Electrochimica Acta 56 (2011) 63186329

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Corrosion of dissimilar alloys: Electrochemical noise

M. Curioni a, , R.A. Cottis a , M. Di Natale b , G.E. Thompson a
a
Corrosion and Protection Centre, The University of Manchester, Manchester M13 9PL, United Kingdom
b
Dipartimento di Matematica e Applicazioni, Universit degli Studi di Milano Bicocca, 20125 Milano, Italy

a r t i c l e i n f o a b s t r a c t

Article history: A new approach for interpreting the electrochemical noise generated by freely corroding electrodes
Received 13 December 2010 is presented. For a single electrode, with well-dened anodic and cathodic regions, it is proposed
Received in revised form 7 May 2011 that the instantaneous values of the corrosion current and open circuit potential are functions of the
Accepted 10 May 2011
time-invariant potential difference between the anodic and cathodic reactions and the time-dependent
Available online 19 May 2011
impedances associated with the anodic and cathodic reactions. The uctuations in the values of anodic
and cathodic impedances are determined by the interaction between the aggressive environment and the
Keywords:
oxide, hydroxide or adsorbed surface layer covering the anodic and cathodic regions; the instantaneous
Electrochemical noise
Corrosion
values of impedances modulate the corrosion current. The mathematical implications of these assump-
Aluminium alloys tions are discussed and the results are compared with the traditional approach, based on time-dependent
Light alloys current sources acting on constant impedances. Subsequently, the ndings for a single electrode are trans-
Galvanic coupling ferred to two dissimilar electrodes and an experimental technique that enables the estimation of the time
evolution of anodic and cathodic resistances for each of the dissimilar electrodes is presented.
2011 Elsevier Ltd. All rights reserved.

1. Introduction properties of the oxide, hydroxide or adsorbed layer covering the

The measurement of electrochemical noise is nowadays a well-
developed technique for monitoring the corrosion behaviour of a
variety of metalenvironment conditions. Electrochemical noise
measurements can be performed on a single electrode, with only
the potential noise measured (or the current noise if the electrode
potential is held constant), or on multiple electrodes connected
through a zero resistance ammeter (ZRA), enabling the simulta-
neous recording of the electrochemical potential of the coupled
electrodes and the current ow between them. Once recorded, the
potential and current can be analyzed to obtain information related
to the type of corrosion [1,2], the mean frequency and magnitude of
a corrosion event [1,35] and the noise resistance [68] or the noise
impedance [7,912]. The noise resistance and the low frequency
limit of the noise impedance are of particular interest since their
physical meaning is similar to that of the polarization resistance
but they can be obtained without perturbing the freely corroding
surface with an external potential or current [10].
In order to formalize the process of electrochemical noise gen-
eration and to generate suitable equations for the calculation of
the relevant parameters, equivalent circuits, representative of the
corroding surfaces of one or more electrodes, have been proposed.
For systems where the corrosion behaviour is dominated by the
Corresponding author. Tel.: +44 0161 306 5971.
E-mail address: michele.curioni@manchester.ac.uk (M. Curioni).
electrode surface and a low frequency plateau is observed, at suf-
ciently low frequencies, the capacitive effects can be neglected and
the electrode impedance can be treated as resistance. Traditionally,
in the equivalent circuit representing a single electrode, the anodic
and cathodic reactions are represented as time-dependent cur-
rent sources in parallel with time-independent anodic and cathodic
resistances [13]. The equivalent circuit for a corroding electrode can
be readily extended to the case of two connected corroding elec-
trodes; in this case, the equivalent circuit is given by two anodic
and two cathodic time-dependent current sources and two anodic
and two cathodic reaction resistances all connected in parallel. In
this equivalent circuit, each electrode is represented by one anodic
current source and one anodic resistance and by one cathodic cur-
rent source and one cathodic resistance. Frequently, the anodic
and cathodic time dependent current sources for each electrode
are grouped together as it is common to group the anodic and
cathodic impedances of one electrode [7]. The resulting circuit con-
sists of two time-dependent current sources, each representative
of the process of noise generation on one electrode, and two time-
independent impedances, each representative of the individual
electrode impedance. It has been demonstrated [7] that this circuit
is electrically equivalent to a circuit with time-dependent poten-
tial sources in series with time-independent electrode impedances;
therefore, the choice between the current sources model and the
potential sources model is purely arbitrary.
For current sources, the measurable potential and current noises
are the response of the constant electrode resistances to the time-

