Corrosion Science 45 (2003) 1647–1660

www.elsevier.com/locate/corsci

An impedance model for the estimation of

water absorption in organic coatings.
Part II: A complex equation of mixture
~es
A.S. Castela, A.M. Simo *

Department of Chemical Engineering, Instituto Superior T

ecnico, Av. Rovisco Pais,
Lisboa 1049-001, Portugal
Received 17 March 2001; accepted 17 January 2003

Abstract

An impedance model for the estimation of water absorption in organic coatings is pre-
sented. In part I, the model was developed taking a high frequency approximation. In part II
the model is generalized by removing that approximation and by treating the film as a mul-
ticomponent system. Comparison with weight variation data has shown an improvement of
the estimates made with the classical model of Brasher and Kingsbury. A low frequency ap-
proximation of the model has given good results with freestanding films.

2003 Elsevier Science Ltd. All rights reserved.

Keywords: Water uptake; A. Organic coatings; Electrochemical impedance; Corrosion

1. Introduction

In the first part of this work a simple model for the determination of the water
uptake in binary or ternary coatings has been developed. The equations derived were
based on the assumption that the film resistance is high enough to justify the high
frequency approximation, i.e., it assumed that at the working frequency the response
is purely capacitive and reflected the dielectric properties of the coating. In many
cases, however, the phase angle in the impedance spectrum presents values well

*
Corresponding author. Tel.: +351-21-841-7234; fax: +351-21-840-4589.
E-mail address: pcsimoes@alfa.ist.utl.pt (A.M. Sim~
oes).

0010-938X/03/$ - see front matter
2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0010-938X(03)00015-5
1648 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660

below 90, due to a non-ideal character of the coating capacitance. This effect is
particularly important in freestanding films, where ionic conduction is facilitated by
the absence of the coating/metal interface. In a previous study [1] it was observed
that the impedance spectra of freestanding films are dominated by a strong decrease
of the coating resistance during immersion, in contrast with the relatively stable
capacitive behaviour of applied coatings. The phase angle of the capacitive part of
the spectrum was also significantly lower than that of applied films and application
of the classical Brasher–Kingsbury model has lead to excessive estimates of the water
content, above 35%. In this case the model presented in part I of this work, in which
the high frequency approximation is considered, can also lead to erroneous results.
Therefore, in this second part a more general solution for this model is presented, in
which the high frequency approximation is eliminated. A wider film definition is also
envisaged, which considers all the components such as pigment, plasticizer, binder,
water, air, etc.

2. Model development

2.1. Multicomponent system

In this deduction, the following assumptions will be considered:

(a) The film components are not soluble among them.

(b) There will be neither swelling nor contraction of the film as a result of water pen-
etration.
(c) The film composition is constant throughout the thickness.
(d) The components are homogeneous, with constant densities and electric para-
meters (ei ¼ constant) for all the points of the film, and remain constant for
the duration of the test. The same can be stated for the ionic strength of the so-
lution contained in the film.
(e) The electric behaviour of the film can be described by a circuit consisting of RC
networks in series.

In this deduction, the film shall be envisaged as being composed of a finite number
of thin layers. Since the film composition is considered as being constant across the
film, then the layers will all be equivalent. Under these conditions, and like in part I
of this work, the system can be described by an equivalent circuit of a finite series of
parallel RCÕs that degenerates in a circuit of a single parallel RC [2]. For most real
systems, however, the impedance response is more accurately described by a resis-
tance in parallel with a constant phase element (CPE) [3–6] or by an RC network
with a depression angle, according to the Cole and Cole [7,8] definition. In this work
this last approach is chosen although any of the two approaches are valid. Taking
this approach, the impedance, Z, for a RC circuit with a symmetric depression is
given by:
 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660 1649

