Journal of Electroanalytical Chemistry 540 (2003) 35 /44

www.elsevier.com/locate/jelechem

Application of polypyrrole/TiO2 composite films as corrosion

protection of mild steel
Denise M. Lenz a, Michel Delamar b, Carlos A. Ferreira a,

a

Department of Materials, Escola de Engenharia, LAPOL-PPGEM-Universidade Federal do Rio Grande do Sul, Av. Osvaldo Aranha, 99, sala 702,
90035-190 Porto Alegre, RS, Brazil
b
ITODYS-Universite Paris 7 Denis Diderot, 1, Rue Guy de la Brosse, 75005 Paris, France
Received 16 November 2001; received in revised form 2 September 2002; accepted 27 September 2002

Abstract
This work is a study of the anticorrosion protection of polypyrrole (PPy) on AISI 1010 steel (mild steel) by the incorporation of
TiO2 pigment into the PPy matrix during electrochemical synthesis. The influence of parameters such as stirring, concentration, pH
and nature of the electrolyte were investigated. The degree of pigment incorporation into the polymeric matrix with respect to time
and current densities of the electrodeposition process were also investigated. The influence on the current efficiencies of the process
was evaluated. The morphology of the composite film was studied by scanning electron microscopy (SEM) and the distribution of
the pigment within the polymeric matrix by X-ray photoelectron spectroscopy (XPS). The PPy/TiO2 composite showed a
considerable improvement in anticorrosion properties with respect to PPy films after being submitted to salt spray and weight loss
tests. These composite films can be applied as a primary coating replacing the phosphatized layers on mild steel.
# 2002 Published by Elsevier Science B.V.
Keywords: Polypyrrole; Titanium dioxide; Composite films; Anticorrosion protection

1. Introduction
Organic coatings on metals are not perfect physical
barriers against corrosion when they are in contact with
aggressive species such as O2 and H . These corrosive
species can reach the substrate via coating defects.
Electrically conductive polymers (ECP), for example
polypyrrole (PPy) and polyaniline (PANI), are capable
of providing corrosion protection. This protection
involves the use of chemical and electrochemical techniques such as chemical inhibitors, cathodic and anodic
protections. They are thus materials of considerable
practical interest for corrosion inhibition and many
papers on this subject have been published [1 /13].
The corrosion inhibition on steels using ECP coatings,
mainly as primary coatings, is partly due to the
formation of passivating stable oxide films such as
Fe3O4, a-Fe2O3 and g-Fe2O3 at the metal j ECP interface [3,9]. The oxide layers are dense and act as a

Corresponding author.
E-mail address: cafjzf@vortex.ufrgs.br (C.A. Ferreira).

physical barrier that protect the metal surface from

further corrosion [3].
Pigments can be added to organic coatings in order to
improve their protection. The pigments may protect the
metal by physicochemical (barrier mechanism), electrochemical or ion exchange mechanisms [14]. The combined effects of pigments and appropriate binders in
such coatings should be studied in order to improve
their anticorrosion properties.
The incorporation of minerals into a PPy matrix with
the aim of changing or improving its properties has been
reported [15 /19]. Yoneyama and coworkers [15 /18]
were the first to attempt the codeposition of TiO2 and
WO3 in a PPy matrix using inert electrodes made of Au
or ITO in an electrolytic system. This was done without
stirring and using a suspension with a pH value greater
than the isoelectric point of the oxides. Oxides are
negatively charged in this method and are attracted to
the positively charged PPy. An oxide incorporation into
the PPy matrix of up to 1.15% by weight was achieved.
Beck et al. [19] have shown that strong convection is
an important factor for the incorporation of TiO2 into

0022-0728/02/$ - see front matter # 2002 Published by Elsevier Science B.V.

