A study on mechanism of corrosion protection of

polyaniline coating and its failure

Jianjun Fang, Ke Xu, Lihua Zhu
*
, Zhixiong Zhou, Heqing Tang
*
Department of Chemistry and Chemical Engineering, Huazhong University of Science and Technology,
Wuhan 430074, PR China
Received 27 November 2006; accepted 1 May 2007
Available online 19 July 2007
Abstract
Polyaniline (PANI) coatings were electrochemically deposited on substrates of stainless steel and
platinum in solutions of 0.2 M H
2
SO
4
and 0.1 M aniline by cyclic voltammetry. The corrosion pro-
tection of the PANI coatings and their failure were investigated in 0.2 M H
2
SO
4
solution. It was
observed that the corrosion protection ability of the coating to steel substrate was increased with
the increase of the coating thickness. The corrosion protection ability was mainly attributed to
the passivating eect of PANI due to its oxidizing ability in its emeraldine state. During its opera-
tion, the PANI coating in emeraldine state tended to gradually lose its corrosion protection ability.
This gradual failure of the PANI coating, but faster than expected, was conrmed to be related to a
gradual reduction of the emeraldine PANI and a gradually increased resistance between the PANI
coating and the stainless steel substrate. These ndings lead to a new mechanism for the corrosion
protection of PANI coating and its failure.
2007 Elsevier Ltd. All rights reserved.
Keywords: A. Polyaniline; A. Stainless steel; C. Corrosion; C. Electrodeposited lms; C. Galvanic coupling
1. Introduction
Intrinsically conducting polymer, because of its specic properties, has a wide range
of applications. One of the important and promising applications is corrosion protection.
0010-938X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2007.05.017
*
Corresponding authors. Tel.: +86 27 87543432; fax: +86 27 87543632.
E-mail addresses: lhzhu63@yahoo.com.cn (L. Zhu), hqtang62@yahoo.com.cn (H. Tang).
Corrosion Science 49 (2007) 42324242
www.elsevier.com/locate/corsci
Of the conducting polymers the polyaniline (PANI) families have been the most widely
studied, due to their environment stability and ease of synthesis. In the eld of corrosion
protection, PANI can be used either as corrosion inhibitors or as protective coatings.
PANI can function as inhibitors, because of the presence of the functional group C@N
which can be adsorbed on the metal surface. It was found that soluble PANI absorbed
on the metal restrain the anodic or cathodic reaction [1,2]. In much more cases, PANI
was used as protective coatings. Since DeBerry [3] showed in 1984 that the electrochemi-
cally deposited PANI protected stainless steel by anodic protection, PANI was investi-
gated for protection of stainless steel [3,4], iron [5,6], mild steel [7], copper [4],
aluminum [8] and zinc [9]. It was also shown that PANI protects mild steel in chloride
medium [7,10]. PANI can also be used as a blend with epoxy resin, or as an under layer
with an epoxy top-layer [1012]. Pereira da Silva et al. [13] studied PANI acrylic coatings
for corrosion inhibition and found that counter-ions were a crucial factor for determining
the protective performances of the coatings.
Many researches have been done to clarify the mechanism for the corrosion protection
of PANI coatings. Wessling [4] found that coats of chemically synthesized PANI induced
