Conducting Polymers For Corrosion Protection A Review

Conducting polymers for corrosion protection: a review
Pravin P. Deshpande, Niteen G. Jadhav,

Victoria J. Gelling, Dimitra Sazou
American Coatings Association 2014
Abstract Conducting polymers (CPs) such as polyan-
iline (PANI), polypyrrole (PPy), and polythiophene
(PTh) are used for the corrosion protection of metals
and metal alloys. Several groups have reported diverse
views about the corrosion protection by CPs and hence
various mechanisms have been suggested to explain
anticorrosion properties of CPs. These include anodic
protection, controlled inhibitor release as well as
barrier protection mechanisms. Different approaches
have been developed for the use of CPs in protective
coatings (dopants, composites, blends). A judicious
choice of synthesis parameters leads to an improve-
ment in the anticorrosion properties of the coatings
prepared by CPs for metals and their alloys. This
article is prepared as a review of the application of CPs
for corrosion protection of metal alloys.
Keywords Conducting polymers, Pigments,
Corrosion protection, Surface coating technology
Introduction
Metals and their alloys are thermodynamically favored
to undergo corrosion events. Corrosion can be dened
as the destruction or deterioration of a material
because of reaction with its environment.
1
The inhibi-
tion of corrosion of metals is a subject of theoretical
research but, more importantly, is of practical interest
to multiple industries. The most common corrosion
prevention technique is, perhaps, the application of
paint or an organic coating on a metal substrate.
Ideally, organic coatings would provide long-lasting
corrosion protection. However, this property depends
on the coatings ability to protect an exposed metal
surface when defects appear during their service
lifetime. In recent years, the design and development
of alternative organic coatings with self-healing abili-
ties [i.e., shape memory materials and intrinsically
conductive polymers (CPs)] have been considered
useful materials in the protection of metals against
corrosion.
214
The interest in CPs stems from the possibility of
formulating CP-based smart coatings, which can
prevent metallic corrosion even in defect areas where
bare metal surface is exposed to the corrosive envi-
ronment. CPs may exist in different states (oxidation-
conductive state/reduction-nonconductive state) and
can easily interchange between them under appropri-
ate conditions. The CPs undergo redox processes and
thereby allow for the binding and expelling counter-
ions (dopants) in response to the variation of the metal
surface potential triggered by local electrochemical
reactions due to the corrosion. The dopants, which may
be inserted or expelled by the CP depending on the
local corrosive conditions, are often inhibitors prevent-
ing the local corrosion process upon release.
15,16
This is
one of the strategies that is suggested in exploiting the
advantages provided when a CP is used as a key
constituent of a corrosion-resistant coating.
P. P. Deshpande (&)
Department of Metallurgy and Materials Science, College of
Engineering, Shivajinagar, Pune 411005 MH, India
e-mail: pravinpd@hotmail.com
N. G. Jadhav, V. J. Gelling
Department of Coatings and Polymeric Materials, North
Dakota State University, 1735 NDSU Research Park Drive,
NDSU Dept #2760, P.O. Box 6050, Fargo, ND 58108-6050,
USA
N. G. Jadhav
e-mail: niteen.jadhav@my.ndsu.edu; n3.uict@gmail.com
V. J. Gelling
e-mail: v.j.gelling@gmail.com
D. Sazou
Department of Chemistry, Aristotle University of
Thessaloniki, 54 124 Thessaloniki, Greece
e-mail: sazou@chem.auth.gr
J. Coat. Technol. Res., 11 (4) 473494, 2014
DOI 10.1007/s11998-014-9586-7
473
The use of CPs for the corrosion protection of metals
has attracted great interest over the last 30 years.
DeBerry
2
has indicated the Polyaniline (PANI) induced
stabilization of the passive state for 400 series stainless
steels in sulfuric acid solutions since 1985. The key
feature of this process is that CPs are able tomaintainthe
surface potential of the substrate into the passive state
where a protective oxide lm is formed on the metal
substrates. This is due tothe fact that CPs-based coatings
are pinhole and defect tolerant in a manner similar to
that of the coatings based on the environmentally
hazardous hexavalent chromium. This is explained by
the fact that oxygen reduction within the CP layer
replenishes the CPcharge consumedby metal oxidation.
Along with the switching of the CP into the oxidation
state, the potential turns into the passive state of the
metal preventing the corrosion process.
Despite the extended work devoted to the anticorro-
sive properties of CPs there are still many issues to be
resolved for CP-based coatings to fulll physico-electro-
chemical and mechanical requirements of high-perfor-
mance anticorrosive coatings under widely varying
practical conditions. Limitations of CPs as anticorrosive
coatings include: (i) irreversible consumption of the
charge stored in the CP which is capable of oxidizing the
base metal and resulting in the formation of a passive
oxide layer, (ii) porous structure and poor barrier effect,
(iii) anion-exchange properties, (iv) poor adhesion to
the metal substrate. All the above-mentioned disadvan-
tages are especially magnied under severe corrosion
conditions as in the presence of chlorides, which may
reach the metal-substrate surface either due to the CP-
layer permeability or to its anion-exchange properties if
chlorides replace CPdoping anions. Then, chlorides may
induce extended localized corrosion and the stored
charge might be irreversibly consumed during the redox
reactions of the metal |metal oxide |CP system.