0013-4686/$ see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.05.034
 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329
varying current sources. If the electrodes are symmetrical, i.e. they
have the same resistance, the resistance can be estimated by calcu-
lating the square root of the ratio between the potential variance
and the current variance [14,15]. Similarly, the spectrum of the
noise impedance can be estimated by calculating the square root of
the ratio between the potential power spectral density and the cur-
rent power spectral density. The two operations are closely related
since the variance of a given signal in the time domain is equal to
the integral of the power spectral density over the valid frequency
range of original signal [16].
When the electrodes are dissimilar, i.e. their resistances can-
not be considered identical, it is impossible to determine precisely
the resistance values of each electrode. Bautista et al. analyzed
this problem in detail, pointing out that if it is possible to know
(or assume) which of the two dissimilar electrodes generates the
majority of the noise, then an approximate value for the resis-
tance of the less noisy electrode [13] can be estimated. The same
authors also pointed out that the limitations to the analysis deriving
from such an assumption are relatively strong; in corrosion studies,
the electrode that is corroding more severely generally generates
more noise, and the information on its resistance is important.
Other techniques that have been proposed for the measurement
of electrochemical noise on dissimilar electrodes include the use
of a platinum current probe [17] coupled with the electrode of
interest, or the application of a small potential difference between
two identical specimens [18]. The analysis presented for the former
technique has been demonstrated to depend on an invalid assump-
tion, and it measures only the impedance of the platinum probe
electrode; the latter technique may have useful application in forc-
ing electrodes to pit, but it does not normally achieve the benets
proposed by its authors [13,19].
Considering the case of metastable pitting, the conventional
EN analysis effectively treats the pit as a high impedance current
source; thus, the remaining electrode(s) can be treated as having
unchanged impedance. In this work, a new model representative
of the process of electrochemical noise generation is proposed; in
the model presented here, the metal/lm interface in the anodic
regions is treated as being at the equilibrium potential of the anodic
reaction, with the current being controlled by the resistance of
the lm or the pit. When a discrete anodic corrosion event takes
place, the metal surface is transiently activated at some location
to allow metal dissolution. Thus, locally, the resistance transiently
decreases and, at least transiently, it cannot be considered identi-
cal to that of the other electrode(s), as in the case of the traditional
EN approach. The model is based on the premise that the equilib-
rium potentials (Ea and Ec ) of the anodic and cathodic reactions are
time-independent and provide the thermodynamic driving force
for corrosion. The instantaneous value of the corrosion current is
determined by the instantaneous values of the time-dependent
anodic and cathodic resistances, associated with surface layers (i.e.
oxides, hydroxides or adsorbed species) covering the anodic and
cathodic regions. Therefore, noise is generated by the interaction
of the environment with the metal surface, producing uctuations
in the anodic and cathodic resistances and, thus, transiently modi-
fying the anodic and cathodic kinetics. The underlying assumptions
required to develop the model are: (i) at sufciently low frequen-
cies, anodic and cathodic impedances can be treated as resistances,
(ii) linear currentpotential behaviour for the anodic and cathodic
reaction and (iii) time-invariant equilibrium potentials for the
anodic and cathodic reaction. The signicance of these assumptions
is discussed further below, but it will be apparent that assump-
tion (i) implies that the Bode plot of the impedance spectrum
displays a plateau at low frequency, which might not be observed
for some metalenvironment combination within practical mea-
surement frequencies. For systems where such assumptions can
be considered acceptable, it is possible to develop an experimental
6319
V
Ref
Cathodic Surface Layer
Defect leading to Defect leading to
anodic reacon Corrosion Current cathodic reacon
Anodic Surface Layer
Cathodic Metal
Anodic Metal Phase Phase
Fig. 1. Schematic view of a multiphase material with anodic and cathodic phases
covered by an oxide/hydroxide/adsorbed layer. Interaction with the aggressive envi-
ronment produces localized uctuations in the oxide/hydroxide/adsorbed layer
properties, resulting in uctuations of the corrosion current and electrochemical
potential.
technique for the estimation of anodic and cathodic resistances of
each of the dissimilar electrodes, provided that for each individual
electrode it is possible to estimate appropriate values of Ea and Ec .
2. Theory
2.1. The corroding surface
Fig. 1 presents a schematic view of a metal with two dis-
tinct metallurgical phases (anodic and cathodic phases). On the
anodic phase, at sufciently positive potentials, metal oxidation
can take place while, on the cathodic phase, at sufciently negative
potentials, the cathodic reaction, for example oxygen reduction, is
possible. Under conditions where corrosion is possible, the elec-
trode potential is more negative than the equilibrium potential
for oxygen reduction and is more positive than the equilibrium
potential for metal oxidation. The difference between the equi-
librium potentials of the anodic and cathodic reactions provides
the thermodynamic driving force for the onset of corrosion and
its associated current, but kinetic parameters control the corrosion
rate and current density. For the majority of alloyenvironment
combinations of practical interest, the metallic phases are covered
by a surface layer of relatively high electronic or ionic electrical
resistance (oxide, hydroxide or adsorbed species), and the proper-
ties of this layer control the corrosion current density. In the case
of passive alloys, often used as corrosion resistant materials, this
is particularly true and most of the kinetic effects can be related
to the properties of the oxide covering the anodic and cathodic
phases or regions. The corrosive environment interacts locally with
the surface layer, modifying transiently its thickness, properties or
integrity. At locations where the interaction produces damage or
an increase in electronic or ionic conductivity, current concentra-
tion is possible. According to this view, the sequence of phenomena
producing an anodic event is: (i) localized oxide damage/thinning
with a small reduction in resistance, (ii) progressive current con-
centration at the defect region until localized de-passivation occurs,
(iii) dramatic reduction in localized resistance due to depassiva-
tion, (iv) potential drop due to reduction in anodic resistance with
unchanged cathodic resistance, (v) possible repassivation due to
the reduced potential and (vi) increase in the anodic resistance and
potential recovery.
2.2. Electrical equivalents
For the purpose of the identication of an equivalent circuit
representing the previously described view of the corroding sur-
6320 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329

Fig. 2. Equivalent electrical circuits for a single electrode: (a) the proposed model of noise generation based on uctuating resistances and (b) the traditional model of noise
generation based on uctuating potential sources.

