Corrosion Science 47 (2005) 649–662

www.elsevier.com/locate/corsci

Corrosion performance of conducting

polymer coatings applied on mild steel
P. Ocón *, A.B. Cristobal, P. Herrasti, E. Fatas
Departamento de Quımica Fısica Aplicada, Facultad de Ciencias,
Universidad Autónoma de Madrid, 28049 Madrid, Spain

Available online 13 August 2004

Abstract

Conducting polypyrrole electrodes were obtained by galvanostatic electropolymerisation

on mild steel electrodes from an aqueous solution. The electrochemical response of the coated
electrodes in doped and in undoped state was compared with bare mild steel electrodes. The
undoped polypyrrole coated electrode offered a noticeable enhancement of protection against
corrosion processes.

2004 Elsevier Ltd. All rights reserved.

Keywords: A. Mild steel corrosion; C. Polymer coatings; C. Polypyrrole; B. Impedance

1. Introduction

The development of conducting polymer films has given rise to many advantages
which will continue to encourage researchers to find improved properties [1–5].
The use of barrier coatings on metal substrates is common in corrosion protec-
tion. With steel substrates, surface treatments such as the application of a zinc layer
and rinsing with chromate-containing agents are often performed before applying
the barrier coating in order to ensure long-lasting protection and self-healing

*
Corresponding author. Tel.: +34 91 497 4831; fax: +34 91 497 4785.
E-mail address: pilar.ocon@uam.es (P. Ocón).

0010-938X/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2004.07.005
650 P. Ocón et al. / Corrosion Science 47 (2005) 649–662

properties. Unfortunately these techniques involve heavy metals which are prefera-
bly kept out of the environment.
Interest has recently been focused on the possible use of conducting polymers as
either film-forming corrosion inhibitors or in protective coatings [5–11]. Polypyrrole
(PPy) is one of the most promising conducting polymers in view of its high conduc-
tivity, stability and ease of synthesis.
Beck et al. [12] showed that it is possible to obtain strongly adherent, smooth PPy
films on iron by the electrodeposition of pyrrole and oxalic acid from aqueous solu-
tions. PPy films on iron constitute a physical barrier to aggressive chemical reagents
and can act as polymeric inhibitors and shift the potential of the coated material to
values where the corrosion rate is lower. Hence the degree of corrosion protection
afforded by a conducting polymer coating depends on both its structural and elec-
tronic properties [13–16].
The advantage of electrochemical synthesis is that it achieves the direct synthesis
of a polymer on the metal surface without any organic additives.
The aim of this study is to investigate the electrosynthesis of an adherent polymer
coating on mild steel, determining the conditions in which synthesis takes place and
the protective properties that are achieved. Polypyrrole coatings are compared in
doped and undoped states using open circuit, potentiodynamic and impedance tech-
niques to study their protective effect.

2. Experimental

Measurements were performed in a standard one-compartment three-electrode

cell, synthesising the coatings on mild steel samples. The counter electrode was a
graphite foil and the reference electrode was Ag/AgCl/ (3 mol dm
3 KCl). All the
potentials cited in this work refer to this reference electrode.
The working electrode consisted of 2 cm2 of mild steel sheet. The steel samples
were polished using 600 grit emery paper, washed with bidistilled water and placed
in acetone in an ultrasonic bath for 5 min before use. Chemical treatment was per-
formed prior to electrosynthesis. The electrode was immersed in 13.8% HNO3 for
different times and rinsed with bidistilled water. This treatment produces a passi-
vated area, allowing the polypyrrole to oxidise in similar conditions to those meas-
ured when using a Pt electrode.
Polypyrrole electrodeposition on a mild steel electrode was performed in 0.1
mol dm
3 Na2SO4 and 0.5 mol dm
3 pyrrole (Merck product). The pyrrole was
freshly distilled and stored in a nitrogen atmosphere until its use. The reagents were
stored at 0 C in the dark. The electrolytes were dissolved in bidistilled water. PPy
electropolymerisation experiments were conducted at room temperature in an aer-
ated atmosphere and a non-stirred solution. Electrochemical growth was performed
by the galvanostatic method.
Electropolymerisation and electrochemical characterisations were carried out
using the computerised Autolab Mod. PGSTAT 30 electrochemical instrument
 P. Ocón et al. / Corrosion Science 47 (2005) 649–662 651