One of the efcient strategies to eliminate the above
disadvantages is to consider CP-based composite systems
usually comprising a CP in which different inorganic
llers suchas metal oxides havebeenencapsulated. These
CP-based composite materials combine the redox prop-
erties and hence the self-healing feature of CP with
qualities of inorganic materials. Thus, CP-based compos-
ites have shown better mechanical and physicochemical
properties improving the barrier effect, adhesion and
perhaps hydrophobicity. The more these properties are
improved the better the metal is protected against
corrosion. Furthermore, the design and development of
CP-based coating systems with commercial viability is
expected to be advanced by applying nanotechnology,
17
which has received substantial attention recently. Nano-
composite CP-based coatings seem to combine more
efciently the properties of CPs and organic polymers to
that of inorganic materials.
18
This paper reviews the
application of CP-basedcoatings for corrosion protection
of metals and alloys emphasized in recent advances.
Corrosion basics
Corrosion is mostly caused by an electrochemical
inhomogeneity in metal or its environment. When in
contact with an electrolyte, metals corrode when areas
of higher free energy or higher potential behave as
anodes and those of lower free energy or lower
potential behave as cathodes, thereby creating a
corrosion cell. Metal ions are formed at the anode
and dissolve into the electrolyte. The electrons pass
through the metal to the adjacent cathode areas where
they react with the environment. This ow of electrons
from the anode to cathode and the associated charge
transfer through the electrolyte from the cathode to
the anode constitute the corrosion current. The corro-
sion rate is, therefore, associated with the corrosion
current. The process of corrosion can be represented
by the following reactions
1,19
:
(1) Anodic reaction The electrochemical reaction at
the anode or metal dissolution can be written as
M M
n
ne:
The released electrons migrate to the cathode through
the metal producing corrosion current.
(2) Cathodic reaction The nature of the reaction at
the cathode (in which the electrons released in
anodic dissolution are consumed) depends upon
the nature of the environment. The most common
cathodic reactions that are encountered in corro-
sion are as follows:
(A) Oxygen reduction (Acid solution)
O
2
4H
4e 2H
2
O:
(B) Oxygen reduction (Neutral or basic solution)
O
2
H
2
O 2e 2 OH
:
(C) Hydrogen evolution
2H
2e H
2
:
(D) Metal ion reduction Metal ions present in solu-
tion may be reduced:
M
n
e M
n1
:
This can occur only if there is a high concentration of
M
n+
ions. In this reaction, the metal ion decreases its
valence state by accepting an electron.
474
(E) Metal deposition
Metal may be reduced from an ionic to a neutral
metallic state:
M
n
e M:
Hydrogen evolution is common since acidic media
are frequently encountered. Oxygen reduction is also
common since any aqueous solution in contact with air
is capable of promoting this reaction. Metal ion
reduction and metal deposition are less common
reactions. These partial reactions can be used to
understand most of the corrosion processes; for exam-
ple, corrosion of plain carbon steel in water (Fig. 1).
The corrosion occurs in two steps. In the rst stage,
regions covered by a water droplet are precluded from
supply of oxygen and become anodic compared to the
other areas that are freely exposed to air. Thus, plain
carbon steel, in contact with any electrolyte, low in
dissolved oxygen will be anodic with respect to plain
carbon steel, in contact with electrolyte, rich in
dissolved oxygen. A principal reason for this is that
in an area with water rich in oxygen the following
reaction will take place:
O
2
2H
2
O 4e
4 OH
:
This is a cathodic reaction in the sense that it absorbs
electrons. There will be a greater amount of oxygen
available near the edge of the water droplet and this
area will become cathodic with hydroxyl ions that are
formed. The electrons will be supplied from another
part of metal where there is less oxygen and so such
areas act as anodes. At the anodic area under the
center of the water droplet electrons will be generated
by the reaction:
Fe Fe
2
2e
:
The Fe
2+
cations will move through the electrolyte
toward the cathode and the (OH)
anions will tend to

move toward the anode. Migration of the oxidative
product (Fe
2+
) from the anode and the reduction
product (OH
) from the cathode occurs until they

combine to form ferrous hydroxide.