face, the anodic and cathodic reactions can be represented as The interaction between corrosive environment and surface layer
time-independent potential sources (Ea and Ec respectively), each results in localized uctuation in the layer electrical properties.
connected in series with a time-dependent resistance (Ra (t) and Where the surface layer is weakened, damaged or thinned, the cur-
Rc (t) respectively), representative of the kinetic contributions of rent localizes and an anodic or cathodic event takes place, and an
the surface layer in the presence of the corrosive environment associated uctuation in the electrode potential is generated.
(Fig. 2a). In parallel with Ea Ra and Ec Rc , a capacitance Cdl
can be added to account for charge separation across the surface 2.3. Statistical models single electrode
layer. The equivalent circuit of Fig. 2a, representative of the pro-
cess of noise generation due to uctuations in the resistance of the It is of interest to discuss in detail the implications of the sta-
surface layer covering the anodic or cathodic phases, differs signi- tistical assumption that the electrochemical noise is generated by
cantly from the traditional circuits used to represent the process of uctuations of the resistances rather than by uctuations of the
electrochemical noise generation [7]. According to the traditional potential sources. For the purpose of the comparison between the
interpretation (Fig. 2b), the noise is generated by a time-dependent results given by the noise analysis on a single electrode by the tradi-
potential (current) source in series (parallel) with time invariant tional method and the proposed method, linear currentpotential
electrode resistances. A corrosion event results from a uctuation behaviour for the anodic and cathodic reaction are assumed in both
in the current (potential) source, and the response to such a uctua- cases so that the traditional circuit of Fig. 2b is representative of a
tion is determined by the constant anodic and cathodic resistances. single electrode analyzed with the traditional method. The assump-
The choice of time-dependent current or potential sources in paral- tion of linear currentpotential behaviour enables introduction of
lel or series respectively with constant resistances is purely formal potential noise sources with non-zero average values in Fig. 2b,
in such a case (although one or other representation may have a representing the anodic and cathodic reactions. The use of poten-
more direct relationship with the physical processes occurring). tial noise sources with non-zero averages does not impact on the
In this work, to facilitate the comparison between the proposed calculation of the expected power spectral densities and is appro-
equivalent circuit (based on potential sources due to the physical priate to describe a single corroding electrode, where a non-zero
meaning introduced) and the traditional approach, a circuit with average corrosion current is expected.
time dependent potential sources and time-independent resis- Electrically, the circuits of Fig. 2 can be regarded as potential
tances has been selected to represent the traditional case. In the dividers. Thus, in the time domain, the electrode potential, V(t),
following discussion, for simplicity, the effects due to the pres- is readily obtained in both cases by applying the superimposition
ence of the double layer capacitance and solution resistance are theorem for linear circuit. Specically, in the case of the circuit of
neglected. This does not introduce severe limitations to the anal- Fig. 2b:
ysis provided that only relatively low frequencies are considered
Rc Ra
and corrosion tests are performed in conductive environments. V (t) = Ea (t) + Ec (t) (1)
Ra + Rc Ra + Rc
For systems where the properties and integrity of the oxide
or hydroxide layer covering the surface change locally due to If Ea (t) and Ec (t) have average values Ea and Ec and power spectral
microstructural and compositional variations of the base alloy and densities  a and  c , the expected value of the electrode potential,
the interaction between the environment and oxide produces uc- V , is given by:
tuations of the layer properties with time at each given location,
Rc Ra
the presented model may be particularly suitable to interpret the V = Ea (t) + Ec (2)
Ra + Rc Ra + Rc
process of noise generation. Specically, the model considering the
potential noise generation as a consequence of the uctuation of Further, if Ea (t) and Ec (t) are independent, the power spectral
the values of the resistances of the surface layers, modulating the density of the electrode potential,  V , is given by [7]:
amplitude of the corrosion current, has a direct physical meaning,  Rc
2  Ra
2 Rc2 + Ra2
a c
since the uctuations of the resistances value reect the uctua- V = a + c = (3)
Ra + Rc Ra + Rc (Ra + Rc )2
tions in the oxide properties. For the described systems, according
to the traditional representation, when a corrosion event takes Conversely, in the proposed model involving constant potential
place the current (potential) sources uctuate, but there is no uc- sources and time-varying resistances, the potential in the time-
tuation of the electrode impedance. Conversely, in the proposed domain is given by:
model with uctuating resistances, the sequence of phenomena
leading to a corrosion event appears more logical. Specically, a Rc (t) Ra (t)
V (t) = Ea + Ec (4)
constant potential difference is always available to onset the cor- Ra (t) + Rc (t) Ra (t) + Rc (t)
rosion current, but the corrosion current is limited by the resistance where Ea and Ec are the equilibrium potentials for the anodic and
of the surface layers covering the anodic and cathodic phases. cathodic reaction, respectively. In this case, precise formulae for
 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329
the expected mean potential and for the power spectral density
of the potential are not available, because the potential is not lin-
early dependent on the time-varying resistance, since these appear
in both the numerator and the denominator of the time domain
expression. For our purposes it is useful to consider the rst order
Taylor approximation of the potential about the expected values
(averages) of Ra and Rc in order to obtain estimates of the expected
value and power spectral density of the potential. Assuming that
Ra and Rc have average values of Ra and Rc and power spectral den-
sity Ra and Rc and they are independent, according to [20], the
expected value of the potential and power spectral densities are
approximated by:
Rc Ra
V
= Ea + Ec
Ra + Rc Ra + Rc
 2  2
V V
V = (Ra , Rc ) Ra + (Ra , Rc ) Rc
Ra Rc
The partial derivatives of the potential calculated at the average
values of resistances are given by:
V (Ec Ea )Rc
(Ra , Rc ) = 2
(Ra ) (Ra + Rc )
V (Ea Ec )Ra
(Ra , Rc ) = 2
(Rc ) (Ra + Rc )
which, substituted in Eq. (6), give the nal formula for the power
spectral density of the potential:
(Ea Ec )2 Rc2 Ra + Ra2 Rc
V = 2 2
(Ra + Rc ) (Ra + Rc )
By comparing Eqs. (3) and (9), it is evident that the assumption
that the noise is generated by uctuations in the value of the resis-
tances rather than by uctuations in potential (or current) sources
has an impact on the calculation of the expected power spectral
density of the measurable electrode potential. Specically, in the
case of noise generation by uctuating potential sources, Eq. (3)
shows that the measured noise on the electrode potential depends
on the power spectral densities of the potential noise sources and
on the resistances. Conversely, under the assumption of noise gen-
erated by uctuations of the values of the anodic and cathodic
resistances, Eq. (9) shows that the potential power spectral den-
sity depends explicitly not only on the average values and on the
power spectral densities of the resistances but also on the differ-
ence between the equilibrium potentials of the anodic and cathodic
reaction, assumed time invariant. The time-invariance of the equi-
librium potential of anodic and cathodic reactions appears to be
an acceptable assumption, considering that the basic idea behind
the presented model is that the corrosion process, and the associ-
ated generation of electrochemical noise, is the consequence of a
thermodynamic driving force (Ec Ea , time independent) and the
presence of dissipative phenomena accounted by the anodic and
cathodic resistances in the model, determining the kinetic of the
corrosion process. Although when an anodic or cathodic event takes
place, there might be localized variations in ionic concentration and
localized changes in the diffusion regimes that in principle could
affect slightly the equilibrium potential of the associated reaction,
it seems convenient (and probably practically equivalent) to treat
such variation as intrinsically kinetic. This derives from the consid-
eration that it is difcult to discriminate if, in a localized corrosion
condition, a uctuation in the surface concentration of species is
due to the local current distribution or vice versa. However, the
conclusion that the power spectral density depends also on the
difference between the equilibrium potentials of the anodic and
cathodic reaction points out that there is a signicant difference
6321
between the proposed and the traditional approaches. This differ-
ence can be seen most clearly by considering the case of Ec = Ea
(for example, for a metal electrode immersed in a deaerated solu-
tion of its ions) when the anodic and cathodic reactions of metal
oxidation and reduction occur at the same potential and the open
circuit potential of the metal is given by the equilibrium potential
of the oxidationreduction reaction. For the traditional approach,
in this case the potential power spectral density would reason-
ably be considered negligible (or more accurately approaching the
thermal noise appropriate to the electrode impedance), but this is
not explicitly obtained from the analysis. In contrast, for the pro-
posed model, considering the noise generation as a consequence
of the uctuations of values of resistances, when Ea approaches Ec ,
(5) the rst term of Eq. (9) approaches 0, predicting correctly that the
uctuations of potential of a metal in the presence of its ions in
a deaerated solution are negligible compared to the uctuations
(6) typical of corroding systems where Ec  Ea .
2.4. Thevenin equivalent of a single electrode and extension to
multiple electrodes
The proposed model, which involves resistance uctuations, has
(7)
been shown to provide an adequate representation of the process of
noise generation on a single electrode; progressing further, the case
of two connected electrodes is examined. In order to simplify the
(8)
calculation procedure, it is convenient to treat each electrode as an
equivalent Thevenin potential source (Fig. 3). Thevenins theorem
states that any combination of potential sources, current sources,
and resistors with two terminals is electrically equivalent to a sin-
gle potential source in series with a single resistor. The equivalent
(9) potential source, Veq (t), is given by the potential at the terminals
when the circuit is disconnected from any load, and the equiva-
lent resistance, Req (t), is obtained by replacing the potential sources
with short circuits and evaluating the circuit resistance from the
two terminals. As a result (Fig. 3), in the time domain, the Thevenin
equivalent potential source, Veq,i (t), and resistance for one elec-
trode, Req,i (t), described by the equivalent circuit of Fig. 2a, for i = 1, 2
are given by:
Rc,i (t) Ra,i (t)
Veq,i (t) = Ea,i + Ec,i (10)
Ra,i (t) + Rc,i (t) Ra,i (t) + Rc,i (t)
 1
1 1 Ra,i (t) + Rc,i (t)
Req,i (t) = + = (11)
Ra,i (t) Rc,i (t) Ra,i (t) + Rc,i (t)
Consequently, each of the two electrodes (which may be dis-
similar), with anodic and cathodic reaction potentials of Ea,i and
Ec,i , and time varying anodic and cathodic resistances of Ra,i (t) and
Rc,i (t), is electrically described as an equivalent Thevenins poten-
tial sources with appropriate Veq,i (t) and Req,i (t) values (Fig. 3). With
this approach, each electrode is analyzed independently from the
other, thus the values of Ea,i and Ec,i can be different for the two
electrodes when the expected anodic and cathodic reactions are
different on the two electrodes.
If the electrodes are dissimilar, the new method presents advan-
tages over the traditional method for the evaluation of the anodic
and cathodic resistances on each electrode. When two discon-
nected dissimilar electrodes are immersed in the environment,
each electrode displays a uctuating open circuit potential, rep-
resented by Eq. (10), dependent on the electrode composition,
microstructure and interaction between surface layers and the
environment. When the dissimilar electrodes are galvanically cou-
pled, i.e. by using a ZRA, they achieve a new potential, V(t), resulting
from the new balance of anodic and cathodic reactions after the
coupling. The operation of couplingdecoupling of the dissimilar
electrodes can be repeated periodically in order to measure the
current owing across each electrode, Ii (t), when they are coupled
6322 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329

