposit roughness were present which
could alter the rate of mass transport. Figure 2b shows in a similar
way that the partial current density of Co is enhanced by the code-
positing Ni. Again, the limiting current density of Co is the same in
single metal and alloy deposition. The data of Fig. 1b and 2b show
that depending on the codepositing metal the rate of Co deposition
may be enhanced or slowed. A decrease in partial current density of
Influence of electrolyte concentration.—The influence of the
concentration of reacting species on the extent of inhibition and
enhancement was investigated. Figure 3a illustrates the influence of
Co21 concentration on the partial current density of Ni. The Ni21
concentration in these experiments was kept constant at 0.2 M, the
Co21 concentration was 0, 0.025, or 0.2 M, respectively. The results
show that at a higher Co concentration, the inhibition of Ni is more
important. A similar behavior is observed when Ni is codeposited
with Fe as shown in Fig. 3b, but the effect of concentration is less
obvious, because even at small concentrations Fe21 has a pro-
nounced inhibiting effect on Ni (Fig. 2a and b). The effect of code-
positing Fe on the partial current density of cobalt is shown in
Fig. 3c. At potentials more positive than approximately 21.35 V the
value of iCo decreases with increasing Fe21 concentration in the
solution. At potentials more negative than approximately 21.4 V, the
inhibiting effect disappears for both Fe21 concentrations. Figure 4
shows the partial current density of Fe deposited from electrolytes
containing 0 M, 0.05 M, and 0.2 M Ni21, respectively. In the 0.2 M
Ni21 solution at potentials up to 21.4 V the partial current density
of Fe is strongly enhanced compared to that of single metal deposi-
tion. The behavior is similar but less pronounced in the solution con-
taining 0.05 M Ni21.
The partial current densities for the side reaction of (a) FeNi, (b)
CoNi, and (c) FeCo are shown in Fig. 5. In all cases, a kinetic region
is observed at potentials below 21.4 V followed by a limiting current
plateau due to proton reduction. At more cathodic potentials, the par-
tial current of the side reaction increases due to water decomposition.
Single metal deposition.—A series of experiments was per-
formed in which Fe, Ni, and Co were deposited as single metals,
using otherwise the same conditions as in the described alloy depo-
sition experiments. Iron was deposited from solutions containing
0.2 M, 0.05 M, and 0.025 M FeSO4 and nickel and cobalt from solu-
tions containing 0.05 M, and 0.2 M NiSO4 or 0.025 M and 0.2 M
CoSO4, respectively. The detailed compositions of the solutions
used are given in Table I. The partial current densities for Fe, Co, and
Ni, respectively, measured in these experiments are given in Fig. 6.
Generally, a higher metal ion concentration yields a higher partial
current density. The Tafel lines for Fe below approximately 21.5 V
are parallel for different electrolyte concentrations. At more negative
potentials, a limiting current plateau is reached. The partial current
densities for Ni and Co do not exhibit well-defined Tafel slopes, in-
dicating that the rate-determining step may vary with potential. At

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2888 Journal of The Electrochemical Society, 146 (8) 2886-2891 (1999)
S0013-4651(98)10-079-4 CCC: $7.00 © The Electrochemical Society, Inc.