2Fe 2H
2
O O
2
2Fe
2
4 OH
2Fe OH
2
:
Ferrous hydroxide (Fe(OH)
2
) precipitates, due to its
insolubility, from the oxygenated aqueous solution and
settles as deposit near the cathode area. In the second
stage, at the outer surface of the Fe(OH)
2
layer, access
to dissolved oxygen converts the ferrous hydroxide to
insoluble and the hydrous ferric hydroxide as follows:
2Fe OH
2
1/2 O
2
2H
2
O 2Fe OH
3
:
Reddish brown ferric hydroxide, Fe(OH)
3
, is known
normally as red rust which forms in the initial stages of
corrosion and gradually changes to ferric oxy-hydrox-
ide, FeOOH. Different forms of ferric oxy-hydroxides
are also termed as red rust. When Fe(OH)
3
is dehy-
drated it becomes ferric oxide:
2Fe OH
3
Fe
2
O
3
3H
2
O:
In the case of limited oxygen supply, this reaction
results in the formation of black magnetite (Fe
3
O
4
).
Once a rust deposit has formed on the steel surface, the
area under the porous deposit will become oxygen
decient and, hence, anodic compared to the bare
steel. In addition, the rust layers are not protective
because they are permeable to air and water. There-
fore, the dissolution of steel can continue, unobserved,
below the layer of rust.
Thermodynamics of corrosion
Metals have a propensity to revert to their lower
energy forms (metal oxides). This thermodynamic
tendency is responsible for corrosion of metals. The
extent to which a metal corrodes depends not only
upon its electrode potential but also upon pH of the
aqueous solution. The combined effect of the potential
and pH of the aqueous medium on the products of
corrosion has been well summarized in Pourbaix
diagrams.
1
Figure 2 shows a schematic Pourbaix dia-
gram for iron.
As shown in the Pourbaix diagram (Fig. 2), iron and,
therefore, steel (say at point A) can be protected from
aqueous corrosion by
(1) Use of inhibitors The electrolyte can be made
more alkaline by increasing its pH by adding
inhibitors (from point A to 1),
(2) Anodic protection Changing the potential of
metal in positive direction by applying external
voltage (from point A to 2),
(3) Cathodic protection By applying potential in
negative direction, for instance using zinc coating
on steel substrate (from point A to 3).
Corrosion current
Air
Water droplet
OH
OH
OH
OH
Fe
++
Fe
++
Fe
++
Rust Rust
e e
Anode
Steel
Cathode Cathode
Fig. 1: Electrochemical corrosion showing rusting of plain
carbon steel
475
In addition to essentially pure zinc, as in the
conventional electrodeposition or hot-dip galvanizing,
the zinc-based coatings may consist of different zinc-
based alloys with the aim of improving subsequent
paintability while conserving the capacity to impart
galvanic protection and, thereby, providing corrosion
resistance. These alloys include galfan (Zn with
approximately 5% Al) and galvanneal (Zn with
approximately 10% Fe). However, the corrosion rate
of coated zinc increases rapidly in humid air. Various
surface treatments have been developed to improve its
corrosion resistance such as chromate conversion
coating, phosphate conversion coating and organic
painting, etc. For example, chromate conversion coat-
ing is widely used because of its superior corrosion
resistance, good paint adhesion, low cost, and a simple
application process. Chromate conversion coating is
generally performed by immersing the zinc-coated
specimens in a chromic acid solution, which leads to
the formation of a passive layer containing zinc oxides
with mixed trivalent and hexavalent chromium oxides.
Unfortunately, the hexavalent chromium species pres-
ent in the chromate solution and layer are toxic and
carcinogenic.
Coatings basics
While the variety in pretreatments and coating forma-
tion is nearly limitless, examples of common tech-
niques employed in corrosion control for steel
substrates by paint coatings are detailed below.
1921
Zinc-rich coatings
Zinc-rich coatings contain zinc particles and, hence
protect the steel by a sacricial mechanism or by
cathodic protection. To have sufcient electrical con-
tact with the steel, the coating must contain 8595% w/
w of zinc. In addition, the resulting zinc corrosion
products, which preferentially form upon exposure to
the environment, tend to block the pores in the coating
and improve the barrier properties of the coating.
Therefore, there are two modes of corrosion protection
via this technique: sacricial followed by increased
barrier properties as the zinc is consumed.
Impervious or barrier coatings
Impermeable barrier coatings tend to reduce both
water and oxygen permeation to a sufcient extent so
that corrosion is precluded. The prevention of oxygen
access to the metal stops the cathode reaction and
current transfer between the anodic and cathodic areas
is prevented due to ionic transfer resistance.
Inhibitive coatings
Inhibitive coatings, generally used as primers, are
obtained by adding pigments that release corrosion-
inhibiting substances. The pigments react with the
moisture absorbed in the coating and passivate the
steel. However, all effective inhibitors such as stron-
tium chromates have harmful effects on the environ-
ment. As the release of inhibitors is based on leaching,
coatings need to be highly pigmented in order to insure
sufcient leaching. Toxic inhibitors, therefore, are
constantly released into the environment even when
they are not needed.
To sum up, paint coatings are essential in one way or
another to protect steel products from corrosion and
there is a need to replace conventional paint contents
by environmental friendly and nontoxic formulations.
