Synthetic Metals 114 Ž2000.

105–108
www.elsevier.comrlocatersynmet

Anti-corrosive properties of polyaniline coating on iron

Abdolreza Mirmohseni ) , Ali Oladegaragoze
Polymer Research Technology Laboratory, Faculty of Chemistry, UniÕersity of Tabriz, Tabriz, I.R., Iran

Accepted 10 November 1999

Abstract

Polyaniline has been synthesized chemically and cast from 1-methyl-2-pyrrolidone ŽNMP. solution over iron samples. A series of
electrochemical measurements, including corrosion potential and corrosion current has been made on polyaniline-coated iron samples in
various environments. Results showed that polyaniline can offer some degrees of protection in the corrosive environments. Protective
properties of the conducting polymer were compared with a conventional polymer such as polyvinyl chloride ŽPVC.. Comparative
experiments revealed that emeraldine base form of polyaniline has better protective properties. q 2000 Elsevier Science S.A. All rights
reserved.

Keywords: Conducting polymer; Polyaniline; Corrosion; Iron

1. Introduction The early work of David DeBerry w13x demonstrated a

Corrosion is one of the most serious problems in the
industrial world. In the last few years the use of conduct-
ing polymers for protection of metals against corrosion has
been investigated w1,2x. Among the family of conducting
polymers there are a number of reports on the protection
effects of the electroactive polyaniline w3–5x.
The term ‘‘polyaniline’’ is descriptive of a class of
conducting polymers that can be reversibly oxidized and
reduced over a large range of potentials. Unlike other
conducting polymers such as polypyrrole w6x, the polyani-
line can be doped to a highly conducting regime in acidic
media w7,8x without removing electrons from the polymer
backbone Žnon-oxidative doping.. The polymer can also
undergo oxidative doping which is a reversible process
within the potential range that the polymer is stable w9–11x.
This ability enables polyaniline to act as a versatile poly-
mer in anti-corrosion studies.
It has been shown that polyethoxyaniline can protect
iron in some degrees against acidic aqueous solution w12x.
In this study, it was shown that the existence of delocal-
ized p-electrons and the quaternary ammonium nitrogen
on iron surface perform better corrosion inhibition.
)
Corresponding author.
change in corrosion potential and corrosion current of
stainless steel plate with polyaniline coating. The corrosion
protection properties of emeraldine base when coated on
iron and cold rolled steel was discussed by Jasty and
Epstein w14x utilizing XPS and corrosion protection studies.
The polyaniline film was also used as an anti-corrosion
coating on aluminum substrates. The results showed a
significant protection of the aluminum surface with a two
order of magnitude decrease in the corrosion rate relative
to an uncoated surface w15x. In another study, a reduction
in corrosion rate of cold rolled steel by polyaniline coating
was reported. The base form of polyaniline was found to
offer good corrosion protection. The conjugated polymers
such as polystyrene did not show the same electrochemical
behavior w16x.
The emeraldine base form of polyaniline has been used
as a corrosion protecting undercoat on steel and iron
samples using XPS. Emeraldine base polyaniline under-
coats were found to offer corrosion protection for both the
cold rolled steel and iron samples w17x. Using XPS and
potentiodynamic studies, the emeraldine base-coated cold
rolled steel coupons were compared with non-coated cold
rolled steel and a shift in the open circuit potential for the
emeraldine base-coated samples was observed w18x.
More recently, the corrosion protection effect of several
forms of polyaniline including emeraldine base on alu-