equipped with an FRA module (Ecochemie, Utrecht, Netherlands). All measure-

ments were made at room temperature.
Potentiodynamic polarisation curves were obtained in a 3% NaCl dissolution by
firstly locating the EOCP and from that value polarising the electrode in the cathodic
direction to obtain the cathodic branch. With another new electrode, grown in the
same conditions, the EOCP was once again located and polarisation performed in
the anodic direction to obtain the anodic branch.
The galvanostatically grown PPy was obtained in oxidised state, and therefore in
the doped state. The backbone had a delocalised p-system and the polymer film
incorporated SO¼ 4 anions, stabilising the load on the polymerÕs backbone. In order
to obtain more compact structures the PPy was subjected to a reduction process
in a 0.1 mol dm
3 Na2SO4 dissolution, imposing a cathodic potential of
1200
mV for 1200 s. In this way the polymer film was partially reduced, expelling part
of the anions in the chain from the polymer film, which gave rise to the compaction
of the film due to the reduction in its volume. The coating thus obtained was less
conductive, being termed as undoped.
The perturbation voltage for EIS measurements was 5 mV and the frequency
range went from 105 to 10
2 Hz. The electrodes were held for 500 s at the open cir-
cuit potential (EOCP) before starting the measurements.
Scanning electron microscopy and EDX analysis were performed using a Philips
instrument.

3. Results and discussion

3.1. Galvanostatic deposition of PPy on mild steel

In the case of mild steel or iron, anodic or chemical oxidation is accompanied by

dissolution of the metal. The oxidation potential of most monomers is in the region
of metal dissolution. The metal is able to retard or to inhibit the oxidation of the
monomer and thus the formation of an adherent polymer film. Therefore the mild
steel surface must be pretreated in order to avoid strong corrosion parallel to the film
formation.
Homogeneous and adherent PPy film have been obtained when treating a mild
steel surface with HNO3 [17]. Nitric acid significantly changes the electrochemical
behaviour of the mild steel surface and produces a considerable shift in the oxidation
barrier. When mild steel is immersed for 4 min in 13.8% HNO3 acid and polarised in
0.1 mol dm
3 Na2SO4 (Fig. 1), the treatment is seen to cause considerable passiva-
tion of the electrode. The electropolymerisation of pyrrole can be obtained at current
density values close to those measured when using a Pt electrode.
Galvanostatic deposition has been performed using weak current densities in
order to keep the mild steel electrode in the passivation region. From an industrial
point of view, galvanostatic deposition produces turn out in a one-step process,
which is a key criterion for most electrochemical deposition processes.
652 P. Ocón et al. / Corrosion Science 47 (2005) 649–662

60

50

40

30
i (A m-2)

20

10

-10

-1.0 -0.5 0.0 0.5 1.0 1.5

E(mV/Ag/AgCl)
Fig. 1. Cyclic voltammogram obtained for chemically passivated mild steel electrode in 0.1 mol dm
3
Na2SO4. Scan rate 50 mV s
1.