Fig. 3. (a) Thevenins potential source, equivalent to the circuit of Fig. 2a for Veq,i (t) and Req,i (t) described by Eqs. (10) and (11) and (b) equivalent circuit according to the
proposed model based on uctuating resistances for one electrode exchanging current, Ii (t), with another electrode.

and Veq,i (t) when decoupled. If the uctuation in the values of Veq,i (t)
is small compared with the difference between the potential when
the electrodes are decoupled and when the electrodes are coupled,
it is possible to assume that the Veq,i (t) of each electrode does not
change signicantly with time during the coupling period between
two successive measurements. If this approximation can be intro-
duced, it is possible to substitute Veq,i (t) in Eq. (10), with the value
of the potential of the electrode measured when it is decoupled and
assumed constant, Veq,i ; consequently, during the coupling stage,
the potential and the coupling current are given by:
Req,1 (t) Req,2 (t)
V (t) = Veq,2 + Veq,1
Ra,1 (t) + Req,2 (t) Req,1 (t) + Req,2 (t)
Veq,2 Veq,1
I(t) =
Req,1 (t) + Req,2 (t)
with the current I(t) owing from electrode 1 to electrode 2. Thus,
the values of Req,i (t) during coupling can be then estimated by
V (t) Veq,1
Req,1 (t) =
l(t)
Veq,2 V (t)
Req,2 (t) =
l(t)
In Fig. 3b, the equivalent circuit for the electrode i exchanging
current, Ii (t), with another galvanically coupled electrode is pre-
sented. According to Fig. 3b, the anodic and cathodic currents on
electrode i are:
V (t) Ea,i
Ia,i (t) =
Ra,i (t)
V (t) Ec,i
IC,i (t) =
Rc,i (t)
Combining Eqs. (16) and (17), following the directions of cur-
rent identied in Fig. 3b, for the balance of the charge, the current
owing across the electrode i is:
V (t) Ea,i V (t) Ec,i
Ii (t) = + (18)
Ra,i (t) Rc,i (t)
It should be noted that in the present case of two electrodes,
for the balance of charges and according to the current directions
identied in Fig. 3b, it is always veried that I1 (t) = I2 (t). Having
obtained the values of Req,i (t) from the experimental data by Eq.
(14) or (15), it is then possible to write system 1 with Eqs. (11) and
(18), enabling the estimation, at each time t, of the values of the
anodic and cathodic resistance on the electrode. In practice, system
1 is required to fully characterize the behaviour of the circuit of
Fig. 3b and, consequently, of the electrode i; the parallel between
the anodic and cathodic resistances, Ra,i (t) and Rc,i (t), must equal to
Req,i (t), calculated from the experimental data with Eq. (14) or (15),
and the measured galvanic coupling current, Ii (t), depends on the
relative magnitude of the anodic and cathodic current on electrode
i, as suggested by Fig. 3b and by Eq. (18)
Ra,i (t)Rc,i (t)
Req,i (t) = R (t) + R (t)
a,i c,i
i = 1, 2 (sys. 1)
V (t) Ea,i V (t) Ec,i
Ii (t) = +
Ra,i (t) Rc,i (t)
Ra,i (t) can be obtained by manipulating the rst equation of
system 1 (see Appendix A) to express Ra,i (t) as a function of Rc,i (t)
and Req,i (t) and subsequently replacing the expression of Ra,i (t)
in the second equation of system 1. Rearranging the resulting
(12)
equation provides the expression of the anodic resistances on the
electrode i:
(13) Ec,i Ea,i
Ra,i (t) = Req,i (t) (19)
Req,i (t)li (t) V (t) + Ec,i
And, with a similar procedure, the expression of the cathodic
resistance can be obtained:
Ea,i Ec,i
(14) Rc,i (t) = Req,i (t) (20)
Req,i (t)li (t) V (t) + Ea,i
The described procedure (that must be applied to each of the
(15)
coupled electrodes) has been implemented in a purpose-made Lab-
view program and employed to obtain the anodic and cathodic
resistance data presented in Figs. 11 and 12 for high purity alu-
minium galvanically coupled with AA2024T3 aluminium alloy.
3. Experimental
(16)
All the materials were degreased by immersion in acetone
for 5 min, followed by deionised water rinsing and drying in a
(17) cold air stream. After degreasing, aluminium specimens, namely
99.99 wt% Al and AA2024T3, were etched by immersion for 30 s
in 10 wt% NaOH at 60 C and subsequently desmutted by immer-
sion in 30 vol% HNO3 for 30 s at room temperature. Magnesium
specimens, namely AZ31 alloy, were grounded up to 2000 grit
emery paper, a subsequently mechanically polished with 1 m dia-
mond paste. After degreasing, copper specimens were immersed
in 30 vol% HNO3 for 30 s at room temperature, and subsequently
rinsed in deionised water and dried. Mild steel specimen were
degreased and subsequently immersed in concentrated HCl for 30 s,
prior to rinsing and drying. All the specimens were masked by
using beeswax, to expose a well dened area to the test electrolyte.
The test electrolyte (400 ml) was naturally aerated, with variable
concentration of NaCl and variable pH (controlled by addition of
NaOH or HCl), depending on the materials under test. The simul-
taneous acquisition of impedance spectra and current/potential
time records was performed by using a Solartron Modulab. The
experiments of galvanic coupling/decoupling (not requiring the
simultaneous acquisition of an impedance spectrum) were per-
formed by using a Concerto Multichannel potentiostat.
 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329 6323