Recently, the use of conducting polymers has shown
this promise.
4,6,7,9,10
The environmental friendly nature
of conducting polymers along with their stability and
redox properties makes them promising coating mate-
rials for the corrosion protection of metal alloys.
Conducting polymers in coatings
Various CPs are available in commercial forms. These
include PANI, polypyrrole (PPy), polythiophene (PTh)
and a few more, such as polycarbazole.
2224
Chemical
or electrochemical oxidation methods are used for the
synthesis of CPs.
2529
Since the 1980s, CPs have found
their applications in the eld of corrosion protection
for metals and metal alloys. Their ease of synthesis
both via chemical and electrochemical methods cou-
pled with electrical conductivity makes them even
more attractive as anticorrosive materials.
7,8,12
Several mechanisms of interactionare possible for the
performance of CPs on a variety of substrates.
3,10,15,30
0 7
pH
P
o
t
e
n
t
i
a
l
,

V
Immunity
3
1
0
1
2
Corrosion
Corrosion
Passivity
1
2
A
14
Fig. 2: Schematic Pourbaix diagram for iron or steel
476
These mechanisms mainly depend on the type of
substrate used, use of specic conducting polymer, its
chemical composition, physical properties, amount and
type of dopant used, amount of CP used, and its relative
proportion with other active ingredients in the coating.
Surface preparation also has a large effect on the
functional properties of the CPs. This becomes more
important when there are issues related to adhesion and
growth of possible corrosion products underneath the
coating. The exposure environment and pHof local area
also have a strong effect on the performance of these
polymers as coatings. For electropolymerization, sur-
face cleaning is very important. Poor surface prepara-
tion compromises the consistency of the deposited layer
resulting in surface defects giving rise to poor corrosion
protection. A CP can be used as a primer alone or as a
primer coating with conventional topcoat or it can be
blended with conventional polymer coatings or can be
used as anticorrosive additive in the coating formula-
tion. All these approaches are explored in the following
discussion under the heading of various conducting
polymers.
Polyaniline
PANI can be employed for corrosion protection of
various metallic substrates. PANI and its substituted
derivatives are widely used in anticorrosion coatings
because they are easily synthesized chemically or
electrochemically, have an increased environmental
stability and different redox states allowing regulation
of their properties. Emeraldine salt [ES, a protonated
form of emeraldine base (EB)] is electronically con-
ductive and widely accepted as responsible for the
active corrosion control of the metal substrate. Depend-
ing on the synthetic method and isolation procedure,
PANI may contain localized/delocalized polarons and
bipolarons in various proportions. The well-dened
insulating forms of PANI are the leucoemeraldine base
(LB), EB, and pernigraniline base (PB) differentiated
from one another by the number of benzenoid (x) and
quinoid (y) rings. The ES in which x = y is the result of
the oxidation of LB or the protonation of EB.
28,31,32
Protonation and doping by anions are possible by using
various acids such as sulfuric, phosphoric, phosphonic,
hydrochloric, perchloric, oxalic, and sulfonic acid.
Electrodeposition of PANI and its substituted deriva-
tives on iron or mild steel was rst carried out from
oxalic acid solutions
5,3338
and other organic acids
39
since the main problem arising when using active metals
for the electrochemical polymerization of aniline in acid
solutions is the simultaneous anodic dissolution of the
support metal. Passivation of the metal substrate is
required before the growth of the PANI. It was shown
that the choice of the proper electrolyte, pH, and
electrochemical technique for the growth of a protective
passive layer is crucial. Potentiostatic electropolymer-
ization of aniline carried out in phosphoric acid
solutions (pH 4.5) in the presence of metalinic acid
leads to PANI lms on mild steel that shift the open
circuit potential (OCP) of the metal substrate to
positive values for relatively longer periods than the
PANI formed from oxalic or sulfuric acid solutions.
4042
Homogeneous strongly adherent PANI lms on mild
steel were also obtained under galvanostatic conditions
at certain applied current values from 2 M LiClO
4
solutions
43
as well as from acetonitrileLiClO
4
solu-
tions.
44
Electropolymerization on various types of
stainless steel and other metal substrates where passiv-
ation precedes easily the polymerization process was
readily performed from different media of both organic
and inorganic acids resulting in adherent PANI coatings
with sufcient protective properties in corrosive med-
ia.
2,4552
In practice, PANIcan be used for the protection of
concrete steel bar reinforcement. Saravanan et al.
53
have studied epoxy primer containing PANI for steel
bars. In this study, it was found that the base metal
repassivates due to the presence of PANI in the
coating. Epoxy PANI coating showed a better perfor-
mance against chloride attack, which is one of the
major causes of steel bar corrosion in concrete. This
was determined from accelerated corrosion studies
such as anodic polarization, cathodic disbondment test,
and salt spray test. Chemical resistance studies of these
coatings showed better alkali resistance, giving much
more protection against alkaline environment of con-
crete. Time to cracking study of coated and uncoated
bars in concrete was performed. Maximum current was
reached within 4 days in case of uncoated bars whereas
it took nearly about 50 days for ones coated with epoxy
PANI primer. Authors claim that this extra protection
was provided by repassivation induced by PANI.