PII: S 0 0 2 2 - 0 7 2 8 ( 0 2 ) 0 1 2 7 2 - X

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D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

PPy. The use of strong convection gives up to 17% TiO2

by weight when using platinum or stainless steel as
working electrodes (WE) in a 0.1 M LiClO4 aqueous
medium.
Previous studies [20] have shown that TiO2 incorporation into a PPy matrix during electrochemical synthesis
on AISI 1010 steel under magnetic stirring leads to the
formation of PPy/TiO2 composite films containing up to
6.5% TiO2 by weight. These composite films show a
slight improvement in the PPy corrosion protection of
mild steel.
Further studies of TiO2 incorporation onto mild steel
during electrochemical synthesis of PPy using a stronger
electrolyte convection with looping to increase TiO2
concentration into PPy are shown in this work. The mild
steel coated with the PPy/TiO2 composite films were
then submitted to corrosion tests.

2. Experimental
2.1. Electrochemical synthesis
AISI 1010 steel sheets (100 /20 /1 mm) were used as
WEs. They were degreased with an industrial alkaline
solution (DUROCLEAN 107) at 80 8C for 5 min
followed by a treatment with 10% HNO3 [13]. Pyrrole
(Aldrich) was bidistilled under an N2 atmosphere. The
electrolytes used were 0.1 M oxalic acid and 0.1 M
KNO3. TMDD (2,4,7,9-tetramethyl-5-decyne-4,7 diol,
2 /103 M) was added to the electrolyte medium in
order to improve electrode wetting by the electrolyte
solution and avoid dendritic growth of the polymer. The
average particle size of the TiO2 pigment (rutile, Merck)
was 0.76 mm and its solubility in aqueous medium is
about 1% by weight. Its specific gravity is 4.2 g cm 3
and PPy average specific gravity is around 1.5 g cm 3
[2,10].
A rectangular 110 /85 /50 mm3 acrylic cell was used
for the experiments without electrolyte stirring. Two
stainless steel sheets and a saturated calomel electrode
(SCE) were also used as counter (CE) and reference
electrodes (RE), respectively. The electrodes were positioned symmetrically 20 mm from the WE. For experiments with electrolyte stirring a loop system, similar to
the one described by Beck et al. [19] was employed. A
stationary sheet anode was fixed between two stainless
steel CEs (Fig. 1). An Ag/AgCl (/0.034 V vs. SCE) wire
was used as a RE, as explained elsewhere [21], which was
positioned exactly behind the sheet anode. The suspension was pumped around a loop with the aid of a PSM
suction pump which can produce flow rates from 1 to 15
ml s 1.
All syntheses were performed galvanostatically at
room temperature onto an exposed area of 12 cm2 on
each side of the sheet.

Fig. 1. Representation of the electrolytic cell with looping stirring. B,

buffer volume; V, valve; and P, pump.

2.2. TiO2 concentration in the PPy/TiO2 composite film

After degradation of the composite films in hot
concentrated sulphuric acid, the titanium content was
quantitatively analysed by ultra-violet spectroscopy. A
JASCO 7800 spectrophotometer was used at 420 nm
according to the colorimetric method [22]. Plasma
spectroscopy (ICP) using an ARL 3410 spectrophotometer at 323.452 nm was also used. The iron content in
the same solution was measured at 510 nm.
For the X-ray photoelectron spectroscopy (XPS)
experiments an SSI X100 photoelectron spectrometer
with an aluminum monochromatic source (Al /Ka
radiation 1486.6 eV) was used. XPS was carried out
using a spot size of 600 mm and a vacuum of 10 9 Torr
(1.33/107 Pa). An analysis angle of about 908 with
respect to the sample surface was used. Ar  ion
bombardment was applied to remove thin layers of the
composite film using an AG2 ion gun supplied by
Vacuum Generators. The conditions of bombardment
were an acceleration voltage of 4.8 kV, an Ar  pressure
of 5 /106 mbar and 200 mA of ion current. The
sputtering rate was approximately 2.5 mm per h, as
estimated from calculated and measured thicknesses of
the composite films.
The composite film thicknesses were measured using a
FISCHER model DUALSCOPE MP 20 coating
thickness metre. The SEM experiments were performed
with a PHILIPS XL20 scanning electron microscope.
2.3. Anticorrosion protection of the PPy/TiO2 composite
films
Salt spray corrosion tests (ASTM B 117) were carried
out in a test chamber (BASS EQUIPAMENTOS) using
6 /2 cm samples (only one side of the sheet). The weight
loss tests were performed by dipping samples of PPy and
PPy/TiO2 films into a 3.5% NaCl solution. The exposed
electrode area was 4 cm2. The amount of iron released
from the samples was measured as a function of