an oxide formation on the metal surface, making corrosion potential of stainless steel shift
to the direction of noble metals and leading to a decreasing of corrosion current. Hugot-Le
Go and coworkers [14,15] reported the iron coated with electrochemical PANI was actu-
ally in the passive state by means of in situ micro-Raman spectroscopy. Gasparac and
Martin [16] showed that the presence of conducting polymers could even passivate the
pre-introduced pinholes, and found by XPS analysis that the outer part of oxide lm
was Fe
2
O
3
, while the under-lm was Fe
3
O
4
. It is generally accepted that the oxidation
of the metallic surface during the exposure to an aggressive environment is linked to the
reduction of PANI [17], which is re-generated by the reoxidation of PANI coating through
the reduction of dissolved oxygen at the PANI/electrolyte interface.
Until to the present time, various and even contradictive experimental results and opin-
ions on the corrosion protection of PANI coating and its mechanism have been reported,
because of the complicated corrosion systems (dierent metals to be protected, dierent
corrosion media, dierent methods of PANI synthesis, and dierent synthesis conditions).
In the aspect of experimental ndings, most of reported research works claim that PANI
protects when doped [6]. The protection can be achieved with undoped PANI [5,18], which
is in contradiction with Araujos work [19] that undoped PANI give little protection com-
paring with common paint. The reports that PANI protects in chloride medium [7,10] are
against the claim that PANI does not protect in chloride medium [6]. Kenneths nding
[20] that electrochemically deposited PANI had little protection on pure aluminum is dif-
ferent from the work of Racicot et al. [8] that it can protect aluminum. Santos et al. [21]
reported excellent adhesion properties for undoped PANI tested in 3% NaCl solution,
whereas Lu et al. [22] found poor adhesion in 3.5% NaCl solution. In the aspect of the
protection mechanism, both the presence of metallic oxides [23] and metallic complexes
[17] at the metallic surface were proposed as components in the passive layer. In contrast
to the general opinion that the reoxidation of PANI coating through the reduction of dis-
solved oxygen at the PANI/electrolyte interface takes an important role in the passivating
eect of PANI coating [17], Rammelt et al. [24] claimed that the reduction of both the dis-
solved oxygen and the conductive polymer form a redox couple with the metal oxidation
reaction, and that the less noble substrate would corrode even much faster through
the pores, because a local element would be formed with the pores acting as anodes.
J. Fang et al. / Corrosion Science 49 (2007) 42324242 4233
Also Tan and Blackwood [25] believed that PANI accelerated the corrosion of carbon steel
in a manner akin to bimetallic corrosion.
The above-mentioned divergent research results and contradictions in the mechanism
for corrosion protection of PANI coating inspired us to further study on mechanism of
corrosion protection of PANI coating and its failure. In the present work, the corrosion
protection of PANI to stainless steel and its gradual loss were investigated in 0.2 M
H
2
SO
4
. The use of H
2
SO
4
instead of HCl favors avoiding the inuences of aggressive
Cl