Different dopants can be used in order to improve
conductivity and corrosion performance of conducting
polymers. Poly(methylmethacrylate-co-acrylic acid)-
doped PANI lms were used on an aluminum alloy
AA3104-H19 by immersion of the pretreated surfaces
into a saturated ethyl acetate solution of the polymer.
54
In this study, it was found that even though these
primers were porous, nonuniform and allowed electro-
lyte permeation, they were found to provide better
corrosion performance when compared with a com-
mercial epoxy resin (ICI 640C692). The type of dopant
and topcoat used has a strong inuence on the
corrosion protection.
55
The type of media used for
the study also has an inuence on the corrosion
performance properties of the nal lm. Benzoate-
doped PANI-containing vinyl coatings were able to
protect steel in neutral media better than in acid
media.
56
A passivating layer of iron oxide stabilized by
PANI was suggested to provide improved protection.
Kalendova et al.
57
studied the inuence of inorganic
pigments like zinc phosphate, calcium borate, and zinc
powder along with PANI for corrosion protection of
metals. They found a synergistic effect that was more
efcient in protecting metal than just using a single
defense mechanism. Loading of PANI in nano partic-
ulate form at 2.5% w/w in water dispersible alkyds
477
resulted in increased corrosion performance of these
water-based alkyd paints for metal substrates.
58
Incor-
poration of PANI in chlorinated rubber (CR) binder
system in 1.5% w/w resulted in increased corrosion
protection as compared to the same amount of zinc
phosphate in marine coatings.
59
PANI powder synthe-
sized chemically and used as pigment within a concen-
tration range 1015% was found to increase the
corrosion resistance of mild steel in 3.5% NaCl by
1015 times.
60
Pigments of PANI-H
3
PO
4
and
Mg
3
(Si
4
O
10
)(OH)
2
in PVC added in metal zinc coat-
ings were proven to slow down the corrosion of steel
and improve the mechanical properties of the coat-
ing.
61
A duplex coating constituted by a cerium
conversion coating as adherence promoter and PANI
used on AA6063 aluminum alloy were shown to
exhibit efcient protective ability.
62
The presence of
the cerium conversion coating increasedthe adherence
of PANI. It is suggested that the corrosion protection
mechanism can be understood by considering the
barrier effect of the cerium coating and the anodic
protection caused by the PANI.
Incorporation of CPs in a conventional polymer
matrix can lead to a useful increase in properties like
conductivity and corrosion performance. Though this
increase may not always be signicant, incorporation of
clay in a polymer matrix enhances the barrier, thermal,
and anticorrosive properties of the coating. Due to the
platelet nature of clay the path of corrosion ion, water,
and oxygen ion ingress lengthens, resulting in better
corrosion resistance. Both PANI and clay have been
added to the polymer matrix in order to have improved
properties. PANI and hydrophilic as well as organo-
philic montmorillonite (MMT) displayed better corro-
sion performance as compared to the pure PANI-
containing coatings. A nanocomposite of PANI and
clinoptilolite (a natural zeolite mineral) was also
prepared.
63
Clinoptilolite was used in order to improve
the barrier properties of the nanocomposite. The
clinoptilolite proportion was varied from 1 to 5% w/
w in the nanocomposite. It was found that in the acidic
media, the corrosion current for 3% w/w of clinoptil-
olite in the nanocomposite was lower than that of 1 and
5% w/w of clinoptilolite in the nanocomposite. This
study determined that optimum concentration of zeo-
lite is necessary for the required performance of the
composite.
The effect of nanostructured particles on the anti-
corrosion properties of PANI/alkyd coatings was
shown by Riaz et al.
64
in comparison with the anticor-
rosion properties of poly(1-naphthylamine) (PNA)/
alkyd coatings. Comparisons between nanosized PANI
and PNA dispersed soya oil-based alkyd composites
applied on mild steel revealed that the PNA/alkyd
coatings have better anticorrosion properties than the
PANI/alkyd coatings. A coating with different amounts
of PANI and PNA was investigated. The higher
protective ability of PNA/alkyd coatings was assigned
to the smaller particle size of PNA as compared with
that of PANI. The smaller particle size of PNA
enhanced the crosslinking of the PNA with the alkyd
matrix providing a better barrier effect. A far superior
corrosion resistance performance compared to that of
single PANI/alkyd was also found in the case of the
PANI/ferrite nanocomposite applied on steel.
65
Hybrid nanocomposite coatings containing dodecyl
benzene sulfonic acid-doped PANI and ZnO as nano-
particles dispersed in poly(vinyl acetate) (PVAc)
appeared to also exhibit an improved barrier effect as
compared to the single-component coating.