D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

immersion time using a JASCO 7800 UV/vis spectrophotometer at 510 nm using the o-phenanthroline
technique. All exposed electrode areas were delimited
by an acrylic-thermoplastic paint layer of approximately
0.5 mm thick.
In this work, all experiments were performed twice,
except weight loss tests which were performed three
times. An average of the results is given.

3. Results and discussion

The electrodeposition of conducting polymers onto
oxidizable metals is indeed not easy because thermodynamic data predict that the metal will dissolve before
the electropolymerization potential of the monomer is
reached. Thus to achieve the deposition of a conducting
polymer on mild steel it is necessary to find the
electrochemical conditions which lead to a partial
passivation of the metal and decrease its dissolution
rate
without
preventing
electropolymerization
[6,7,12,13]. In addition, if a pigment is to be codeposited
with PPy, it must not adversly interfere with the pyrrole
polymerization reaction.
3.1. KNO3 medium (pH 7.5 /8)
The influence of selected parameters on TiO2 incorporation was investigated using a potassium nitrate
medium.
3.1.1. Electrolyte stirring
As described in previous experiments carried out with
TiO2 [19,20] there was a negligible incorporation of
pigment (without stirring of the electrolytic medium) as
well as pigment sedimentation. A strong convection
achieved with the maximum flow rate setting of the
pump (15 ml s 1) was better for pigment incorporation.
Table 1 shows an increase in TiO2 concentration in
the PPy matrix (cc) when the solution is stirred with
small TiO2 electrolyte concentrations (200 mg l1).
Table 1
TiO2 concentration in PPy (cc) with and without electrolyte stirring in
0.1 M pyrrole, 0.1 M KNO3, 2.3/10 3 M TMDD, TiO2 electrolyte
concentration: 200 mg l 1, polymerization time: 10 min
j /mA cm 2

2
5
7
10
15
20

Without strring

With stirring

cc/% TiO2

cc/% TiO2

0.1
0.2
0.4
0.1
0.1
0.1

0.5
/
0.4
/
/
0.4

37

Caution must be taken with strong convection (above

15 ml s 1) because it could repel TiO2 particles from the
anode.
Table 1 also shows that the effect of the current
density on the incorporation of TiO2 in PPy is more
pronounced when no stirring is performed. Current
densities in the range of 5 /7 mA cm 2 favour incorporation, however higher current efficiencies were
found in the 2/5 mA cm 2 range [13,20]. For this
reason 5 mA cm 2 was used for all further experiments
using the KNO3 electrolyte.
The influence of stirring was also analysed using
different experimental conditions. The polymerization
time was increased to 20 min and the electrolyte pigment
concentration (ce) to 50 and 100 g l 1. This led to the
formation of PPy/TiO2 composite films which were
approximately 18 mm thick. The results are shown in
Table 2.
Thus, stirring keeps the TiO2 particles in suspension
and causes the particles to be continuously in contact
with the anode surface where the composite film is being
deposited. The results confirm that this incorporation is
greatly facilitated by mechanical stirring. Indeed, a very
small quantity of TiO2 was observed in the composite
films synthesized in the KNO3 electrolyte without
stirring even using pH values higher than the TiO2
isoelectric point */between 6.0 and 6.7 in aqueous
medium [23] */compared to the same medium with
stirring.
The use of looping stirring and the presence of TiO2
did not alter the current efficiency (about 90%) for the
composite film synthesis. Similar results without stirring
have been obtained in previous experiments [20] and by
Schirmeisen and Beck [2] for PPy synthesis in NO
3
aqueous medium with slow stirring. It is important to
emphasize that only PPy mass is considered in the
current efficiency calculation and TiO2 concentration is
neglected. Thus, PPy deposition onto mild steel is
governed only by charge transfer mechanisms.
3.1.2. Polymerization time
Table 3 shows that for small TiO2 concentrations in
the electrolyte there are no significant changes in TiO2
Table 2
TiO2 concentration (cc) in PPy using higher TiO2 electrolyte concentrations (ce)
ce/g l 1