1 g/l NaCl
-0.50
-0.52
-0.54
Potential vs. SCE / V

-0.56
-0.58
35 g/l NaCl
-0.60
-0.62
-0.64
200 g/l NaCl
-0.66
-0.68
-0.70
0 1000 2000 3000 4000 5000 6000
Time / s

0.01

1E-3
2

1E-4
Potential PSD / V

1E-5

1E-6

1E-7
200 g/l NaCl
1E-8 35 g/l NaCl Fig. 5. Experimental setup for the comparison between the values of Req,i calculated
with the presented approach and values of the low frequency impedance modulus
1E-9 1 g/l NaCl obtained by traditional EIS.

1E-10
0.01 0.1
Frequency / Hz
Fig. 4. (a) Time evolution of the open circuit potential for AA2024T3 alloy specimens
immersed in 1, 35 and 200 g l1 NaCl and (b) corresponding potential power spectral
densities.
4. Results and discussion
4.1. Behaviour of a single electrode
The proposed model can be used to provide qualitative inter-
pretation of the corrosion behaviour of single electrodes immersed
in electrolytes containing different concentrations of the aggressive
ion. To provide an example, AA2024T3 aluminium alloys specimens
(exposed area of 2.25 cm2 ) were immersed in 1 g l1 , 35 g l1 and
200 g l1 NaCl, and the potential noise was recorded at 1 Hz. The
AA2024T3 alloy is highly alloyed in copper and magnesium, and
contains abundant second phase material with high yields of cop-
per that act as very effective cathodic sites [21,22]. According to
the proposed model, accounting for the interaction between the
aggressive environment and the surface layers, increased noise
levels are expected for higher concentration of NaCl, due to the
increased generation of defects on the surface layer, and associated
uctuations in resistances and potential. In Fig. 4a, the poten-
tial noise in the time domain is presented for three AA2024T3
specimens immersed in 1, 35 and 200 g l1 NaCl near-neutral elec-
trolytes. The average potential decreased as the concentration of
NaCl increased. This is explained by considering that the generation
of an increased population of defects in the air-formed oxide cover-
ing the alloy surface impacts on the average values of Ra , reducing
it, while it has only a minor effect on the oxygen reduction reaction
taking place above the cathodically effective, high-copper contain-
ing particles. As a result, for the equivalent values of Ea (aluminium
oxidation) and Ec (oxygen reduction) among the three specimens,
1 an increase in electrolyte aggressiveness due to increased chloride
concentration is associated with a reduced mean value of Ra and
the potential is reduced according to Eq. (5). The power spectral
density of the potential signal was calculated by fast Fourier trans-
form (512 point segments, linear trend removal and Hann window
applied prior to FFT, and 50% overlap between successive segments
[23]). The resulting spectra, presented in Fig. 4b, are obtained by
averaging 25 PSD spectra. As it is evident, the noise levels increase
as the concentration of sodium chloride increases, with the differ-
ence being more signicant at higher frequencies. This behaviour
is qualitatively predicted by the introduced model, accounting for
the interaction with the environment; higher levels of chloride ions
result in more frequent and more substantial damage of the oxide
layer, with associated more frequent and more substantial oscilla-
tions of the corrosion potential.
4.2. Dissimilar electrodes validation of the new EN analysis
method assisted by EIS
In order to validate the procedure described for the mea-
surement of the anodic and cathodic resistances on dissimilar
electrodes, it is necessary to verify the approximation that Veq,i
is constant, or at least predictably changing, during the coupling
time. Further, it must be veried that Veq,i is close to the poten-
tial measured during the decoupling period and, therefore, Eq.
(12) is valid for two dissimilar corroding electrodes. The under-
lying condition behind these hypotheses is that the electrical
behaviour of the corroding surface does not deviate excessively
from linearity during the coupling period. For metals covered by
a relatively stable and resistive surface layer, generally displaying
a quasi-linear electrical response for small potential perturbations,
these hypotheses should be acceptable in most environments. Con-
versely, bare metalelectrolyte interfaces are expected to display
a markedly exponential electrical response (Tafel behaviour) and
the assumption of linearity may introduce unacceptable errors in
6324 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329

0.020
0.015

Potential vs. SCE / V

0.010
0.005
0.000
-0.005
-0.010
-0.015
-0.020
0 100 200 300 400 500 600

20
18
16
Current / A

14
12
10
8
6
4
2
0
0 100 200 300 400 500 600
Time / s

| Z | (Ohm) -140
100000 Phase (Deg)

-120
Impedance Modulus / ohm

-100
10000

Phase / degree
-80

-60

1000 -40

-20

0
100
1E-3 0.01 0.1 1 10 100 1000 10000 100000 1000000
Frequency / Hz

Fig. 6. (a) Potential and current time records measured by the circuit of Fig. 5 with the switch in position B for high purity aluminium coupled with AA2024T3 in 1 g l1 NaCl
(neutral) and (b) resulting impedance spectrum.