Rf
Z ¼ RX þ n ð1Þ
1 þ ðjxsf Þ

where n is the depression coefficient (n ¼ 1 for non-depressed semi-circles), x is the

angular frequency defined has x ¼ 2pf , in which f is the frequency, and the term
sf ¼ Cf Rf represents the time constant where Cf and Rf consist of the film capaci-
tance and the film resistance, respectively. RX is the ohmic resistance (expressed in X).
Considering the Moivre transformation where the real power of a complex
n n
number is given by ðjxsÞ ¼ ðxsÞ ½cosðnp=2Þ þ j sinðnp=2Þ, then the impedance
components of the complex number, Zreal þ jZimag , can be separated in:
8
n 
> Rf 1 þ ðxsf Þ cosðnp=2Þ
>
< Zreal ¼ RX þ

> n 2
n 2
1 þ ðxsf Þ cosðnp=2Þ þ ðxsf Þ sinðnp=2Þ 0
n ð1 Þ
>
> Rf ðxsf Þ sinðnp=2Þ
>
: Zimag ¼ 
2
2
n n
1 þ ðxsf Þ cosðnp=2Þ þ ðxsf Þ sinðnp=2Þ

where Rf and RX represent the resistance associated with the ionic current inside and
outside the film, respectively. The contribution of RX to the real part of impedance is
usually negligible except at the very high frequencies. Considering that approxima-
tion, then the ratio of the impedance components gives:

Zimag ðxsf Þn sinðnp=2Þ

¼ n ð2Þ
Zreal 1 þ ðxsf Þ cosðnp=2Þ

Determination of a mixture equation for the dielectric constant of the film (see
Appendix A), results in a complex correlation that can be decomposed in the fol-
lowing expressions:
8  p  p
> XN
ðxsp Þnp
>
> ðxs Þ
n
sin n ¼ q sin np /
>
< f f
2 p¼1
qp 2 p
 p  p ð3Þ
>
> XN
ðxsp Þnp
> n
: ðxsf Þ cos n 2 ¼ qf
>
q
cos np /
2 p
p¼1 p

in which N is the total number of film components, p a number representing a

specific component, qp , sp , /p and np are respectively the resistivity, the time con-
stant, the volume fraction and the depression coefficient for the component p.
Two new variables

ðxsp Þnp  p ðxsp Þnp  p

nsin
p ¼ sin np and ncos
p ¼ cos np
qp 2 qp 2

which are constituted by parameters related only with component p shall now be
used. For each component, these two variables are constant with time, being only
function of the frequency. Substituting these in Eq. (3), and taking qf ¼ Rf A=d and
kt ¼ Zimag =Zreal then Eq. (2) becomes:
1650 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660

kt d XN
¼ ðnsin  kt ncos
p Þ/p ð4Þ
Rf A p¼1 p

For t ¼ 0, it becomes:

k0 d X N
0
¼ ðnsin  k0 ncos
p Þ/p;0 ð4 Þ
ðRf Þ0 A p¼1 p

where the subscript 0 correspond to t ¼ 0. Subtracting (40 ) from (4):

 N h i
kt k0 d X
 ¼ nsin ð/ p  / p;0 Þ  n cos
ðk t /p  k 0 /p;0 Þ ð5Þ
Rf ðRf Þ0 A p¼1 p p

On the other hand, the summation of the volume fractions of all the components at
each instant has to be equal to 1.
X
N X
N X
N
/p;s ¼ /p ¼ /p;0 ¼ 1 ð6Þ
p¼1 p¼1 p¼1

in which the /p;s corresponds to the volume fraction of the component p at satu-
ration. If one of the components is removed from the summation:
X
N
ð/1  /1;0 Þ ¼ ð/p;0  /p Þ ð7Þ
p¼2

If the term with p ¼ 1 is also separated in Eq. (5), then it becomes:

 N h i
kt k0 d X
 ¼ nsin cos sin
p ð/p  /p;0 Þ  np ðkt /p  k0 /p;0 Þ þ n1 ð/1  /1;0 Þ
Rf ðRf Þ0 A p¼2
 ncos
1 ðkt /1  k0 /1;0 Þ

By substituting Eq. (7) and re-arranging:

 N h i
kt k0 d X
 ¼ ðnsin
p  n sin
1 Þð/p  /p;0 Þ  n cos
p ðk t /p  k 0 /p;0 Þ
Rf ðRf Þ0 A p¼2
 ncos
1 ðkt /1  k0 /1;0 Þ ð8Þ
PN
Considering that /1 ¼ 1  p¼2 /p for any instant t and also for t ¼ 0, then Eq. (8)
can be converted into:

 N h i
kt k0 d X
 ¼ ðnsin
p  n sin
1 Þð/p  /p;0 Þ  ð/p k t  / p;0 k 0 Þðn cos
p  n cos
1 Þ
Rf ðRf Þ0 A p¼2
 ncos
1 ðkt  k0 Þ

Manipulation of the equation with the isolation of the component ‘‘solution’’

(p ¼ 2), allows the determination of the following equation:
 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660 1651


kt k0 d
 þ /0 w0sol  w  w1
Rf ðRf Þ0 A
/¼ ð9Þ
wtsol
with
8
>
>
> w0 ¼ ðnsin sin cos cos
sol  n1 Þ  k0 ðnsol  n1 Þ
> sol
> t sin sin cos cos
< wsol ¼ ðnsol  n1 Þ  kt ðnsol  n1 Þ
PN h i 0
ð9 Þ
>
> w¼ ðnsin  nsin Þð/p  /p;0 Þ  ðncos  ncos Þð/p kt  /p;0 k0 Þ
>
>
p 1 p 1
>
:
p¼3
w1 ¼ ncos1 ðkt  k0 Þ

Eq. (9) is a general equation for the determination of /.

For the determination of the film resistance, Rf and ðRf Þ0 , two different ap-
proaches can be used. The first one results from assuming that the real part of im-
pedance at low frequencies approximately corresponds to the resistance of the film,
i.e., Rf ðZreal Þf !0 where once more the resistance of the outer solution is considered
negligible. For this solution the following conditions need to be fulfilled:

• The spectra acquisition must be obtained down to sufficiently low frequencies, at

which the film resistance is experimentally measurable (h 0).
• The substrate cannot actively corrode, since the equivalent circuit is not the same
in that condition.

Naturally, in most systems these two conditions can only be fulfilled by free-
standing films.
Under these conditions the film resistance at time t and for t ¼ 0 is:
(
Rf ¼ ðZreal Þtf !0
0 ð10Þ
ðRf Þ0 ¼ ðZreal Þf !0

Assuming that the real impedance for low frequencies at the beginning of immersion
time, ðZreal Þ0f !0 , is much higher than at time t, ðZreal Þtf !0 then, at low frequencies, Eq.
(9) becomes:
kt d
t þ /0 w0sol  w  w1
ðZreal Þf !0 A
/¼ ð11Þ
wtsol
A different approach consists in solving the system (10 ) by isolating the variables Rf
n
and ðxsf Þ . The results can be expressed by the following equations:
8 t 2
>
> ðjZjf Þ
>
> R ¼
< f t t
ðZreal Þf þ ðZimag Þf cot gðnt p=2Þ
0 2 ð12Þ
>
> ðjZjf Þ
>
> ðR Þ ¼
: f 0
ðZreal Þ0f þ ðZimag Þ0f cot gðn0 p=2Þ
1652 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660

t t t
ðZreal Þf , ðZimag Þf and jZjf now represent the real and imaginary part and the modulus
of impedance, respectively at frequency f and time t after immersion. Substituting
these equations in the general equation (9) another one as a function of experimental
variable is determined.
At this point, Eq. (90 ) remain difficult to operate since it is necessary to know the
depression coefficient for the various components. Simplification can lead to the
elimination of the depression coefficients by considering that all the RC networks are
ideal. It is also necessary to know the terms ð/p  /p;0 Þ in the expression of w. Since
p ¼ 2 is the solution and taking p ¼ 1 as the air, then for the components in the
summation (p P 3), the variation of the volume fraction, ð/p  /p;0 Þ, is negligible,
provided leaching is not considered and the total film volume is constant (assump-
tion a and b). Under these conditions, w ¼ 0 and w1 ¼ 0. Considering that the film
was dry at the beginning of immersion, /0 ¼ 0, Eq. (9) transform in the following
one:


kt k0

Rf ðRf Þ0
/¼ ð13Þ
xðCsol  Cair Þ

which is the general equation for the water uptake for a film with ideal electric be-
haviour (without depression), in which the Cp ¼ e0 ep A=d corresponds to the capac-
itance that could be observed if all the film was constituted by that component, that
can be the air (Cair ) or the solution (Csol ). Although Eqs. (90 ) were deduced assuming
a multicomponent system, it is interesting to note that, with the approximations
made for Eq. (13), the elimination of w corresponds to the disappearance of the only
summation for the various components. Consequently, the multicomponent system
in fact degenerates in a ternary system.
Again the determination of the film resistance can be determined following two
different paths. Taking the resistance of the film as the real part of impedance at the
low frequencies and making ðRf Þ0  Rf , Eq. (13) becomes:

t
ðZimag Þf
/¼ ð14Þ
xðCsol  Cair ÞðZreal Þtf !0 ðZreal Þtf

which is the low frequency solution (LF) for a film with ideal electric behaviour.
The second possible path for determination of the film resistance results from the
simplification of equation system (12) for the ideal case, and is expressed by:

8 t 2
>
> ðjZjf Þ
>
> R ¼
< f
ðZreal Þtf 0
0 2 ð12 Þ
>
> ðjZjf Þ
>
> ðR Þ ¼
: f 0 0
ðZreal Þf
 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660 1653

Substitution of these equations in Eq. (13) leads to:

t 0
ðZimag Þf ðZimag Þf
t 2
 0 2
ðjZjf Þ ðjZjf Þ
/¼ ð15Þ
xðCsol  Cair Þ
which is another form of Eq. (13). This form of the model will be referred to as the
equation for ideal multicomponent system (EIM), and it can be applied to a system
without leaching, initially dry and with ideal electric behaviour (n ¼ 1).

2.2. Binary system

Starting from Eq. (9), and since the component p ¼ 2 is the solution, then p ¼ 1
must be referred to the coating, and the following equation is determined:


kt k0 d
 þ /0 w0sol  wcoat
Rf ðRf Þ0 A
/¼ ð16Þ
wtsol
with
8 0
< wsol ¼ ðnsin sin cos cos
sol  ncoat Þ  k0 ðnsol  ncoat Þ 0
t sin sin cos cos
w ¼ ðnsol  ncoat Þ  kt ðnsol  ncoat Þ ð16 Þ
: sol
wcoat ¼ ncoscoat ðkt  k0 Þ

The resistance values can be estimated in one of the two ways previously de-
scribed. Also considering that the circuits are ideal, and that /0 ¼ 0, then this general
equation for binary system can be simplified in an equation similar to (13), given by:


kt k0

Rf ðRf Þ0 0
/¼ ð13 Þ
xðCsol  Ccoat Þ
In these conditions Ccoat ¼ e0 ecoat A=d is equivalent to the capacitance of the dry
coating. From now on C0 will be used instead of Ccoat .
The two possible ways of estimating the film resistance give Eqs. (140 ) and (150 ):
t
ðZimag Þf 0
/¼ ð14 Þ
xðCsol  C0 ÞðZreal Þtf !0 ðZreal Þtf

ðZimag Þtf ðZimag Þ0f

t 2
 0 2
ðjZjf Þ ðjZjf Þ 0
/¼ ð15 Þ
xðCsol  C0 Þ
which are equivalent to Eqs. (14) and (15), respectively, but for a binary (coating–
water) system. The terms ðZimag Þ0f and jZj0f can be obtained by extrapolation for t ¼ 0.
Alternatively, if the dry film presents a pure capacitive response then the ratio
0 0 2 0
ðZimag Þf =ðjZjf Þ can be approximated to 1=ðZimag Þf .
1654 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660

Eqs. (15) and (150 ) are generalizations of the expression deduced in part I, since at
t t
high frequency jZjf ðZimag Þf . Like in part I these equations can be simplified if we
consider Csol  Cair Csol and Csol  C0 Csol , since esol ew ð25 CÞ ¼ 78:3 and the
relative dielectric constant of the coating is usually limited between 3 6 ecoat 6 8 and
eair 1. It must be stated that the outer solution resistance, RX , can be considered, if
necessary, by substituting Zreal , by the resulting ffiof the difference Zreal  RX , and the
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2 2
impedance modulus by ðZimag Þ þ ðZreal  RX Þ .