50
100

With strring

Without strring

cc/%

cc/%

6
9.2

B/1
3.1

Electrolyte composition: 0.1 M pyrrole, 0.1 M KNO3 and 2.3/

10 3 M surfactant TMDD, j/5 mA cm 2, polymerization time: 20
min

D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

38

Table 3
Influence of polymerization time on TiO2 incorporation with electrolyte stirring
j /mA cm 2

5
10
20
5
5
5

Ce/g l 1

0.2
0.2
0.2
0.4
8
50

Polymerization time
10 min

20 min

cc/%TiO2

cc/%TiO2

0.5
0.9
0.4
1.5
0.8
1.5

0.8
1.5
0.7
2.5
6.3
6

Electrolyte composition: 0.1 M pyrrole, 0.1 M KNO3, 2.3/10 3 M

TMDD.

incorporation. However, for higher TiO2 quantities in

the electrolyte, the change in polymerization time from
10 to 20 min results in a remarkable difference in TiO2
incorporation into the PPy matrix. Composite films
synthesized over 10 min using 50 g l 1 of pigment in the
electrolyte showed an incorporation of 1.5% by weight,
while 6% by weight of TiO2 was found in composite
films synthesized over 20 min.
TiO2 particles should be distributed in an approximately uniform way within a PPy matrix when small
quantities of TiO2 are present in the electrolyte. This is
because a twofold increase in polymerization time
causes a similar increase in TiO2 concentration in the
PPy matrix. However, for higher TiO2 concentrations in
the electrolyte (above 1 g l 1) the particles should
mainly be in the upper half of the composite film. This is
because the TiO2 concentration in the composite in-

creases more than twice when the polymerization time is

increased from 10 to 20 min.
Thus, TiO2 particles are preferentially incorporated
when there is a polymer layer of considerable thickness
on the metallic surface. This is due to an increase in
polymer surface roughness with a respective increase in
polymer thickness as reported by Dahlhaus and Beck
[24]. Polymerizations carried out with longer times did
not show an increase in TiO2 incorporation.
3.1.3. Electrolyte concentration
Fig. 2 shows a typical chronopotentiometric curve in
a 0.1 M KNO3 medium. It is remarkable that the
potential increases quickly, so polymerization begins
instantaneously and the potential stabilizes at 1.2 V.
This behaviour is typical and independent of TiO2
electrolyte concentration indicating that the pigment
does not interfere with the PPy polymerization mechanism.
With low concentration of KNO3 electrolyte (ca.
103 M), the potential rapidly increased to above 5 V
(current 5 mA cm 2), leading to polymer overoxidation
due to the high electrolyte resistivity [25]. In spite of the
high TiO2 incorporation into PPy (around 18% by
weight) the composite films are porous. The process
has a low current efficiency, i.e. less than 50%. In the
absence of TMDD the incorporation decreases to 8%.
Thus, TMDD promotes electrode wetting and probably
favours TiO2 incorporation by superficial tension diminution at the electrode j solution interface.
3.1.4. TiO2 electrolyte concentration
The experiments were carried out in a range of 200 mg
l 1 to 100 g l1 of TiO2. The results are shown in Fig. 3.

Fig. 2. Chronopotentiometric curve of composite film synthesis in 0.1 M KNO3 medium using 0.1 M pyrrole and 2.3/10 3 M TMDD, j/5 mA
cm 2.