0379-6779r00r$ - see front matter q 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 3 7 9 - 6 7 7 9 Ž 9 9 . 0 0 2 9 8 - 2
106 A. Mirmohseni, A. Oladegaragozer Synthetic Metals 114 (2000) 105–108
minumraluminum alloys was studied by Epstein et al. w19x
using photoelectron and potentiodynamic techniques.
Current investigation provides a series of studies carried
out on corrosion protective properties of a thin layer of
polyaniline coating Ž9–10 mm. in different corrosive solu-
tions such as NaCl Ž3.5% W., tap water and acidic solu-
tions. A comparative study was also carried out using a
conventional polymer coating such as polyvinyl chloride
ŽPVC.. Finally, an attempt was made to describe mecha-
nistically the protective properties of the polyaniline films.
2. Experimental
2.1. Reagents and materials
Analytical reagents ŽAR. grade chemicals were used
through out, unless otherwise stated. Ammonium per-
sulphate, sodium chloride, aniline, hydrochloric acid,
1-methyl-2-pyrrolidone ŽNMP., sulfuric acid, acetone,
ammonia and potassium permanganate were all purchased
from Merck chemicals. Nitric acid and PVC ŽMr ; 48000.
were purchased from Fluka chemicals.
2.2. Instrumentation
To apply constant potential or current, a ZAG Chemie
Model ZCL 73A was used.
2.3. Sample preparation
The iron samples with 2 = 2 cm dimension and 0.7 mm
thickness were cut from a piece of iron plate with the
99.619% iron.
The samples were polished by emery cloth no. 150 and
400, respectively. Prior to coating, all samples were pre-
treated in acetone and ethyl alcohol solution to remove
impurities. Finally, the samples were rinsed with distilled
water and dried by acetone. Prior to any experiment, the
samples were treated as described and freshly used with no
further storage.
2.4. Polyaniline-coated samples
Polyaniline was synthesized chemically and dissolved
in NMP solution w20,21x. This solution was cast drop-wise
onto pretreated iron samples. A level has to be obtained
before casting. The emeraldine base-coated samples were
dried in an oven at 608C for about 12 h.
2.5. PVC-coated samples
One gram of PVC powder was dissolved in 20 ml of
NMP and stirred for 10 h. This solution was poured onto
pretreated iron samples. The so-prepared samples were
dried at 608C for a period of 12 h.
Throughout this work, tafel plots were carried out using
a conventional three-electrode electrochemical cell with a
platinum counter electrode and a AgrAgCl reference elec-
trode. The working electrode was the iron sample Žcoated
or uncoated.. To measure open circuit potential of the
samples, a two-electrode system was used with the sample
as working and a AgrAgCl as reference electrodes.
3. Results and discussion
It has been shown that the equilibrium open circuit
potential of polymer-coated electrode can be considered as
the corrosion potential w16x. The open circuit potential of
coated and uncoated samples were therefore measured and
plotted against time. Fig. 1 shows the equilibrium potential
of coated and uncoated samples in various environments.
In tap water, polyaniline-coated samples have higher cor-
rosion potential values than uncoated samples. This indi-
cates that the corrosion potential of coated sample has
been shifted towards noble potentials. Similar results were
obtained in a solution containing 3.5% W NaCl. Again the
polyaniline-coated samples had better performance against
corrosion.
It was found that the equilibrium open circuit potentials
of coated samples decreased in acidic media compared to
the nonacidic media ŽFig. 1. and the protective perfor-
mance of the coated samples was not as good as non-acidic
media. In the case of this work, various acidic solutions
were employed ŽHCl, H 2 SO4 , HClO4 . and similar behav-
ior was observed. The fact that anti-corrosive properties of
the polymer decreased in the acidic media is perhaps due
to high permeability of the polymer to proton movement.
We have shown this effect in our previous works w20x.
Using a potentiodynamic technique Žtafel plots. further
investigations were carried out. The tafel plots were gener-
ated by applying the potential from Eeq toward negative
and positive potentials against AgrAgCl reference elec-
Fig. 1. Plots of open circuit potential vs. time for uncoated and polyani-
line-coated samples in tap water ŽB,I., 3.5% NaCl solution Ž^,'. and
0.1 M HCl solution Žl,e..
 A. Mirmohseni, A. Oladegaragozer Synthetic Metals 114 (2000) 105–108 107

trode. Fig. 2a,b shows tafel plots for uncoated and polyani-
line-coated iron specimens in NaCl 3.5% W solution. The
corrosion potential of polyaniline-coated samples was
shifted toward anodic direction Ž D E ( 1.65 V. compared
to the uncoated samples. The anodic tafel slope was also
increased for the polyaniline-coated samples indicating a
significant reduction of corrosion current. Also internal
current shows decrease in the corrosion rate of coated
samples with respect to uncoated samples.
The results were compared with the samples coated by
a conventional polymer such as PVC ŽFig. 3.. As shown,
the corrosion current for polyaniline-coated samples soaked
in NaCl 3.5% W solution is much smaller than PVC-coated
samples in the same solution ŽFig. 3a.. The corrosion
potential was also higher indicating proper protection of
polyaniline layers.
Further investigations were carried out in acidic media.
The polyaniline-coated and PVC-coated samples were
soaked in 0.1 M HCl solution and the tafel plots were
recorded ŽFig. 3b.. The equilibrium potential of polyani-
line-coated samples has been shifted toward anodic poten-
tial compared with PVC samples Ž D E ( 0.25 V.. How-
ever, the rate of corrosion of PVC-coated samples was
smaller in particular at higher oxidative and reductive
potentials.

Fig. 3. Tafel plots for polyaniline-coated and PVC-coated samples in Ža.

3.5% W NaCl solution and Žb. 0.1 M HCl solution.

In order to reveal a better understanding of the interest-

ing, but very complex corrosion protection by polyaniline,
further investigations were carried out. It is assumed that
the iron samples may be protected by formation of a
passive layer on iron due to the redox properties of
polyaniline. To investigate this, polyaniline layer of the
samples were removed carefully after treating in corrosive
environments ŽNaCl 3.5% W..

Fig. 4. Tafel plots for passivated sample Ž1. and polyaniline coat removed
Fig. 2. Tafel plots for uncoated Ža. and polyaniline-coated Žb. samples in sample Ž2. in 3.5% NaCl solution. The polyaniline layer was removed
3.5% W NaCl solution. after treating the sample in 3.5% W NaCl solution.
108 A. Mirmohseni, A. Oladegaragozer Synthetic Metals 114 (2000) 105–108
Using another bare iron sample, an oxide passive layer
was produced at the surface of sample by immersing the
iron in 1 grl KMnO4 solution for 2 h. Corrosion behavior
Žcorrosion current. of polyaniline removed sample was
compared with passivated sample ŽFig. 4.. The rate of
corrosion and corrosion potential for both samples are very
similar. This may suggest that polyaniline provides a pas-
sive layer on iron and the protection occurs mainly due to
the formation of this passive layer.
4. Conclusion
A series of electrochemical measurements, including
corrosion potential and corrosion current has been made on
polyaniline-coated iron samples in various corrosive envi-
ronments such as NaCl Ž3.5% W., tap water and acids. It
was found that corrosion potential of the polyaniline-coated
samples was shifted toward noble potentials indicating
better performance of polyaniline coating. A significant
decrease in corrosion current was also observed.
It was also found that polyaniline coating in many cases
can be preferred over a conventional polymer such as
PVC. This has been confirmed by electrochemical mea-
surements in corrosive environments such as NaCl Ž3.5%
W..
Acknowledgements
We are most grateful the continuing financial support of
this research project by the University of Tabriz.
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