2.3. CPE approach

A mixture equation can also be obtained by using the CPE concept of non-ideal
n
behaviour, ZCPE ¼ 1=ðjxÞ Q0 . For a parallel RQ circuit the impedance equation is
then given by:
Rf
Z ¼ RX þ n ð17Þ
1 þ ðjxÞ Q0 Rf
By comparing Eqs. (1) and (17) and determining the low frequency limit of the
impedance, it is easily concluded that Rf corresponds effectively to the resistance of
the film when this is described as a simple RC circuit. On the other hand, the CPE is
related with the global time constant by Q0 Rf ¼ ðsf Þn . The mixture equation will
then be expressed by:

n
X
N
n
ðjxÞ Q0 ¼ ðjxÞ p Qp ðA:8Þ
p¼1

3. Testing of the model

3.1. Experimental

The experimental procedure was described in part I. The electrochemical imped-

ance measurements were made on applied coatings and on freestanding films.
Gravimetric tests were also made. For the applied coatings, measurements were
made in a 3wt% NaCl solution.
For the freestanding films (PVC), the effect of NaCl concentration was analysed
by impedance in solutions with the concentrations of: 0.3%, 1%, 2% and 3%. For
each concentration, the films were allowed to stabilize for one week, before changing
to the following solution of increasing concentration. After the end of the cyclic test
(3% NaCl solution), the films were again re-immersed in the 0.3% NaCl solution, to
confirm the reversibility of the system.

4. Results and discussion

The impedance values were converted into water volume fraction by applying the
model presented above. Both the equations for ideal multicomponent system, EIM
 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660 1655

(15) and for ideal binary system, EIB (150 ) were tested. The results were compared
with the Brasher–Kingsbury model (identified as BK) and also with the equation for
a ternary system derived in part I of this paper (identified as TS). For the free-
standing film, the low frequency solution of the multicomponent model––Eq. (14)––
(identified as LF) was also used.

4.1. Applied films

The water uptake at saturation in PVDF with various pigments applied on nickel
foil is presented in Fig. 1. The water fractions estimated from the two forms of model
now derived––the general equation for multicomponent system and for the binary
system––are very close to those obtained in the high frequency approach for a ter-
nary system (deduced in part I of this paper). The degree of improvement depends on
the exact formulation of the coating, the best being observed in the grey one. On the
other hand, it is interesting to note that in all the formulations tested, the binary
system approach does not bring any improvement to the estimation, but rather in-
creases the values of /, therefore deviating from gravimetric data.
When coatings using different binders are tested (Fig. 2) the conclusions are es-
sentially the same, but in addition it is also confirmed that the shape of the ab-
sorption curve as a function of time is not altered and approximately corresponds to
what could be expected from the mass transfer principles. It is also evident that the
nature of the binder strongly influences the efficiency of the model, which performed
excellently with the polyester, followed by the PVDF, and finally the PVC plastisol,
for which the model gave only a rough approximation.