D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

39

Fig. 3. Relationship between TiO2 concentration in PPy/TiO2 composite film (cc) and its concentration in the electrolyte (ce). Electrolyte: 0.1 M
KNO3, 0.1 M pyrrole and 2.3/10 3 M TMDD, j/ 5 mA cm 2 and t /20 min.

The maximum TiO2 concentration in the composite

film from the KNO3 medium containing 100 g l 1 of
TiO2 in the electrolyte was around 7%. However, it is
also possible to obtain a similar composition using 10 g
l 1 of TiO2 in the electrolyte because of its saturation
within the PPy matrix, as shown by Beck and Dahlhaus
[26].
3.2. H2C2O4 medium (pH 2)
In this medium a polymerization time of 30 min was
used with a current density of 5 mA cm2 and a
monomer concentration of 0.1 M pyrrole. This was

related to previous work that used magnetic stirring [20].

Using different current densities than 5 mA cm 2 in
H2C2O4 medium, the TiO2 concentration in the composite film and the current efficiency will be lower.
However, even for 5 mA cm 2, the current efficiency
in this medium was lower than in KNO3 (around 66%)
due to the presence of an induction time during which
only iron corrosion and an iron oxalate layer formation
occurred [10].
The induction time is illustrated in Fig. 4. After the
first 2 min the potential stabilizes at /0.25 V and iron
corrosion takes place. After this period pyrrole polymerization starts and the potential stabilizes at around

Fig. 4. Chronopotentiometric curve of composite film synthesis in 0.1 M oxalic acid medium using 0.1 M pyrrole, j/5 mA cm 2.

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D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

1.0 V. The thickness of the PPy/TiO2 composite film

synthesized in H2C2O4 medium under these conditions
was around 25 mm.
The influence of polymerization parameters on TiO2
incorporation was also investigated.
3.2.1. TiO2 electrolyte concentration
Experiments with 0.1 M oxalic acid were carried out
in electrolytes that contained from 200 mg l 1 to 50 g
l 1 of TiO2 (Fig. 5). It is possible to incorporate around
14 wt.% of TiO2 in a composite with a concentration
slightly greater than 10 g l1 of pigment in the
electrolyte. Above this concentration TiO2 incorporation no longer increases. The same was observed in the
KNO3 medium.
3.2.2. Electrolyte pH
When the pH value of the oxalic acid medium was
increased to 4 the TiO2 incorporation was found to be
similar to that at pH 2 (Fig. 4). There was no marked
difference in the current efficiency when the pH was
changed.
Experiments carried out with 0.1 M sodium oxalate
solution (pH around 6) gave a similar percentage of
TiO2 incorporation into the PPy matrix as for oxalic
acid under the same experimental conditions. However,
the current efficiency decreased and as a consequence
the films had a lower thickness.
The results showed that the use of oxalic acid as an
electrolytic medium promotes the formation of a PPy/
TiO2 composite film that is visibly smoother and

brighter. The film also has a greater TiO2 incorporation

and a stronger adhesion (Gr0 Grade, as DIN 53151)
than PPy/TiO2 composite films synthesized in a KNO3
medium.
The low roughness and high adhesion of the composite films obtained in this medium, as compared to those
obtained in a KNO3 medium, could be due to the
formation of a thin layer of iron oxalate during the
induction time. Iron oxalate may provide favourable
nucleation sites for electrocrystallization of PPy. PPy
grows as microhemispheres and TiO2 deposits in the
valleys or summits leading to smooth films [10]. Thus,
the organized growth of PPy in a H2C2O4 medium is
more significant than polymeric roughness found in PPy
synthesized in a KNO3 medium for TiO2 incorporation.