Under these conditions, a very adhesive PPy film has been obtained for current
densities reaching 5, 10, 15 and 20 mA cm
2 and different deposition times. PPy elec-
tropolymerisation is characterised by a sharp rise to a maximum positive value, after
which the potential quickly decreases to a steady value where a black PPy coating
starts to form. An increase in the current density leads to a positive shift in the poten-

Fig. 2. Potential transients obtained in 0.5 mol dm
3 Pyrrole and 0.1 mol dm
3 Na2SO4 for different
current densities: (a, b) 15 mA cm
2, (c) 12 mA cm
2 and (d) 10 mA cm
2.
 P. Ocón et al. / Corrosion Science 47 (2005) 649–662 653

Fig. 3. SEM surface micrograph of a PPydoped film obtained on mild steel in 0.1 mol dm
3 Na2SO4, 0.5
mol dm
3 Pyrrole in galvanostatic conditions i = 15 mA cm
2 and deposition time 500 s.

tial of the plateau. There is no inducting period for any of the experiments (Fig. 2).
The result is a strongly adherent PPy film. Fig. 3 shows a grained texture and an
open structure typical of these polymer films. However, when i = 20 mA cm
2, mild
steel dissolution becomes significant, as is indicated by the rapid colouring of the
solution. The best result in terms of the protective effect is obtained with i = 15
mA cm
2.
The coating thickness (dn) has been calculated using FaradayÕs law, assuming a
two-electron mechanism based on the monomer molecule involved in the process
and a current efficiency of 100%. The PPy density (q) is 1500 kg m
3 and the pyrrole
molar mass (M) is 67 · 10
3 kg mol
1:
d n ¼ QM=2F q
where Q is the overall specific charge for electropolymerisation (C m
2).

3.2. Corrosion test

The open circuit potential has been monitored in an aerated corrosive solution
(3% NaCl) for PPy films obtained at different current densities for an electrodeposi-
tion time of 500 s (i.e. of different thicknesses). Monitoring the open circuit potential
(EOCP) of the system allows the corrosion protection of mild steel by PPy films to be
assessed.
In the first step, the aim was to find whether there is an optimum thickness value
for a good protection time. As an example, Fig. 4 shows the evolution of the EOCP
for PPy films of the indicated thicknesses and for mild steel and mild steel coated
with the chemically grown oxide layer. The curves for the latter two surfaces display
654 P. Ocón et al. / Corrosion Science 47 (2005) 649–662

Fig. 4. Open circuit potential electrode EOCP (mV) as a function of immersion time (h) in 3% NaCl. (j)
Mild steel, (n) passivated mild steel, (s) PPydoped 5.0 lm, ( ) PPydoped 10.4 lm, (s) PPydoped 17.5 lm and
(m) PPyundoped 17.5 lm.

a decrease towards a pseudo-plateau around
650 mV. On this plateau some oscil-
lations in the potential can be observed. These oscillations can be associated with the
onset of pitting [18,19]. For all the studied PPy films, the EOCP for zero time shows a
less negative potential, but the evolution is not the same for all the films. When the
thickness is less than 17.3 lm the EOCP decreases towards the corrosion potential of
uncoated mild steel and the metal is no longer protected as some blistering is
detected. For the 17.3 lm thickness, PPy in the doped state shows EOCP =
300
mV at first which evolves to EOCP =
550 mV after 72 h immersed in the corrosive
solution. This value is obtained as a pseudo-plateau for a long time, approximately
24 days. This PPy film was obtained in doped state. Furthermore the PPy (17.3 lm)
was obtained and undoped in the Na2SO4 0.1 mol dm
3 solutions with a potentio-
static method (E =
1200 mV, t = 1200 s). A SEM micrograph for this coated film
is shown in Fig. 5, in which the coatingÕs structure is seen to be more compact. In this
situation the EOCP reaches a less negative value and the prolonged pseudo-plateau at
EOCP =
500 mV is obtained. Fluctuations in the potential may represent anionic
exchanges of sulphate and chlorides and solvent exchanges between the polymer film
and the solution during equilibrating in 3% NaCl solution. This EOCP does not indi-
cate the formation or maintenance of a passive layer on the mild steel. For the thick-
nesses of more than 17.3 lm the results are no better. Experiments were also carried
out after drying the polymer film at 80 C for two days, but the EOCP results were
worse and after 48 h approached those of bare mild steel, revealing their unsuitability
to protect the mild steel substrate.
Cyclic voltammetry in 3% NaCl at a scan rate of 5 mV s
1 was also performed
with the electrodes described in the former paragraph, yielding the results indicated
in Fig. 6. With mild steel and chemically passivated mild steel the current density has
high values, indicating that the substrates are not protected in this aggressive med-
ium (Fig. 6a and b). Compared with the PPydoped film (Fig. 6c) the current density
is somewhat lower, though its value continues to be high, since as well as the contri-
 P. Ocón et al. / Corrosion Science 47 (2005) 649–662 655