ions. Moreover, the ions exchange between the electrolytic solution and the doped
PANI coating can be neglected, and hence we can focus on the impact of interface prop-
erty on the corrosion protection and failure of PANI coatings.
2. Experimental
Aniline (Aldrich) was distilled and stored in the dark before use. PANI coatings were
deposited from solutions of 0.2 M H
2
SO
4
+ 0.1 M aniline. Electrochemical polymerization
of aniline was adopted to prepare PANI coatings on stainless steel (SS) and Pt-foil sub-
strates, because it provides good adhesion between the PANI with the electrode and ease
of control the thickness of the PANI lm. The areas of both SS and Pt working electrodes
were 1 cm
2
. In the preparation, the counter-electrode was Pt-foil and the reference elec-
trode was saturated calomel electrode (SCE), which all the potentials throughout this
work are referred to. Prior to each experiment, the working electrode were polished with
emery paper down to 2400 grit, washed with distilled water and nally with ethanol.
PANI coatings were electrochemically deposited by potential cycling at 10 mV s
1
from
0.2 V to 1.0 V in the rst cycle, and then from 0.2 V to 0.9 V in the successive cycles.
The decreased high potential limit (0.9 V) in the successive cycles favors to avoid degrada-
tion of PANI [26], and the low scan rate (10 mV s
1
) can make sure the lms more com-
pact and adhesion to the substrate. The thickness of PANI coatings was controlled by
adjusting the total number of potential cycling. In the present work, three types of PANI
coatings were obtained on the SS by controlling the total cycle number as 5, 10 and 15.
When these coatings were switched from leucoemeraldine (LE, the reduced form of PANI)
to the emeraldine (EM, the partially oxidized form of PANI) state, they yielded an oxida-
tion charge of 0.381, 2.00 and 4.66 mC cm
2
. According to the correlation between the lm
thickness and the oxidation charge, these lms were estimated with a lm thickness of
0.014, 0.074 and 0.172 lm, respectively. When the electrodeposition was performed on
Pt substrates, the resultant PANI coatings were found to yield an oxidation charge of
0.35, 2.3 and 3.9 mC cm
2
, which were slightly dierent from that of the PANI coating
correspondingly obtained on SS substrates. Because the small dierences between the lm
thickness on SS and Pt substrates did not cause a marked eect on the corrosion protec-
tion ability of the coatings, we could neglect the dierences between the thickness of the
PANI coatings on SS and Pt substrates. For simplicity, these coatings are referred to as
PANI-1, PANI-2 and PANI-3 in the order of lm thickness increasing.
After being cleaned with 0.2 M H
2
SO
4
to wash o the un-reacted monomer, both the
coatings on SS and on Pt were polarized at the potential of 0.4 V to achieve an EM state.
Then, the corrosion protection of PANI coating was studied with measurements of open-
circuit potential (OCP), polarization curves and electrochemical impedance spectroscopy
in 0.2 M H
2
SO
4
. Electrochemical experiments were performed in a single compartment cell
4234 J. Fang et al. / Corrosion Science 49 (2007) 42324242
on a CHI 600 electrochemical analyzer under computer control (CHI). All the experiments
were carried out at room temperature.
3. Results and discussion
3.1. Generation of passive lm and PANI deposits on SS substrate
The active electro-dissolution of SS substrate is unfavorable to the formation of the
PANI electrodeposits on the electrode surface. Thus, the deposition must be performed
on a passive surface. It is approved that H
2
SO
4
is appropriate for polymerization [27].
Fig. 1 gives the polarization curve of SS electrode in 0.2 M H
2
SO
4
. The wide potential win-
dow of the passivation from about 0.2 V to 1.1 V suggests that it is feasible to generate
electrochemical PANI coatings on SS substrates in 0.2 M H
2
SO
4
, and the rather small cur-
rents in the potential window of passivation indicate that the compact structure of the pas-
sive lm permits a good bonding with the polymer lm.
Cyclic votammogram of the SS electrode was recorded in 0.2 M H
2
SO
4
+ 0.1 M aniline.
In the rst cycle of potential scan as shown in Fig. 2a, a peak (A) for the transition from an
active state to a passive state of SS was observed at about 0 V, where a passive lm was
formed on the surface of SS substrate. The increased oxidation current beyond about
0.9 V (peak B) correspond to the aniline monomer oxidation, which leads to the deposition
of PANI, reected by the appearing of the reduction peaks C and D for the reduction of
PANI. Because the passive lm was thin and conductive, PANI could be electrodeposited
on the top of the passive lm. The generation of PANI deposits was conrmed by the cyc-
lic voltammograms shown in Fig. 2b, which are in good agreement with the typical cyclic
voltammograms reported in the literature.
3.2. Corrosion protection of PANI coating and its failure
In our present work, we investigated the corrosion protection of PANI coatings mainly
by monitoring the time course of the OCP during immersion. Before the measurements,
1E-7 1E-6 1E-5 1E-4 1E-3
-0.4
0.0
0.4
0.8
1.2
P
o
t
e
n
t
i
a
l