66
Corro-
sion studies of steel plates dip-coated with these
formulations showed excellent corrosion resistance in
saline water for long periods. The results were
explained by considering an improvement in the three
simultaneously operating mechanisms during protec-
tion: (i) barrier effect, (ii) formation of p-n junction
that prevents easy charge transport, and (iii) redox
behavior of PANI which by storing a high amount of
charge induces a self-healing effect that prevents the
evolution of active dissolution in possible surface
defects by the passive oxide formation.
PANI has also been used for the corrosion protec-
tion of substrates other than steel and aluminum. A
PANI-inorganic pigment (titanium dioxide) composite
was found to perform better than just PANI alone in
acrylic resin binder on magnesium substrate.
67
PANI
was incorporated in epoxy powder coating formulation
with 1, 3, and 5% w/w. Powder coatings are highly
regarded due to their zero volatile organic content
(VOC). It was found that after curing the PANI leads
to a higher crosslink density and even after a scratch
was formed it imparted self-healing behavior to the
coatings.
68
Glass akes containing coatings are tradi-
tionally used for prevention of corrosion in marine
environments, but there is a problem of coating defects
and pinholes. The performance of these kinds of
coatings was modied by incorporation of PANI into
these paints containing glass akes.
69
In this case,
passivation due to the PANI was suggested as the
cause of improved corrosion protection. In electro-
chemical impedance measurements it was found that
resistance of PANI containing coatings remained
about at 10
8
10
9
X cm
2
and in the case of coatings
containing only glass akes it decreased to 105 X cm
2
.
In another study, incorporation of 0.120 parts of
PANI was performed in styrene butyl acrylate copoly-
mer and the coating was applied on mild steel
substrate. This study determined that the lower percent
of PANI displayed better corrosion resistance as
compared with the higher percent of PANI in the
composition on mild steel.
70
There are several problems with the direct applica-
tion of coatings of conducting polymers. Their appli-
cation on active metals becomes difcult owing to the
fact that conducting polymers are insoluble and non-
fusible. Several approaches have been attempted in
order to overcome solubility problems including chem-
ical modications and attachment of well-designed
functional groups, rendering solubility in a given
medium. Dopant anions have been added in order to
478
increase overall conductivity. Functionalization to
render medium solubility has been attempted by
several researchers in last decade. Surface functional-
ization also leads to the alteration of several properties
besides solubility. Addition of sulfonate groups to the
polymer backbone of PANI altered ion exchange
properties of the polymer, giving rise to a self-doping
effect.
71,72
An alkyl and alkoxy modication to con-
ducting polymer backbone resulted in an improved
solubility in commonly used solvents. Thus, several
forms of PANI and their modications can be
employed for corrosion protection of metals and their
alloys.
7,73
Recently, nanocasting was applied to prepared
PANI-based advanced anticorrosion coatings from a
natural Xanthosoma Sagittifolium with biomimetic
superhydrophobic structures (SH-PANI).
74
These
coatings exhibit water-repelling properties with a water
angle equal to 156 and good adhesion to the cold-
rolled steel (CRS). Evaluation of the anticorrosion
performance of the SH-PANI-coated steel in 3.5%
NaCl showed a better protective ability for the SH-
PANI in comparison with the corresponding coating
with a relatively at surface. The improved anticorro-
sion property of the SH-PANI coating was ascribed to
the synergistic effect of the hydrophobicity that repels
the moisture and aggressive ions and the PANI ability
to passivate the steel via the formation of an oxide lm.
Polypyrrole
In the recent past, several reports on the corrosion
protection of metals and their alloys by PPy have been
published. PPy has been added to epoxy polyamide
coatings in 1% w/w. An improvement in corrosion
protection was found as compared to the control
sample, but higher proportions did not improve the
performance. It was observed that the efcacy of CPs
depends on the method of application and the condi-
tions under which the experiments were performed. In
this study, authors claim that the conducting polymers
have a similar electrochemical mechanism of protec-
tion as that of hexavalent chromium.
75
CPs can be synthesized with different anions on
their backbone. Upon oxidation of CPs, dopant anion
is introduced in the conjugated polymer. This dopant
anion is released when this polymer undergoes reduc-
tion. These anions can be released in the coatings on
demand functioning as smart coatings. Dopant ions
used in the synthesis of PPy have a strong inuence on
the properties of the resultant PPy. Kowalski et al.
76
prepared bi-layered PPy coatings on carbon steel. In
this system, the inner layer was doped with molybdo-
phosphate and phosphate ions whereas the outer layer
was doped with naphthalenedisulfonate (NDS) ions.
Molybdophosphate ions incorporated in the inner layer
stabilize the passive oxide lm on the steel and the
outer layer doped by the large size organic ions of NDS
restricts decomposition and release of molybdophos-
phate ions in the inner layer. This resulted in overall
improvement in corrosion protection.