Fig. 5. SEM surface micrograph of a PPyundoped film (E =
1200 mV, t = 1200 s).

3500
a
3000

2500
b
2000
i (A . m-2 )

c
1500

1000

500 d
e
0

-500
-1000 -500 0 500 1000 1500
E (mV/Ag/AgCl)

Fig. 6. Cyclic voltammogram in 3% NaCl, scan rate 50 mV s
1. (a) Mild steel, (b) chemically passivated
mild steel, (c) PPydoped, (d) PPydoped and polarised and (e) PPyundoped.

bution of the corroding substrate it is necessary to take into account that the poly-
mer layer is active from the redox point of view, and therefore the oxidation current
contributes to this density. When the PPydoped is subjected to a polarisation process
(between EOCP and EOCP
1000 mV at v = 2 mV s
1), the polymer film presents
good anti-corrosive properties as a protective film. This process implies a partial
reduction in the polymer layer. Better results are obtained when the PPy
656 P. Ocón et al. / Corrosion Science 47 (2005) 649–662

(17.3 lm) is in the undoped state (Fig. 6e). In this case E =
1200 mV was applied to
the film for 1200 s. The layer is compact and it seems that the partial reduction in the
load on the polymerÕs backbone contributes favourably to the protection process.
As complementary experiments, potentiodynamic polarisation curves have been
plotted (Fig. 7) for the different samples (mild steel, chemically passive mild steel,
PPydoped coated mild steel and PPyundoped coated mild steel) in the corrosive solution.
Corrosion rate information can be obtained by the Tafel extrapolation method,
where the intersection point of a cathodic and anodic polarisation curve provides
both the corrosion potential and the corrosion current.
Tafel extrapolations show that the PPydoped and PPyundoped coatings cause a pos-
itive shift of around 200 mV in the corrosion potential compared with bare mild
steel. The Tafel measurements also show that the i0 values for coated mild steel
are higher than for bare mild steel (Table 1), but in this case i0 is the exchange current
density for the complex process, where there are several electroactive species and sur-
faces with several structural and morphology exchanges. The polymer film also con-
tributes to the exchange current density and thus the value of i0 is not only the
contribution of the corrosion rate.
We propose a complex mechanism for the corrosion process according to the re-
sults obtained
Anodic reactions
Fe
2e
! Fe2þ

PPyundoped
ne
! PPydoped

1000
800
600
400
E (mV/Ag/AgCl)

b
200
0
-200 a
c
-400
d
-600
-800
-1000
-1200
-1400
-1600
-1800
-2.0 -1.0 0.0 1.0 2.0 3.0
-2
log i ( i = A m )
Fig. 7. Potentiodynamic curves in 3% NaCl for: (a) mild steel, (b) chemically passivated mild steel,
(c) PPydoped 17.5 lm and (d) PPyundoped 17.5 lm.
 P. Ocón et al. / Corrosion Science 47 (2005) 649–662 657

Table 1
Interchange current densities
System Current density i0 (A m
2)
Mild steel 3.8
Chemically passivated 2.8
PPydoped (17.3 lm) 24
PPyundoped (17.3 lm) 5.2