3.3. Surface analysis by XPS and SEM

XPS and SEM analysis were carried out on the PPy/
TiO2 composite films synthesized in the oxalic acid
medium which contained 14% by weight of TiO2
particles.
Samples were obtained by cutting the electrode into
three (2 /2 cm) parts. The signal for titanium was
observed at the surface of the PPy/TiO2 composite film
(459 eV for Ti2p3/2 and 465 eV for Ti2p1/2) and each the
three parts displayed a constant Ti/C ratio. Because the
TiO2 is uniformly distributed throughout the sample,
any fraction of the sample will be representative of the
sample as a whole.

Fig. 5. Relationship between TiO2 concentration in PPy/TiO2 composite film (cc) and its concentration in the electrolyte (ce) Electrolyte: 0.1 M
H2C2O4 pH 2.0 and 0.1 M pyrrole, j/5 mA cm2 and t /30 min.

D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

41

Fig. 6. SEM image of the PPy/TiO2 composite film.

After approximately 2 h of Ar  ion bombardment,

corresponding to 5 mm of composite film removal, the
amount of TiO2 was found to be slightly higher than it
was at the surface of the composite. However, the TiO2
concentration was observed to decrease further below
the surface of the film, as was observed after further
exposure to Ar ion bombardment [27].
SEM micrographs confirmed the homogeneous distribution of TiO2 at the surface of the PPy/TiO2
composite film (see Fig. 6, which shows the pigment
particles as white dots).
3.4. Corrosion tests
All samples used for these tests were synthesized in 0.1
M oxalic acid (pH 2.0) and contain 14% by weight of

titanium dioxide in the PPy/TiO2 composite film. The

dedoping process */polymer transition from oxidized to
reduced state [5] */was performed by sample immersion
after polymerization in 0.1 M NaOH applying /0.7 V
(SCE) for 15 min.
3.4.1. Weight loss tests
The weight loss test determined the quantity of iron
released from mild steel during immersion in a 3.5%
NaCl solution. Fig. 7 shows the behaviour of the steel
after three different treatments: (1) as degreased, (2)
coated by a dedoped PPy film and (3) coated by a
dedoped PPy/TiO2 composite film.
With degreased steel iron oxidation takes place
quickly when in contact with NaCl solution. This results
in the formation of a thin layer of iron oxides and

Fig. 7. Iron concentration (mg Fe l1) as a function of immersion time in 3.5% NaCl solution. j degreased 1010 steel; m PPy without TiO2; and '
PPy with TiO2.

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D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

hydroxides. But this protection is limited because the

thin layer is easily damaged and the sample then
undergoes a severe corrosion process.
For the steel coated by dedoped PPy/TiO2 composite
films there is at first an acceleration of the oxidation
process, probably due to initial iron oxidation through
the pores and/or defects of the dedoped polymer film. In
this case, the dedoped process did not yield a homogeneous passive layer throughout the sample. After
approximately 96 h no further iron is released from
the steel and the corrosion process stabilizes at 12.5 mg
of iron per litre of NaCl solution.
For the steel coated with dedoped PPy film, the initial
oxidation rate, attributed to iron oxidation, is slightly
higher than for steel coated with PPy/TiO2 composite
film. Thereafter the corrosion rate is slowed down but
no stabilization is observed. After 7 days the samples
released 25 mg of iron per litre of NaCl solution.
This behaviour can be explained by the low porosity
of PPy/TiO2 composite films due to the filling of
polymer pores by TiO2 particles as was observed by
SEM. This may contribute to the better performance of
PPy/TiO2 composite films in these tests.
Some experiments were performed with doped PPy
and PPy/TiO2 composite films. The weight losses were
slightly greater than those for the dedoped samples;
however as before the presence of TiO2 in the polymer
film contributed to a decrease in the amount of the
corrosion.
There are several explanations for the better performance of the dedoped ECP films. Ahmad and MacDiarmid [4] have concluded that during the reduction of
a chemically synthesized PANI, iron corrosion inhibition occurs by stable oxide layer formation at the
metal j PANI interface. Schauer et al. [9] have reported
that the polyaniline transition from the conductor to the
insulator form (dedoping process) also improves the
barrier properties of the conductive film. This transition
also enhances the pore resistance of the coating due to
the high resistance and sealing effect of the dedoped
polymer.