Electrochemical synthesis of CPs is an often-used
technique for the deposition of CPs on the required
substrates and their synthesis. Bereket et al.
77
studied
the corrosion performance of electrochemically synthe-
sized PPy as well as a topcoat of poly(5-amino-1-
naphthol) on PPy lms by cyclic voltammetry technique.
It was determined that as more layers of this combina-
tion were deposited, an improvement in the corrosion
protection performance was achieved. In another study,
Su and Iroh
78
successively electrodeposited PPy and
poly(N-methylpyrrole) coatings on steel substrates from
aqueous oxalate solutions to reveal the mechanism of
electrodeposition of PPy on metal substrate. It was
determined that a FeC
2
O
4
2H
2
O coating was rst
deposited on the steel substrate resulting in its passiv-
ation. But this formed FeC
2
O
4
2H
2
O, which was
decomposed again when the electropolymerization
potential of pyrrole was reached. Many of the important
properties of the resultant coating, such as adhesion,
were found to depend on local pH and applied current
densities. In this study, it was further demonstrated that
the electropolymerized PPy coating provided better
corrosion resistance as compared to the electropoly-
merized poly(N-methylpyrrole) coatings.
Several researchers have attempted to synthesize
electropolymerized PPy on different substrates other
than steel and aluminum. Herrasti et al.
79
electrode-
posited PPy on the surface of copper. The deposited
layer had low porosity and homogenous surface
characteristics. This was the outcome of constant
growth rate of these conducting polymer lms. These
PPy deposits, which were formed on copper showed
excellent corrosion resistance in 3% sodium chloride
solution. They also showed that a higher monomer
concentration of about 0.3 M should be used in order
to have good barrier layer characteristics and good
redox properties. Jiang et al. electrodeposited yellow-
black colored PPy coatings on AZ91 magnesium alloys
substrates in alkaline solutions. They found that the
different pretreatments have an effect on the charac-
teristics of potentiodynamic curves thereby changing
the resultant growth rate.
80
Tuken et al. attempted
electropolymerization of PPy on the surface of brass
and copper. They determined that these PPy lms have
better adhesion on the oxidized copper, resulting in
better corrosion protection as compared to brass. They
proposed a mechanism of protection by barrier effects
exhibited by these coatings.
81
In another attempt, Attarzadeh et al. added saccha-
rin as a third component in order to yield coatings with
improved and modied properties. They incorporated
saccharin in the electrodeposition bath at concentra-
tions of 0.25, 0.5, and 2.5 g/L for PPy coating of steel.
PPy coatings obtained with an addition of 0.5 g/L
saccharin to the electropolymerization bath showed
greater corrosion resistance and a more compact and
smoother surface. Further they proposed that this
compactness and smoothness might be the reason for
479
an improved corrosion performance of the resultant
coating.
82
Hosseini et al. studied PPy, MMT, and epoxy
nanocomposite materials for their corrosion perfor-
mance on aluminum substrate. It was found that
epoxy-PPy-MMT nanocomposite displayed better cor-
rosion performance as compared to epoxy, epoxy-PPy,
and epoxy-MMT coatings. So the properties of differ-
ent materials can be combined together in order to
yield a better performance.
83
In another study, Tall-
man et al. synthesized a nanocomposite by pyrrole
polymerization on alumina nanoparticles in the pre-
sence of dihydroxybenzene. They used this material in
the coating as ller in less than 2% proportion. It was
found that the presence of dihydroxybenzene im-
proved the adhesion of the coatings to the aluminum
alloy surface. This study signicantly explains the
changes induced in the geometry and volume fraction
of voids in the coatings with the help of electrochem-
ical impedance spectroscopy (EIS). The voids have a
direct inuence on the aging and penetration of
corrosive solution into the coating.
84
Polythiophene
There have been few reports published on PTh for the
corrosion protection of metal substrates. It is possible
to synthesize a range of substituted polymers of PTh.
Some of the derivatives of PTh perform very well as
compared to other conducting polymer derivatives.
This ultimately depends upon the nature of the
environment that these conducting polymers will be
exposed to. With the proper application of voltage,
PTh and its derivatives can be generated on other
conducting polymer substrates like PPy. The combina-
tion of these two has resulted in better corrosion
performance.
Kousik et al. attempted to generate PTh coatings on
a mild steel surface using acetonitrile as a medium.
From AC impedance studies, it was determined that
PTh-coated mild steel was protected by a passivation
mechanism caused by the redox activity of the PTh.
Water uptake and delaminating area studies also
conrmed protective action of electropolymerized
PTh on the mild steel surface.
85
Ocampo et al. have
compared several anticorrosive marine paints with the
addition of a PTh derivative. It was found that the
addition of a low concentration (0.2% w/w) of poly(3-
decylthiophene-2,5-diyl) increased the corrosion resis-
tance performance of epoxy-based paints.