Cathodic reactions
PPydoped þ ne
! PPyundoped

O2 þ H2 O þ 4e
! 4OH

PPyundoped þ ne
! PPy0undoped

Chemical reaction

2OH
þ Fe2þ ! FeðOHÞ2 ! FeðOHÞ3 ! Fe2 O3

This mechanism assumes that mild steel has oxidised by yielding electrons to
PPydoped and that PPydoped has been reduced, as a result of which the SO¼ 4 anions
are ejected and the polymer film is more compact. But the PPyundoped can be reox-
idised by the oxygen from the solution (i.e. from the air), and the time of protec-
tion by the polymer film coating will depend on the relative reaction rate, as well as
the available amount of PPydoped. When the coating film is undoped, its volume
changes and the film is more compact and the corrosion solution less accessible
to the substrate. The depolarisation of mild steel may be modified depending on
the quality of the chemically generated oxide film. In order to study the protection
of PPy films the amount of free (Fe2+) in solution was determined. The reaction
with ortho-phenantroline allows the quantification of these species by spectroscopy,
which is indicative of the corrosion process. Their evolution with immersion time
has been determined and Fig. 8 shows the amount of Fe2+ in parts per million
(ppm). According to these experiments PPyundoped is the best coated film in terms
of anti-corrosive properties. If 1 ppm of (Fe2+) is established as the threshold for
corrosion evaluation, it can be seen that PPyundoped with 17.3 lm, has protected the
substrate for at least 120 h, but that PPydoped can only be considered protective for
a time of less than 24 h; irrespective of the i0 values determined by the potentio-
dynamic curves.
Electrochemical impedance spectroscopy (EIS) measurements confirm the
potentiodynamic and OCP results. The corrosion of a PPy-coated mild steel elec-
trode has been investigated for different immersion times in an aerated 3% NaCl
solution. EIS, as a means of determining the effectiveness of corrosion inhibitors,
provides valuable insight into corrosion mechanisms. The frequency by frequency
response can be modelled by equivalent circuits [20–25].
658 P. Ocón et al. / Corrosion Science 47 (2005) 649–662

Fig. 8. [Fe2+] in solution for different immersion times. ( ) Mild steel, (h) chemically passivated mild
steel, ( ) PPydoped and (j) PPyundoped.

EIS data was recorded after immersing the electrode in the aggressive medium for
500 s. Nyquist plots were constructed and an appropriate equivalent circuit model
was used to correlate the impedance with the capacitance and the resistance of the
film. Figs. 9–11 show Nyquist plots for mild steel, PPydoped and PPyundoped respec-
tively for different immersion times. Equivalent circuit models for these substrates
are assumed and the values are given in Table 2. It can be seen that the models fit
the experimental data reasonably well, considering in all cases e 6 5% for all the

350

300

250
mild steel
200
-Z "/ ohm

150 0h
10 Hz
100

50 10 Hz 0.5 Hz 0.5 Hz
24 h

0
0 50 100 150 200 250 300 350
Z'/ ohm

Fig. 9. The Nyquist diagrams for the mild steel in 3% NaCl for different immersion times.
 P. Ocón et al. / Corrosion Science 47 (2005) 649–662 659

60

50

PPydoped
40
-Z "/ ohm

30
0.1 Hz
20
10 Hz
216 h
10 120 h 10 Hz 0.1 Hz

0h 0.1 Hz
0
0 10 20 30 40 50 60
Z'/ ohm

Fig. 10. The Nyquist diagrams for PPydoped in 3% NaCl for different immersion times.