3.4.2. Salt spray tests (ASTM B117)

In spite of giving only qualitative information about
the behaviour of the metal/coating system when exposed
to an aggressive medium (5% NaCl at 35 8C), the salt
spray test is widely used for comparing the performance
of coatings. Samples of doped films were submitted to 5
and 24 h of exposure to salt spray. Some of the samples
received an X-cut in order to evaluate the underlayer
corrosion.
After 5 h of exposure to salt spray (Fig. 8a and b), the
samples showed evidence of corrosion and the attack
was more severe in the samples which had the X-cut.
The corroded area with an intense red colour was always

larger for the samples that did not contain TiO2

particles.
For films without an X-cut, the red corrosion within
the total exposed area was about 10% in electrodes
coated by the PPy films (Fig. 8a) and only 0.5% for
those coated by the PPy/TiO2 composite films (Fig. 8b).
Fig. 8c and d show the results obtained for samples
exposed for 24 h. The same trends as for 5 h were
observed. As expected the PPy and PPy/TiO2 samples
with the X-cut showed intense red corrosion. Samples
without the X-cut showed a corroded area that was
approximately 70% of the total exposed area for the
PPy/TiO2 samples and 100% for the PPy samples.
No blistering was found on the coating in the zone
outside the region of corrosion in all samples tested.
This indicates an excellent adhesion of both the PPy and
PPy/TiO2 films, to the substrate.

4. Conclusion
In this work we showed that it is possible to synthesize
PPy/TiO2 composite films that show good characteristics for the corrosion protection of mild steel. Some
parameters greatly influence the synthesis and favour
pigment incorporation e.g. looping stirring (there is no
significant incorporation due to electrophoresis phenomena), pigment concentration in electrolyte, electrolyte nature (oxalic acid is better than potassium nitrate
medium) and the applied current density (around 5 mA
cm 2).
XPS experiments have shown that the pigment is
located throughout the sample thickness but mainly at
the superior half part of the composite film. SEM
images confirm that the TiO2 particles are homogeneously distributed at the composite film surface with a
probable decrease in the number of polymer pores as
compared to PPy films alone.
Corrosion tests such as weight loss and salt spray tests
show that TiO2 significantly improves the anticorrosion
properties of PPy. The quantity of iron released from
the electrodes coated by PPy/TiO2 composite film
showed a stabilization of the corrosion process after
96 h of immersion in 3.5% NaCl solution. The electrodes
coated by PPy films showed a continuous increase in the
quantity of iron released. The dedoped PPy/TiO2
samples showed a 50% reduction of the iron quantity
released as compared to the dedoped PPy samples after
7 days of immersion in 3.5% NaCl solution. Salt spray
tests show that the PPy/TiO2 samples without the X-cut
displayed a reduction of about 95 and 30% in the
corroded area as compared to the PPy samples exposed
for 5 and 24 h, respectively.
PPy/TiO2 composite film coatings are a feasible
method for corrosion protection and can be applied as
a primary coating that can replace the conventional

D.M. Lenz et al. / Journal of Electroanalytical Chemistry 540 (2003) 35 /44

43

Fig. 8. Salt spray corrosion test: (A) after 5 h of exposure for PPy films; (B) after 5 h of exposure for PPy/TiO2 composite film. Left, sample after
exposition; Right, X-cut sample after exposition. (C) After 24 h of exposure for PPy films; and (D) after 24 h of exposure of PPy/TiO2 composite film.
Left, sample before exposition; Centre, sample after exposition; Right, X-cut sample after exposition.

system of phosphatized layers on mild steel. These layers

satisfy the demand for an environmentally acceptable
solution.

Acknowledgements
The authors are grateful to CNPq and CAPESCOFECUB (project 184/96) for their financial support.

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