the estimation of the resistances. However, the evaluation of the
accuracy of the resistance estimation is experimentally possible
by using the circuit of Fig. 5. Here, two dissimilar electrodes are
immersed in the corrosive electrolyte and connected alternatively
to a voltmeter (Fig. 5, switch in position A) or a frequency response
analyzer capable of measuring the current time record simulta-
neously to the impedance response (Fig. 5, switch in position B).
The frequency response analyzer applies a sinusoidal potential fre-
quency sweep across the two corroding electrodes and measures
the amplitude and phase of the resulting current, thus producing
the data for the impedance spectra. During the impedance mea-
surement, simultaneously, the current owing between the two
electrodes is recorded. From the current-time record, an approx-
imate value of DC current due to the coupling is extracted and
used in the subsequent calculation of the resistance. Specically,
the average resistance of the system (Req,1 + Req,2 ) can be calculated
according to the approximation introduced by Eq. (12), by divid-
ing the potential measured by the voltmeter during the decoupling
time (Veq,1 Veq,2 , switch in A), by the average current measured
during the coupling time and simultaneous impedance measure-
ment (switch in B), under the assumption that the low-amplitude
potential frequency sweep does not affect the average coupling cur-
rent. The value of resistance calculated by this technique can be
compared with the modulus of the low frequency impedance mea-
sured by the frequency response analyzer when the switch is in
position B. Similarity between the values of resistances obtained
with the two techniques indicates that the hypothesis formulated
to generate Eq. (12) is acceptable. In practice, the measurement and
switching functions were performed directly by a single Solartron
Modulab potentiostat and frequency response analyzer, with the
working electrode terminal connected to one of the two speci-
mens and the counter electrode and reference electrode terminals
connected to the other specimen (two-electrode cell congura-
tion).
 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329 6325

0.30

Potential vs. SCE / V

0.25
0.20
0.15
0.10
0.05
0.00
-0.05

1000 2000 3000 4000 5000

20

15
Current / mA

10

1000 2000 3000 4000 5000

Time / s

40 -25
35
| Z | (Ohm)
30 Phase (Deg)
-20

25
Impedance Modulus / ohm

-15
20

Phase / degree
-10
15

-5

10
0

0.01 1 100 10000

Frequency / Hz

Fig. 7. (a) Potential and (b) current time records measured by the circuit of Fig. 5 with the switch alternatively in position A or B for high purity aluminium coupled with
AA2024T3 in 35 g l1 NaCl with the addition of 10 g l1 (0.25 M) NaOH and (c) impedance spectra acquired sequentially when the switch was in position B. The arrow indicates
the time record segment associated with the presented impedance spectra.

From an experimental viewpoint, the metalenvironment com-
binations selected to validate the hypothesis must be not too noisy,
otherwise the current uctuations generated as a consequence of
the galvanic coupling dominate the current response due to the
application of the sinusoidal potential signal and, consequently, the
impedance measurement is unreliable. This is the case, for example,
of galvanically coupled relatively high purity aluminium (exposed
area of 2.25 cm2 ) and AA2024T3 (exposed area of 2.25 cm2 )
immersed in 1 g l1 NaCl. This combination of material is of par-
ticular interest and relatively well known since it is widely applied
in the aerospace industry. Here, sheets of AA2024T3 are clad with a
0.1 mm sheet of relatively pure aluminium. The cladding procedure
enhances the otherwise poor corrosion resistance of the AA2024T3,
because the number and extension of the cathodic regions on the
relatively pure aluminium is orders of magnitude lower than that
on the AA2024T3. Further, the reduced presence of alloying ele-
ments and of phase heterogeneities results in a reduced population
density of aws in the air-formed oxide above the alloy matrix,
which is capable of better resisting the aggressive environment. It
is expected that the corrosion behaviour of the selected alloys cou-
ple is dominated by effects related to the interaction between the
surface oxides and the aggressive environments, thus the assump-
tion (i)(iii) on which the presented model is based are acceptable.
However, as evident from Fig. 6, the measurement of impedance on
such a system by using the circuit of Fig. 5 (switch in position B) is
unsuccessful; the uctuations in current due to the corrosion pro-
cesses on the two specimens are very signicant and exceed the
response to the sinusoidal potential perturbation. Therefore, the
current signal appears uncorrelated with the stimulating potential
signal, and the impedance spectra are noisy and unable to pro-
vide a reliable value for the low frequency impedance modulus.
Thus, in order to validate the presented approach by using EIS, it is
necessary to modify the environment/materials combination such
as the uctuations generated by the process of noise generation
6326 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329

Fig. 8. (a) Potential and (b) current time records measured by the circuit of Fig. 5 with the switch alternatively in position A or B for electrical grade copper and mild steel
coupled and immersed in 35 g l1 NaCl acidied to pH 3 by HCl and (c) impedance spectra acquired sequentially when the switch was in position B. The arrow indicates the
time record segment associated with the presented impedance spectra.

does not dominate the current response due to the potential fre-
quency sweep applied by EIS. For example, this can be obtained in
practice by immersing the AA2024T3-high purity aluminium cou-
ple in a solution with increased reactivity and alkalinity, 35 g l1
NaCl with 10 g l1 (0.25 M) NaOH, producing a more stable and well
correlated current response (Fig. 7a). For this couple, as the reac-
tivity of the solution increases, the stability of the oxide covering
the metal surface decreases, corrosion becomes less localized and
the associated uctuations in potential and current are reduced,
but the assumption of linear anodic and cathodic kinetics required
for the proposed noise analysis might not be completely appro-
priate. However, the reduced uctuations in corrosion current and
potential enable the acquisition of a reliable impedance spectrum
displaying a low frequency limit of the impedance (23 , Fig. 7b).
The potential difference between the specimens measured during
the decoupling stage, Veq,1 Veq,2 , was 0.23 V and the DC current
was 11.7 mA (Fig. 7a). As a result, the resistance calculated from
Eq. (12) was 19.7 , in good agreement with the values from
the impedance measurement (23 ). The agreement between
the resistance estimated with the proposed method and the low
frequency impedance obtained by EIS suggests that, in this case,
the violation of non linearity does not introduce an unacceptable
error. Thus, for the specic alloys couple immersed in less aggres-
sive environments where the oxide-related effects are expected to
dominate and the linearity assumption appears more acceptable,
the estimation of resistances provided by the proposed method is
expected to be reasonably accurate.
In order to further evaluate by EIS the accuracy of the pro-
posed approach on a metalsenvironment combination where
the assumptions of linearity and existence of a low frequency
impedance plateau are violated, similar experiment were per-
formed on coppermild steel couple in acidied solutions and
AA2024T3AZ31 (Al alloyMg alloy) couple in quasi neutral NaCl
solution. The rst experiment was performed by using electri-
 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329 6327