sufficiently negative potentials, a limiting current is reached. The
partial current densities for the side reactions during single metal
deposition are given in Fig. 7. The behavior corresponds to that ob-
served for the alloys. The potential for the onset of water decompo-
sition is more cathodic for Ni and Co than for Fe.
Discussion
The present results confirm that nickel deposition is inhibited by
codeposition of Fe or Co and deposition of Co by codeposition of Fe
(Fig. 1). The inhibition of nickel increases in the order Fe > Co and
with the concentration of the codepositing element (Fig. 3). All these
observations are in qualitative agreement with the literature.2,20 Ac-
cording to the data of Fig. 2, the codeposition of Ni and Co increas-
es the rate of Fe deposition in the order Co > Ni, and codeposition of
Ni increases the rate of Co deposition. These results confirm those
obtained previously by the present authors using the RCH cell7 and
therefore, corroborate the validity of that technique for alloy deposi-
tion studies. The thermodynamic nobility of the three elements stud-
ied increases in the order Fe < Co < Ni, the respective standard poten-
tials being 20.440 V (Fe/Fe21), 20.270 V (Co/Co21), and 20.257 V
(Ni/Ni21). 21 The present data indicate that during codeposition of
iron group metals, the rate of deposition of the more noble species is
inhibited while that of the less noble species is enhanced. The less
noble element seems to have a stronger influence on the behavior of
its partner, since Ni is inhibited more by Fe than by Co and Fe depo-
sition is enhanced more by Co than by Ni. Although the observed
effects seem to follow thermodynamic criteria the interactions be-
tween codepositing species leading to a decrease or an increase of the
rate of codeposition are kinetic in nature19 and must be described by
kinetic not thermodynamic models.
The inhibiting and enhancing effects described in the present
study are based on a comparison of the partial current densities of
alloy deposition with those of single metal deposition under identi-
cal conditions with respect to concentration, pH, and hydrodynam-
ics. The latter are easily controlled with the RCE. To keep the sulfate
concentration constant, the codepositing metal salt during single
metal deposition was replaced by sodium sulfate. A further condition
when comparing partial polarization curves of metals and alloys is
that the surface roughness is the same and no dendritic or powdery

Figure 1. Inhibiting effect due to codeposition of a less noble element. (a)
Partial current density of Ni during deposition from electrolytes containing
0.2 M Ni21 with and without addition of 0.025 M Co21 or Fe21. (b) Partial
current density of Co from electrolytes containing 0.2 M Co21 with or with-
out addition of 0.025 M Fe21.
Figure 2. Enhancing effect due to codeposition of a more noble element. (a)
Partial current density of Fe during deposition from electrolytes containing
0.025 M Fe21 with and without addition of 0.2 M Co21 or Ni21. (b) Partial
current density of Co from electrolytes containing 0.025 M Co21 with or
without addition of 0.2 M Ni21.

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 Journal of The Electrochemical Society, 146 (8) 2886-2891 (1999)
S0013-4651(98)10-079-4 CCC: $7.00 © The Electrochemical Society, Inc.
Figure 3. Effect of concentration of the less noble element on inhibition. (a),
(b) Partial current density of Ni during deposition from electrolytes contain-
ing 0.2 M Ni21. Co21 and Fe21 concentrations are 0.025 M and 0.2 M. (c)
Partial current density of Co during deposition from electrolytes containing
0.2 M Co21 and 0.025 M or 0.2 M Fe21. The partial current density for sin-
gle metal deposition is shown also in each figure.
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2889
deposits are formed. For the present experiments these conditions
were fulfilled, because the deposits were compact and the surface
topography of different deposits observed by scanning electron mi-
croscopy was comparable. The observed inhibition or enhancement
of the deposition rate, therefore, was not due to differences in sur-
face roughness, but to interactions between codepositing species.
Electrodeposition of iron group alloys in the pH range used here
is accompanied by production of hydrogen from reduction of pro-
tons or water. Proton reduction is largely mass transport controlled
and covers most of the potential range studied. In Fig. 7, the mass
transport limit corresponds to the partial current plateau indicated.
Water decomposition becomes important at more negative potentials
and leads to an increase in the partial current of the side reaction at
more negative potentials and a corresponding decrease of the current
efficiency for metal deposition. The data of Fig. 5 and 7 show that
the potential leading to water decomposition depends on the alloy
system studied, it is higher for Co and Ni than for Fe and its alloys.
The role of hydrogen evolution, if any, in the inhibition and enhance-
ment of codeposition in these systems cannot be clearly discerned.
The kinetics of single metal dissolution and deposition of Fe, Co,
and Ni have been studied by many authors and excellent reviews are
available.22,23 Iron dissolution and deposition is usually described by
a mechanism involving two consecutive reactions (Bockris mecha-
nism) 24 or by a catalytic mechanism involving an intermediate
species adsorbed at kink sites (Heusler mechanism).25 Nickel and
cobalt deposition and dissolution were interpreted by similar con-
secutive26-28 or catalytic reaction schemes.29-31 Modifications of the
two classical mechanisms for iron dissolution and deposition were
proposed in a series of papers by Lorenz and co-workers32,33 and by
Keddam.22 The latter author presented a comprehensive model in-
volving different reaction paths in order to simulate impedance
measurements on anodically polarized electrodes over a wide fre-
quency range. For the present purposes only the dc behavior needs
to be considered further. A critical study of the literature34 indicates
that published results on the polarization behavior of iron and nick-
el by different authors do not agree well. This applies to the reaction
order of OH2 and to the shape of the metal partial current-potential
curves which varies with pH and often does not correspond to sim-
ple Tafel behavior. It was shown by Hilbert et al.35 that the dissolu-
tion mechanism on cold-worked iron differs from that on annealed
iron electrodes, showing the importance of the substrate pretreat-
ment. In view of these difficulties, no detailed mechanistic interpre-
tation of the present data for single metal deposition was attempted
since the main purpose of this study was to characterize interactions
between codepositing species. The comparison of obtained results
for single metal and alloy deposition demonstrates that codeposition
Figure 4. Effect of Ni21 concentration on partial current density of Fe. Elec-
trolyte: 0.2 M Fe21, with 0.05 M or 0.2 M Ni21. Also shown is the current
density for single metal Fe deposition.
2890 Journal of The Electrochemical Society, 146 (8) 2886-2891 (1999)
S0013-4651(98)10-079-4 CCC: $7.00 © The Electrochemical Society, Inc.