120

100
PPyundoped
80
-Z "/ ohm

60
72 h
0.1 Hz
40
10 Hz 192 h
10 Hz
20 0.1 Hz
0.1 Hz
oh
0
10 Hz
0 20 40 60 80 100 120
Z'/ ohm

Fig. 11. The Nyquist diagrams for PPyundoped in 3% NaCl for different immersion times.

parameters of the corresponding equivalent circuits. From these EIS results it can be
seen that immersion time has a significant effect on the impedance of the samples.
For mild steel and timmersion = 0 the Rp is 500 X and the CPE 4.5 · 10
7 and
n = 0.55. With an immersion time of 24 h the corrosion rate rises and the parameters
are as shown in Table 2. Furthermore the value of n = 0.64 indicates a greater degree
of roughness of the substrate compatible with the formation of iron oxide and
hydroxide type corrosion products. In the case of coated samples and short immer-
sion times the impedance plots present a linear region in the low frequency region,
which means that the film behaves like a blocked electrode. The corrosion reaction
is inhibited by mass transfer limitation and a redox reaction may be taking place
660 P. Ocón et al. / Corrosion Science 47 (2005) 649–662

Table 2
The values obtained from the equivalent circuit for different samples
System immersion Rs Rct QCPE n W Equivalent circuit
time (h) (X) (X) (F) (X
1 s1/2)
Fe, t = 0 2.00 500 4.5 · 10
7 0.55 Rs
Q

Rct

Q
Fe, t = 24 6.74 321 8.3 · 10
4 0.64 Rs
Rct

Q
Fe/PPydoped, t = 0 6.89 5.50 8.4 · 10
4 0.44 0.20 Rs
R ct
W

Q
Fe/PPydoped, t = 120 9.25 46.4 6.7 · 10
5 0.66 0.03 Rs
R ct
W

Q
Fe/PPydoped, t = 216 2.16 32.6 7.7 · 10
5 0.73 0.02 Rs
R ct
W

Q
Fe/PPyundoped, t = 0 5.96 75.3 1.2 · 10
5 0.37 Rs
Rct

Q
Fe/PPyundoped, t = 72 11.55 3500 3.6 · 10
7 0.35 Rs
Rct

Q
Fe/PPyundoped, t = 192 8.79 73.2 6.0 · 10
5 0.68 0.03 Rs
R ct
W

n indicate the capacitive like behaviour of the constant phase element Q. The impedance of the constant
phase element is ZQ = A(jx)
n, where 0 < n < 1, A is the frequency independent constant, and x is the
angular frequency.

within the coating. When the immersion time is short the chemically passive film con-
structed in the initial process before the PPy is grown can continue to prevent the
corrosion of mild steel. When the immersion time is longer, the linear region is trans-
formed into a capacitative loop and the resistance is decreased. The capacitative
behaviour can be attributed to the interface inside the polymer layer.
In summary, Table 2 shows the circuit that correspond to the bare mild steel elec-
trode. The parallel net RQ is in series with the ohmic resistance. Where R represents
the charge transfer resistance and Q is related with the double layer capacity. In Fe/
PPydoped electrode, Warburg impedance appears which is related with anionic
exchange between the solution and inside of the polymer layer. This impedance
parameter W decreases when the immersion time increases, because of the saturation
 P. Ocón et al. / Corrosion Science 47 (2005) 649–662 661

of the polymer layers with the arrival of Cl
anions. In the Fe/PPyundoped we can see
that there is no impedance associated with mass transfer which indicates that there is
no ionic exchange with the solution until a time longer than 192 h. Above this con-
siderations, explain the observed protective behaviour of this polymer coating
against corrosion in that strongly corrosive media.

4. Conclusion

The results show that the coated polymer films shift the electrode potential
towards more positive potentials, but that this shift does not lead to passivation.
However, a notable synergy exists between PPyundoped film, oxygen reduction and
iron dissolution. The potential of mild steel remains in the active dissolution region
and a passive oxide layer is not possible in this region. PPy separates the metal dis-
solution process from the oxygen reduction process. This would prevent the local pH
increase at the metal surface and subsequent delamination. The polarisation curves,
EOCP and impedance measurements show that PPyundoped layers promise to be a
good candidate for corrosion protection of reactive metals.

Acknowledgement

Financial support of this research by the Spanish Ministry of Science and Tech-
nology is gratefully acknowledged (BQU2001-0149).

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