0.8

Potential vs. SCE / V

0.6

0.4

0.2

0.0

-0.2
2000 4000 6000 8000 10000 12000
Time (s)

25
Current / mA

20

15

10

2000 4000 6000 8000 10000 12000

Time / s

30

25 | Z | (Ohm)
Phase (Deg)
-20
20
Impedance Modulus / ohm

Phase / degree
15

-10

10

5
1E-3 0.01 0.1 1 10 100 1000 10000 100000

Frequency / Hz

Fig. 9. (a) Potential and (b) current time records measured by the circuit of Fig. 5 with the switch alternatively in position A or B for AZ31 Mg alloy and AA2024 aluminium
alloy coupled and immersed in 35 g l1 NaCl (neutral) and (c) impedance spectra acquired sequentially when the switch was in position B. The arrow indicates the time
record segment associated with the presented impedance spectra.

cal grade copper (exposed area of 1.88 cm2 ) and mild steel resistance can be estimated to be between 109 and 129 k, in
(exposed area of 2.82 cm2 ) immersed in 35 g l1 NaCl acidied acceptable agreement with the impedance at 1 mHz of 100 k
to pH 3 by HCl. This system is expected (i) to deviate to some (Fig. 8b). For the case of AZ31 magnesium alloy (exposed area of
extent from linearity during the coupling time, due to the non- 2.25 cm2 ) coupled with AA2024 (exposed area of 2.25 cm2 ) in
passive behaviour of iron and copper in the selected environment quasi-neutral 35 g l1 NaCl the agreement between the two meth-
and (ii) to not display a well-dened low-frequency impedance ods was acceptable (Fig. 9), even if abundant hydrogen evolution
plateau. In this case, during the decoupling time, the potential and a signicant transient in the coupling current were observed
difference between the two electrodes drifted more signicantly and the impedance spectra appeared relatively noisy (Fig. 9a and b).
with time compared with the coupled aluminiumaluminium alloy For a potential difference of 0.5 V, a coupling current of 22 mA
system. However, the drift was relatively small compared with was measured, giving an estimated resistance of 22 , in rela-
the absolute value of Veq,1 Veq,2 and, in this case, it is possi- tively close agreement with the low frequency impedance limit
ble to extract two values of resistance, one for the Veq,1 Veq,2 of approximately 15 . In summary, the experiments presented
measured prior to coupling and one for the Veq,1 Veq,2 mea- in Figs. 79 suggest that the estimation of the resistance with the
sured after the coupling. For example (Fig. 8a), the potential proposed method is in acceptable agreement with the values of
varies between 0.17 and 0.2 V before and after coupling respec- low-frequency impedance obtained by EIS even for systems that
tively. The DC current values were 1.55 A (Fig. 8a). Thus, the violate to some extent the assumption on which the proposed
6328 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329

90000
Anodic Resistances
80000 AA2024T3
Al-99.9%
70000

Resistance / ohm
60000

50000

40000

30000

20000

10000

0
0 5000 10000 15000 20000 25000 30000
Time / s

Cathodic Resistances
120000 AA2024T3
Al-99.9%
100000

Resistance / ohm
80000

60000

40000

20000

0
0 5000 10000 15000 20000 25000 30000
Time / s

Fig. 11. (a) Anodic (Ra,i ) and (b) cathodic (Rc,i ) resistances for AA2024T3 and high
purity aluminium immersed in 35 g l1 NaCl under couplingdecoupling conditions.

the AA2024T3 alloy was close to 0.675 V at the beginning of

Fig. 10. (a) Potential and (b) coupling current time records measured dur-
ing immersion of AA2024T3 and high purity aluminium in 35 g l1 NaCl under
couplingdecoupling conditions.
method is based. Thus, the application of the proposed method
to metal couplesenvironment combinations where the assump-
tion of linearity, existence of a low-frequency impedance plateau
and constant equilibrium potentials for the anodic and cathodic
reaction appears correct should provide reliable estimation of
the anodic and cathodic resistances on each dissimilar elec-
trode.
4.3. Dissimilar electrodes application of the new EN analysis
method
Having shown that the new approach provides values of
resistance (Req,i ) that are comparable with those obtained by
impedance measurements, the electrochemical noise generated by
two coupled dissimilar specimen can be interpreted without the
application of any external signal. Fig. 10 shows the potential and
current time records (a Concerto multichannel potentiostat was
used) for a couplingdecoupling experiment on AA2024 and high
purity aluminium in 3.5% NaCl. The coupled system displayed a
potential close to 0.775 V, showing little drift for the duration
of the immersion experiment. When decoupled, the potential of
the experiment and drifted to approximately 0.65 V toward the
end of the experiment. A similar behaviour was observed for the
decoupled high purity aluminium, with an initial potential of about
1.010 V that drifted progressively toward 0.985 V at the end
of the immersion. In both cases, the drift was small compared
with the potential change associated with the couplingdecoupling
effect. From Fig. 10a, the horizontal dashed lines joining the poten-
tial measured during the decoupled time represent the values of
Veq,1,2 used for the calculations, obtained by averaging the last
50 s of the measured potential in the decoupled stage. The current
time record showed a relatively steady value of coupling current,
but the levels of noise on the current increased signicantly with
the immersion time. In the following calculations, Ec and Ea are
assumed to be +0.5 and 2 V (SCE) respectively for both the high
purity aluminium and the AA2024T3 alloy. By solving Eqs. (19)
and (20), at each time t, the anodic and cathodic resistances may
be estimated for both the electrodes (Figs. 11 and 12). Thus, the
cathodic resistance was very high for the high purity aluminium,
due to the lack of effective cathodic sites on the surface. Further
the anodic resistance for high purity aluminium was signicantly
higher than that for the AA2024T3, in agreement with the presence
of a more resistant, less awed oxide on the aluminium surface,
compared with that present on the AA2024T3 alloy. Finally, the
low value of cathodic resistance measured for the AA2024T3 is
in agreement with the presence of a high population density of
active cathodic sites, corresponding to the abundant presence of
high-copper containing second phase material at the alloy sur-
face.
 M. Curioni et al. / Electrochimica Acta 56 (2011) 63186329 6329

100000
Req,i (t)Rc,i (t)
Al-Cathodic Ra,i (t) =
Rc,i (t) Req,i (t)

Then, substitute the expression of Ra,i (t) in the second equation

80000
Resistance / ohm

of system 1
Al-Anodic V (t) Ea,i V (t) Ec,i
60000 Ii (t) = +
Req,i (t)Rc,i (t)/(Rc,i (t) Req,i (t)) Rc,i (t)