/

V
Current / A
Fig. 1. Polarization curve of SS in 0.2 M H
2
SO
4
recorded at a scan rate of 0.5 mV s
1
.
J. Fang et al. / Corrosion Science 49 (2007) 42324242 4235
the PANI electrode was polarized at the potential of 0.4 V for 60 s to achieve the EM.
When PANI was coated on Pt substrate, the OCP of the PANI/Pt electrodes was very sta-
ble and kept almost the same value of about 0.4 V during the immersion in both aerated
and de-aerated 0.2 M H
2
SO
4
for several days. This indicates that oxygen dissolved in solu-
tion has little inuence on the oxidation state of PANI which was pre-polarized at 0.4 V
for 60 s.
The time-courses of OCP of the SS electrodes coated with PANI of dierent thickness
were recorded in 0.2 M H
2
SO
4
solutions. As shown in Fig. 3a, the OCP variation for the
coating with dierent thickness obviously has the same evolution discipline [27,28]. Three
stages are observed in the time-course curves. The OCP decreases from 0.4 V to 0.1 V
slowly in stage I, then rapidly decreased to about 0.3 V in stage II, and changed little
in stage 3. The shape of the curves recorded for the OCP changes of the PANI-coated
SS electrodes is very similar to that observed for pre-passivated SS electrode without
-0.2 0.0 0.2 0.4 0.6 0.8 1.0
-0.002
0.000
0.002
0.004
0.006
1
D
C
A
B
C
u
r
r
e
n
t

/

A
Potential / V
-0.2 0.0 0.2 0.4 0.6 0.8 1.0
-0.01
0.00
0.01
0.02
C
u
r
r
e
n
t

/

A
Potential / V
15
10
5
a b
Fig. 2. Cyclic voltammograms of SS electrode recorded at 10 mV s
1
in 0.2 M H
2
SO
4
+ 0.1 M aniline. The
numbers indicate the cycle numbers in the preparation.
1000 10000 100000
-0.4
-0.2
0.0
0.2
0.4
III
II
I
PANI-3
PANI-2
PANI-1
P
o
t
e
n
t
i
a
l

/


V
Immersion time / s
10 100 1000
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
P
o
t
e
n
t
i
a
l

/

V
Immersion time / s
a
b
Fig. 3. OCP measurements on PANI/SS electrodes (a) and pre-passivated SS electrode (b) during immersion in
0.2 M H
2
SO
4
.
4236 J. Fang et al. / Corrosion Science 49 (2007) 42324242
any PANI coating in 0.2 M H
2
SO
4
(Fig. 3b). As illustrated in Fig. 3b, the passivity break-
down of naked SS which was pre-polarized at 0.4 V for 15 h in 0.2 M H
2
SO
4
is instanta-
neously (on the order of 10 s) [28]. Therefore, in the cases of PANI-coated SS, the
EM-state PANI lm makes the substrate of stainless steel be passive, and the metal is well
protected in stage I. After being immersed in the acid solution for a (long) period of time,
the passivity of the SS substrate may instantaneously break down in stage II due to the
attacking of the corrosive media, and the metal substrate is actively corroded in stage
III. It can be found from Fig. 3a that the time (s) required for the breakdown of the
passivity of the PANI/SS is increased with the increase of the PANI lm thickness. That
is, a thicker PANI coating provides better corrosion protection to SS substrate. Hereafter,
the protection time is measured by the elapsed time between the immersion of the samples
into the corrosive test medium and the end of the second stage [28].
3.3. Mechanism of corrosion protection of PANI coating and its losing
We are interested in why and how the passivity of the SS substrate coated with PANI
coating breakdown in the acid solution. This was considered from several aspects.
(1) Serious degradation of the PANI coating may lead to loss of corrosion protection
ability of PANI. However, our experiences suggest that it is impossible to create a
serious deterioration of PANI by a immersion in 0.2 M H
2
SO
4
solution for several
days, and the OCP of PANI/Pt pre-polarized at 0.4 V was observed to change little
during the immersion in both aerated and de-aerated 0.2 M H
2
SO
4
for several days.
Thus, the loss of corrosion protection ability of PANI in our work is not due to its
degradation.
(2) The passive lm of SS is thermodynamically unstable in 0.2 M H
2
SO
4
solution
(Fig. 3b), and the electrodeposited PANI lm is porous to some extents and cannot
function as an excellent physical barrier to the diusion of corrosive media across it.
(3) PANI in EM state can passivate SS in 0.2 M H
2
SO
4
solution. We recorded the OCP
of a SS electrode galvanic-coupled with PANI/Pt electrodes in 0.2 M H
2
SO
4
solution
as shown in Fig. 4. Before all the coupling experiments, the SS electrode was rst
1000 10000 100000
-0.2
0.0
0.2
0.4
P
o
t
e
n
t
i
a
l