4.2. Freestanding films

In this case the discrepancy between the classical models and the gravimetric
data was enormous for the films tested (Fig. 3). Although the ternary system

Fig. 1. Water absorption at saturation for PVDF applied on nickel foils, in the following order (left to
right): BK: Brasher–Kingsbury equation; TS: equation for ternary system; EIB: equation for ideal binary
system; EIM: equation for ideal multicomponent system; Grav.: gravimetry.
1656 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660

φ (%)
3

0
0 50 100 150 200 250
t (h)

3
φ (%)

0
0 50 100 150 200 250
t (h)

30

20
φ (%)

10

0
0 50 100 150 200 250

Fig. 2. Water absorption for coated Ni foils and calculated by different models (from impedance) and also
from the gravimetric data: (a) PVDF, (b) polyester and (c) PVC plastisol. n: Brasher–Kingsbury equation,
þ: equation for ternary system, h: equation for ideal binary system, }: equation for ideal multicomponent
system and - - -: gravimetry.

approximation at the high frequencies (TS) and the multicomponent equation (EIM)
decrease the estimation, it was the low frequency approximation that gave the best
results, in a remarkable agreement with gravimetry. This approximation, as men-
tioned above in the deduction, can neither be applied to highly protective coatings––
since they have a fully capacitive response––neither to applied coatings with intense
corrosion underneath, when the effective resistance of the coating may be difficult to
determine. For freestanding films of measurable resistance, however, the approxi-
mation has revealed very good.
It is interesting to note that the model is almost exact at the lowest concentration,
decreasing its efficiency for higher ionic concentrations. This is a limitation that can
 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660 1657

φ s (%)
4
φ s (%)

25
0
0 1 2 3
C (% NaCl)

0
0 1 2 3

Fig. 3. Water absorption at saturation for freestanding PVC plastisol films, calculated by different models
(from impedance) and also from gravimetric data. n: Brasher–Kingsbury equation, þ: equation for ter-
nary system, }: equation for ideal multicomponent system, h: low frequency solution and - - -: gravimetry.

be caused by the approximations applied to the model, namely the ideal electric
behaviour.

5. Conclusions

A model was derived for the estimation of the water content in an organic coating.
In part I, the model was developed for ternary and for binary systems, based upon
the high frequency approximation. In part II, the model was generalized by re-
moving the high frequency approximation and by considering the film as a multi-
component system.
The equations obtained for systems with ideal electric behaviour were applied to
experimental impedance data. A significant improvement of the water content esti-
mation was achieved with the model, when compared to the classical Brasher–
Kingsbury equation. The correlation with gravimetric data was slightly poorer in the
binary system equation when compared with the ternary/multicomponent system.
The low frequency approximation has given excellent results with freestanding
films, not just when compared with the Brasher–Kingsbury equation, but also with
the other forms of the model.

Acknowledgements

The experimental data used in this work were obtained under EU/ECSC contract
7210-TS/941. The concession of a Ph.D. grant to A. Castela by Program Praxis XXI
(FCT, Portugal) is also greatly acknowledeged. Finally, the authors would like to
thank Dr. Kauko Jyrkas/Rautaruukki Oy, Finland, for providing the samples.
1658 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660

Appendix A

For a capacitor of parallel plates with dimensions much larger than the distance
between them the capacitance can be given by the following equation:
ee0 A
C¼ ðA:1Þ
d
in which e0 represents the dielectric constant of free space, (8.854  1014 F/cm), e is
the relative dielectric constant of the material, A is the exposed area and d is the
thickness of the material.
Since the layers in the film are heterogeneous, a number of discrete areas can be
considered in each layer, with the corresponding capacitors. The thickness of each
layer, dd, has to be sufficiently small to make those discrete capacitors equivalent to
parallel plate capacitors. The general admittance of each component, p, for a layer
can be obtained by the addition of the admittances associated with each discrete area
of that component. Since current lines are perpendicular to the surface the following
series results:
" #npi;k
jxe0 ep Ai;k
p Rp
i;k
1 þ
X
M X
M dd
Ypk ¼ Ypk ¼ ðA:2Þ
i¼1 i¼1
Ri;k
p

in which p is a number corresponding to the component, k is the number of the layer,

M is the total number of capacitors of the component p at the k layer, Ai;k i;k i;k
p , Rp and np
are respectively the area, the ionic transport resistance and the depression coefficient
in the i capacitor and Ypk is the total admittance of the p component in the k layer.
Taking np as the depression coefficient for each component, and considering that the
resistance can be correlated by the resistivity of the material, qp , given by Ri;k
p ¼
qp dd=Ai;k
p then the admittance comes as:

1 þ ½jxe0 ep qp 
np X
M
Ypk ¼ Ai;k
p ðA:3Þ
ddqp i¼1

Manipulating the expression we can derive the following one:

n np
1 þ ½jxe0 ep qp  p 1 þ ½jxCpk Rkp  0
Ypk ¼ Akp ¼ ðA:3 Þ
ddqkp Rkp

in which Rkp , Akp and Cpk are the ionic transport resistance, the total area and the
capacitance of the component p in the k layer, respectively. This corresponds to the
admittance of one component in that layer. The global admittance in k the layer is
represented by the following equation:
1 XN
1 þ ½jxskp np k
Yk ¼ Ap ðA:4Þ
dd p¼1 qp
 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660 1659

In each layer, one capacitor can then be associated with each component. The time
constant for that component will be given by skp ¼ Cpk Rkp , N being the number of
components. The impedance of the film can be obtained by adding the impedance of
all the layers, and assuming that the layers have identical thickness, the resulting
equation is given by:
XH XH
dd
Zf ¼ Zk ¼ n ðA:5Þ
k¼1 k¼1 PN
1 þ ½jxskp  p k
p¼1 Ap
qp
in which H is the total number of layers. The thickness of each layer has to be given
by dd ¼ d=H .
Considering uniform film composition, and knowing that the time constant is
given by skp ¼ ep qp , then the summation can be eliminated, since all the terms are
equivalent:
d
Zf ¼ n ðA:6Þ
PN 1 þ ½jxskp  p k
p¼1 Ap
qp
Also,
PNforAuniform composition, Akp ¼ Ap . Manipulation of Eq. (A.6) knowing that
1 p
Rf
¼ p¼1 qp d leads to the following one:
1 0
Zf ¼ ðA:6 Þ
1 XN n Ap
þ ½jxsp  p
Rf p¼1 qp d
Both Eqs. (A.60 ) and (1) describe the impedance of the film, provided RX is neg-
ligible. By comparing the two equations, the following correlation can be derived:
XN
n Ap n
Rf ðjxsp Þ p ¼ ðjxsf Þ ðA:7Þ
p¼1
qp d

Since Rf ¼ qf ðd=AÞ and knowing that

Ap  d Vp
Ap ¼  A ¼  A ¼ /p A
Ad V
if we considered the assumption d, then the mixture equation is obtained:

n
X
N
np qf
ðjxsf Þ ¼ ðjxsp Þ / ðA:8Þ
p¼1
qp p

Applying again the Moivre transformation the following system is determined:

8  p  p
> XN
ðxsp Þnp
>
> ðxs Þ
n
sin n ¼ q sin np /
>
< f f
2 p¼1
qp 2 p 0

 p   ðA:8 Þ
>
> XN
ðxsp Þnp
p
> ðxsf Þn cos n
> ¼ qf cos np /
: 2 q 2 p
p¼1 p
1660 A.S. Castela, A.M. Sim~oes / Corrosion Science 45 (2003) 1647–1660

If we consider the ideal behaviour (n ¼ 1) then the mixture relation is identical to the
one derived in part I:
X
N
ef ¼ ep /p ðA:800 Þ
p¼1

References

[1] A.S.L. Castela, A.M. Sim~oes, M.G.S. Ferreira, Prog. Org. Coat. 38 (2000) 1.
[2] F. Bellucci, L. Nicodemo, Corrosion 49 (1993) 235.
[3] H. Fricke, Philos. Mag. 14 (1932) 310.
[4] J.R. MacDonald, J. Chem. Phys. 36 (1962) 345.
[5] U. Rammelt, G. Reinhard, Corros. Sci. 4 (1987) 373.
[6] J.R. MacDonald (Ed.), Impedance Spectroscopy, John Wiley and Sons, New York, 1987.
[7] K.S. Cole, R.H. Cole, J. Chem. Phys. 9 (1941) 341.
[8] K.S. Cole, R.H. Cole, J. Chem. Phys. 10 (1941) 98.