Figure 5. Partial current density of side reactions for (a) FeNi, (b) CoNi, and
(c) FeCo alloy deposition from solutions of different metal ion concentration. Figure 6. Current density for (a) Fe, (b) Ni, and (c) Co during single metal
The straight lines are drawn to assist in visualizing the trends in the data. deposition from solutions of different concentration.

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 Journal of The Electrochemical Society, 146 (8) 2886-2891 (1999)
S0013-4651(98)10-079-4 CCC: $7.00 © The Electrochemical Society, Inc.
Figure 7. Partial current densities of side reactions during single metal depo-
sition. Electrolyte concentration for Fe deposition: 0.025 M, 0.05 M, and 0.2
M; for Co deposition: 0.025 M and 0.2 M; for Ni deposition: 0.05 M and 0.2
M. The straight lines are drawn to assist in visualizing the trends in the data.
of iron group metals can lead not only to a decrease but also to an in-
crease of partial reaction rates.
Models for anomalous codeposition of iron group metals based on
the consecutive reaction mechanism and blocking of surface sites by
adsorbed intermediates were proposed by a number of authors.5,6,15
These models describe well the observed decrease in the partial reac-
tion rate of the more noble components, but they cannot account for
the enhancement of the deposition rate of the less noble component
observed in the present experiments. Two of the present authors re-
cently developed a theoretical model for the description of induced
codeposition of molybdenum with iron group metals involving cat-
alytic interactions between the codepositing species.36 It has been
proposed that the same approach can be extended to anomalous code-
position.18 Such a model including inhibition and enhancement ef-
fects will be presented in a subsequent paper.11
Conclusions
The experimental results of the present study demonstrate that
codeposition of iron group metals leads to a reduction of the reaction
rate of the more noble component and an increase of the reaction rate
of the less noble component compared to single metal deposition.
This behavior can not be explained with existing theoretical models
for anomalous codeposition and it suggests that similarities may
exist between the mechanisms of anomalous and of induced code-
position.
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2891
Acknowledgments
This work was supported by Fonds National Suisse de la
Recherche Scientifique, Bern.
Ecole Polytechnique Fédérale de Lausanne (EPFL) assisted in meeting
the publication costs of this paper.
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