/

V
Immersion time / s
PANI-1/Pt
PANI-2/Pt
PANI-3/Pt
0 1 2 3 4 5
0
60000
120000
180000
PANI/SS
SS coupled with PANI/Pt
P
r
o
t
e
c
t
i
o
n

t
i
m
e

/

s
Oxidation charge of PANI / mC cm
-2
a b
Fig. 4. (a) OCP of a pre-passivated SS electrode coupled electrically with dierent PANI/Pt electrodes in 0.2 M
H
2
SO
4
and (b) protection time of PANI/SS and PANI/Pt with dierent PANI lm thicknesses.
J. Fang et al. / Corrosion Science 49 (2007) 42324242 4237
swept to 0.4 V to make it passivated. The OCP-time curves for the coupled systems
(Fig. 4a) are very similar in shape to those for individual PANI/SS electrodes
(Fig. 3a) in the rst two stages, but dierent in the third stages. In addition, the
SS electrode which is coupled with PANI/Pt electrodes gave OCP-time behaviors
similar to that of passivated SS electrode (Fig. 3b) when the electrically coupling
was cut o between the SS electrode and the PANI/Pt electrode in the rst stage
(coupling for a long time). These suggest that the EM-state PANI can passivated
SS substrate. Relative to the PANI/SS electrodes, the SS electrode coupled with
PANI/Pt electrode gives much increased protection time s as illustrated in Fig. 4b.
However, the PANI coating cannot prevent the SS substrate completely from corro-
sion. Relative to the PANI/SS structure, the PANI/Pt structure can provide much
increased protection to the coupled SS substrate. This indicates that the corrosion
protection ability of PANI coating is related to the interface of PANI/SS, which will
be discussed later.
(4) The main reason for the failure of the corrosion protection of PANI coating is
related to some changes at the SS/PANI interface. Because the PANI coating on
Pt gives much increased protection time to SS substrate than the PANI coating on
SS, we may conclude that the PANI lm coated on SS may lose its corrosion protec-
tion ability much faster than expected. To clarify the reason for this requires the
understanding what will happen during the immersion in acid solution. Therefore,
we compared the cyclic voltammograms of PANI/SS electrode before and after
the OCP test in 0.2 M H
2
SO
4
. The typical cyclic voltammogram before the OCP test
in Fig. 5a is in well agreement with that reported for PANI in acid solutions. How-
ever, after the OCP test, the cyclic voltammograms changed markedly. In the rst
scan of Fig. 5b, an oxidation peak (A) appears at 100 mV, which corresponds to
passivation of steel substrate. The appearing of the passivation peak demonstrated
that the surface of the steel substrate is at least partially exposed directly to the elec-
trolytic solution, indicative of any damages of the PANI coating or the disbonding
of the coating from the substrate. In successive potential scans, peak A disappears
due to recovering of the passive layer on steel substrate. Peak B in Fig. 5b may be
attributed to the oxidation of PANI from LE to EM state. Once the corroded
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
-0.004
-0.002
0.000
0.002
0.004
0.006
C
u
r
r
e
n
t