AA2024T3-Anodic
40000 V (t) Ea,i V (t) Ec,i
Ii (t) = [R (t) Req,i (t)] +
Req,i (t)Rc,i (t) c,i Rc,i (t)
AA2024T3-Cathodic Multiply both sides by Rc,i (t)
20000
V (t) Ea,i
Ii (t)Rc,i (t) = [Rc,i (t) Req,i (t)] + V (t) Ec,i
0 5000 10000 15000 20000 25000 30000 Req,i (t)
Time / s
V (t) Ea,i V (t) Ea,i
Fig. 12. Smoothed (100 point moving average) anodic (Ra,i ) and cathodic (Rc,i ) resis- Ii (t)Rc,i (t) = Rc,i (t) Req,i (t) + V (t) Ec,i
tances for AA2024T3 and high purity aluminium immersed in 35 g l1 NaCl under Req,i (t) Req,i (t)
couplingdecoupling conditions.

V (t) Ea,i
Ii (t)Rc,i (t) = Rc,i (t) V (t) + Ea,i + V (t) Ec,i
5. Conclusions Req,i (t)

A technique for the measurement and interpretation of the

 
V (t) Ea,i
electrochemical noise generated on dissimilar electrodes has been Rc,i (t) = Ii (t) = Ea,i Ec,i
Req,i (t)
presented. The interpretation of the electrochemical noise relies on
the assumption that the process of electrochemical noise genera-
Ea,i Ec,i
tion results from uctuations in the values of resistance of a surface Rc,i (t) =
layer covering the anodic and/or cathodic phases. As a result of the Ii (t) ((V (t) Ea,i )/Req,i (t))
potential difference between the anodic and cathodic reactions, and
of the uctuations of the electrical resistances associated with the Ea,i Ec,i
Rc,i (t) = Req,i (t)
presence of surface layers above the anodic and cathodic phases, the Req,i (t)Ii (t) V (t) + Ea,i
corrosion current and the electrode potential uctuate with time.
With identical procedure Ra,i can be obtained, provided that in
The analysis performed on one electrode is applicable to dissimi-
the rst step the expression of Rc,i instead of that of Ra,i is obtained.
lar electrodes and enables estimation of the time evolution of the
anodic and cathodic resistances on each coupled electrode. The the-
References
oretical approach is validated by comparison of the resultant values
of resistances with the low frequency impedance modulus limit [1] R.A. Cottis, Proceedings of Corrosion06, NACE, San Diego, 2006, paper 643.
obtained by traditional EIS. Analysis of the relatively predictable [2] F. Mansfeld, Z. Sun, Corrosion 55 (1999) 915.
coupling between AA2024T3 and high purity aluminium provided [3] J.M. Sanchez-Amaya, R.A. Cottis, F.J. Botana, Corr. Sci. 47 (2005) 3280.
[4] J.M. Sanchez-Amaya, M. Bethencourt, L. Gonzalez-Rovira, F.J. Botana, Elec-
further validation. trochim. Acta 52 (2007) 6569.
[5] A.M. Kuznetsov, Russ. J. Electrochem. 44 (2008) 1327.
[6] U. Bertocci, C. Gabrielli, F. Huet, M. Keddam, P. Rousseau, J. Electrochem. Soc.
Acknowledgement
144 (1997) 37.
[7] U. Bertocci, C. Gobrielli, F. Huet, M. Keddam, J. Electrochem. Soc. 144 (1997) 31.
EPSRC is acknowledged for provision of nancial support [8] J.F. Chen, W.F. Bogaerts, Corr. Sci. 37 (1995) 1839.
[9] F. Mansfeld, L.T. Han, C.C. Lee, C. Chen, G. Zhang, H. Xiao, Corr. Sci. 39 (1997)
through the LATEST2 Programme Grant.
255.
[10] F. Mansfeld, C.C. Lee, J. Electrochem. Soc. 144 (1997) 2068.
Appendix A. Procedure to calculate Ra,i (t) and Rc,i (t) from [11] F. Mansfeld, C.C. Lee, G. Zhang, Electrochim. Acta 43 (1998) 435.
[12] N.C. Rosero-Navarro, M. Curioni, R. Bingham, A. Durn, M. Aparicio, R.A. Cottis,
system 1 G.E. Thompson, Corr. Sci. 52 (2010) 2489.
[13] A. Bautista, U. Bertocci, F. Huet, J. Electrochem. Soc. 148 (2001) B412.
R (t)R (t)
Req,i (t) = a,i c,i [14] R.A. Cottis, Corrosion 57 (2001) 265.
Ra,i (t) + Rc,i (t) [15] R.A. Cottis, M.A. Al-Ansari, G. Bagley, A. Pettiti, Mater. Sci. Forum 289292
i = 1, 2
V (t) Ea,i V (t) Ec,i (1998) 741.
Ii (t) = + [16] R.A. Cottis, S. Turgoose, Mater. Sci. Forum 192194 (1995) 663.
Ra,i (t) Rc,i (t)
[17] J.F. Chen, W.F. Bogaerts, Corrosion 52 (1996) 753.
[18] M.L. Benish, J. Sikora, B. Shaw, E. Sikora, M. Yaffe, A. Krebs, G. Martinchek,
Firstly, express Ra,i (t) as a function of Rc,i (t) and Req,i (t) Proceedings of Corrosion98, NACE, Huston, 1998.
[19] R.A. Cottis, Electrochim. Acta 52 (2007) 7585.
Ra,i (t)Rc,i (t) [20] A.M. Mood, F.A. Graybill, D.C. Boes, Introduction to the Theory of Statistics, 3rd
Req,i (t) = ed., McGraw-Hill, New York, 1974, p. 180.
Ra,i (t) + Rc,i (t)
[21] M. Saenz de Miera, M. Curioni, P. Skeldon, G.E. Thompson, Corr. Sci. 52 (2010)
2489.
[22] M. Curioni, M. Saenz De Miera, P. Skeldon, G.E. Thompson, J. Ferguson, J. Elec-
Req,i (t)[Ra,i (t) + Rc,i (t)] = Ra,i (t) + Rc,i (t) trochem. Soc. 155 (2008) C387.
[23] P.D. Welch, IEEE Trans. Audio Electroacoust. AU-15 (1967) 70.

Req,i (t)Ra,i (t) + Req,i (t)Rc,i (t) = Ra,i (t)Rc,i (t)

Req,i (t)Rc,i (t) = Ra,i (t)[Rc,i (t) Req,i (t)]