/

A
Potential / V
-0.002
0.000
0.002
0.004
0.006
0.008
B
C
B
C
u
r
r
e
n
t

/

A
Potential / V
A
1
2
3
4
a b
Fig. 5. Cyclic voltammograms of PANI/SS in 0.2 M H
2
SO
4
before (a) and after (b) the OCP measurements. The
numbers in (b) indicates the cycle numbers.
4238 J. Fang et al. / Corrosion Science 49 (2007) 42324242
PANI/SS electrode was oxidized in the rst potential cycle, the peak B decreased sig-
nicantly in current in the successive potential cycles. The cyclic voltammograms
recorded in the successive cycles are very dierent from that before the OPC test,
and look like one observed for an electrode coated with very thick and resistive
PANI lm. The decreased currents of the redox peaks in the successive cycles also
suggest that the immersion in the OCP test makes the polymer-coated electrode be
more resistive. Because it is impossible to consider the degradation of the polymer
itself, the increased resistance of the PANI/SS electrode should be attributed to
the (mild) corrosion of SS substrate and the accumulation of corrosion products
at the PANI/SS interface. Not only the corrosion products are resistive, but also they
can disbond the polymer lm from the substrate, leading to increase of the interfacial
resistance.
(5) Electrochemical impedance spectroscopic measurements demonstrated that the inter-
facial resistance at PANI/SS electrodes was increased after the OCP test. When the
EIS measurement was performed at 0.38 V in the rst stage of the OCP measurement
(Fig. 3a), the PANI/SS electrode was observed to show pure capacitive behavior.
After the OCP measurement was ended at the third stage (Fig. 3a), the open-circuit
potential of the PANI/SS electrode was shifted to 0.26 V. We re-polarized the
PANI/SS electrode at 0.38 V for 20 min to avoid the eect of any reduced nonconduc-
tive PANI, and then conducted the EIS measurement at 0.38 V again. It was found
that at high frequency the electrode showed an interfacial resistance, which was esti-
mated to be about 2 X. Before the re-polarization at 0.38 V for the EIS measurement,
the actual resistance during the OCP test may be larger than the estimated 2 X.
(6) The increased interfacial resistance was conrmed to decrease the corrosion protec-
tion ability of PANI coating to SS substrate. Being similar to the experiment
described (Fig. 4), we made a galvanic coupling between a pre-passivated SS elec-
trode PANI/Pt electrodes via a small resistor (R) in series, and measured its OCP
in 0.2 M H
2
SO
4
solution, It is easily seen from Fig. 6 that the protection time of
PANI/Pt to the corrosion of SS was markedly decreased as the resistor R was
increased slightly.
0 2000 4000 6000 8000 10000
-0.2
0.0
0.2
0.4
R = 0 R = 3.5
R = 5
P
o
t
e
n
t
i
a
l

/

V
Immersion time / s
Fig. 6. OCP of SS electrode coupled electrically with a PANI/Pt electrode via an in-series resistor (R) in 0.2 M
H
2
SO
4
. Before the measurement, both SS and PANI/Pt electrodes were simultaneously pre-polarized at 0.4 V for
60 s.
J. Fang et al. / Corrosion Science 49 (2007) 42324242 4239
(7) Dissolved oxygen in solution may favor to re-oxidize the partially-reduced PANI in
the PANI-SS corrosion system, but it cannot recover the corrosion protection ability
of PANI. The coupling of SS and PANI/Pt electrodes was done both in aerated and
deaerated 0.2 M H
2
SO
4
solutions. The two curves for the OCP variation in Fig. 7 are
almost the same except for the region of stage III. Relative to the deaeration, the dis-
solved oxygen almost did not increase the corrosion protection time. Once the pas-
sivation of SS brokendown (at stage III), the OCP of the coupled electrodes kept
almost constant at about 0.25 V in deaerated solution, whereas it gradually
increased up to about 0.1 V in aerated solution. The slow increasing of the OCP
in aerated solution is attributed to the oxidizing ability of dissolved oxygen, which
may re-oxidize the partially-reduced PANI, but cannot re-passivate the corroded
SS substrate.
(8) The losing of the corrosion protection ability of PANI coating is not due to its losing
of electrochemical activity. After the above experiment of coupling the SS electrode
with PANI/Pt electrodes, we cut o the connection of PANI/Pt to SS, and observed
the recovery of the OCP of PANI/Pt alone. After the PANI/Pt electrode was discon-
nected from the SS electrode, the OCP of PANI gradually increased and nally
achieved about +0.4 V as shown in Fig. 8. This demonstrates that the electrochem-
ical activity (or the nature of the EM state) of the PANI coating has been remained
substantially even after the PANI/Pt lost its corrosion protection ability to the cou-
pled SS electrode.
(9) The third stages in Fig. 3a and Fig. 4a are obviously dierent, which is related to the
dissolved oxygen. In Fig. 3a dissolved oxygen has little impact on the potential, and
the nal potential stays almost the same as the naked electrode in 0.2 M H
2
SO
4
. But
in Fig. 4a the nal potential stays at the potential at which the steel would corrode
much faster. For PANI/SS electrode in the rst two stages stainless steel is passiv-
ated, and in the third stage PANI has little impact on stainless steel. Therefore,
we believe that in the case of PANI/SS there is no probability of bimetallic corrosion.
Based on the above considerations from (1) to (8), we may summarize the mechanism of
corrosion protection of PANI coating and its failure as followings. Electrochemical depo-
sition of PANI on SS substrate favors to the passivation of the SS substrate, and the PANI
0 10000 20000 30000 40000
-0.2
0.0
0.2
0.4
deaerated
aerated
P
o
t
e
n
t
i
a
l

/

V
Immersion time / s
Fig. 7. OCP of the SS coupled with PANI-1/Pt in aerated and deaerated 0.2 M H
2
SO
4
solutions.
4240 J. Fang et al. / Corrosion Science 49 (2007) 42324242
coating at EM state can help the SS substrate to hold at its passivation state. The corro-
sion protection ability of the PANI coating is mainly due to two factors. One is that the
PANI coating at emeraldine state has a positive potential, at which the SS substrate can be
passivated. The other one is that the PANI coating can function partially as a physical
barrier to the diusion of corrosive media across it, leading to increasing of the protection
time. Therefore, the corrosion protection ability of the PANI coating is increased as its
thickness is increased. However, the electrodeposited PANI coating is intrinsically porous,
leading to accessing of corrosive media to the surface of the SS substrate and then the
breakdown of the passivation of SS. The PANI coating in emeraldine state lost its corro-
sion protection ability considerably faster than expected. It is not due to a rapid reduction
of PANI in EM state, but because the corrosive media accessing the SS substrate react
with the substrate, producing some corrosion products and then worsening the adherence
of the PANI coating onto the substrate. This kind of failure cannot be recovered by the
possible redox cycle consisting of PANI and the dissolved oxygen. Therefore, a better pro-
tective PANI coating requires at least to be thick, compact, and with excellent adherence
to the metal substrate.
4. Conclusion
PANI lm with dierent thickness was synthesized on SS in 0.2 M H
2
SO
4
+ 0.1 M ani-
line by potential cycling. PANI in its EM state was found to be able to protect SS substrate
in 0.2 M H
2
SO
4
and the protection ability was increased as the coatings became thicker.
The PANI lm coated on a Pt substrate could provide much better protection to SS than
that coated directly on a SS substrate. The dissolved oxygen was conrmed not to show
observable eect on the corrosion protection of PANI coatings in H
2
SO
4
solutions. The
PANI coating in emeraldine state lost its corrosion protection ability considerably faster
than expected. This is because the diusion of corrosive species (such as H
+
) can cause a
gradual damage of the passive layer on the SS substrate and a slight or mild corrosion of
the substrate will produce an increased interface resistance between PANI and the SS sub-
strate, which results in the failure of the corrosion protection of the PANI coating to the
SS substrate. Our observed experimental results and proposed mechanism strongly suggest
0 5000 10000 15000 20000
0.0
0.2
0.4
P
o
t
e
n
t
i
a
l

/

V
Immersion time / s
Fig. 8. Recovery of OCP of PANI/Pt electrode when it was cut o electrically from the SS electrode after the
coupling test in 0.2 M H
2
SO
4
.
J. Fang et al. / Corrosion Science 49 (2007) 42324242 4241
that a low porosity of the PANI coating and a strong adhesion to the substrate are pre-
requisites for excellent corrosion protective coatings.
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