86
Rammelt et al. investigated the role of special
surface treatment on the substrate. After the treatment
with 2(3-thienyl) ethylphosphono acids, homogeneous
and very adherent polymethylthiophene lms were
formed on the surface of mild steel. These lms of
polymethylthiophene were ultrathin (thickness was ca.
1 lm) and highly ordered. So they exhibited better
protection with material savings by utilizing ultrathin
lms. These lms were found to effectively separate
the electrochemical processes of oxygen reduction and
iron dissolution in the surface region.
87
This rationale
of adhesion promoter incorporation can be very easily
used for the preparation of different homogenous
coatings with improved corrosion protection.
Corrosion protection mechanisms of conducting
polymers
The mechanisms of corrosion protection due to con-
ducting polymers are not understood completely.
There are four possible proposed hypothe-
ses
2,3,6,9,10,15,17,48,88,89
:
(1) Anodic protection mechanism: This mechanism
suggests that CP coatings may lead to the forma-
tion of protective layers of metal oxides on the
metal surface thus preventing corrosion.
2,3,48,89
(2) Controlled inhibitor release mechanism: Accord-
ing to this mechanism, the oxidized and hence
doped CP-based coating deposited on a base
metal substrate may release the anion dopant
upon reduction, which is driven by a defect on the
coating from coupling to the base metal.
15
In the
case of doped PANI, the anions are released not
only through reduction mechanism but also due
to a simple elimination of acid-dopant if it is
soluble in water.
(3) It is believed that when a metal comes into
contact with a doped semiconductor or an elec-
tronically conducting polymer, an electric eld is
generated that would limit the ow of electrons
from the metal to an oxidizing species, thus
preventing or reducing corrosion rate.
25
(4) Conducting polymer coatings form a dense, adher-
ent, low porosity lm and maintain a basic envi-
ronment on a metal surface thus restricting access
of oxidants and preventing the oxidation of the
metal surface.
90,91
The less porous the CP layer the
better is the barrier effect and the lower is the
transport rate of O
2
and H
2
O into the polymer. By
increasing the compactness and adherence to the
substrate, the reaction site of the O
2
reduction
moves from the M|CP-coating interface to the CP-
coating|solution interface.
92
The shift of the oxy-
gen-reduction site on the polymer surface results
in the decrease of the reduction products (i.e.,
OH
) across the M|CP-coating interface, prevent-

ing disbondment and delamination of the coat-
ing.
15,93
On the other hand, O
2
reduction is
involved in the local reoxidation of the CP and
constant active role of the CP coating in case that
local pinholes or small-size defects are formed.
Thus, increasing the barrier effect by processes
that inactivate CPs should be avoided. As far as
the CP is in its conductive form the OCP of the
metal |CP-coating| solution system is in the passive
state. The site and the kinetics of the oxygen
480
reduction are important for the long-term protec-
tive properties of the coating. It is generally
observed that dehydration of CP electrodeposited
lms on metals from aqueous medium improves
the barrier effect.
Recent experimental evidence shows that protection
of the metallic substrate provided by aniline oligomers
(AO) is mainly connected with the change of the
oxygen-reduction kinetics from a four- to a two-
electron path on the AO-covered mild steel. As a
consequence, the formed hydrogen peroxide may
oxidize during corrosion Fe
2+
to Fe
3+
resulting in the
formation of Fe(OH)
3
in the AO pores.
94
The forma-
tion of Fe(OH)
3
reduces the corrosion rate and may
explain the self-healing ability of metal coatings
consisting of AO and perhaps of thin CP lms. Thin
PANI lms formed often electrochemically are con-
sidered to be more likely AO than real PANI.
28
Several researchers show the protective efciency of
AO in chloride-containing solutions either deposited
alone on low-carbon steel
95
or incorporated into epoxy
thermosets,
96
polyamide,
97
polyimide,
98100
and poly-
urethane,
101
deposited on CRS. The AO deposited on
iron surfaces modies the AO|iron oxide interface
leading to a band bending in the oxide and a decrease
in the substrate work function.
102
Among the above mechanisms, the rst two are
considered the most important ones by which corrosion
inhibition by CPs can be rationalized in terms of the
active role of CP layer. The other two mechanisms
should contribute simultaneously to a remarkable
degree in cases where either the anodic protection or
the controlled inhibitor release mechanism determined
the corrosion inhibition for a specic metal |CP-
coating| solution system. The anodic protection mech-
anism dominates discussions related to the way by
which CPs prevent general corrosion (mostly in halide-
free solutions) in most of the metal substrates
and alloys. In particular, this mechanism has been
explained in more detail for the PANI-based coatings
as it is analyzed in Anodic protection mechanism:
thermodynamics of passivation and the role of PANI
section. The controlled inhibitor release mechanism
has been suggested in cases where CP-based coatings
prevent localized corrosion in chloride-containing
solutions as it is described in the Controlled inhibitor
release mechanism section.
Anodic protection mechanism: thermodynamics of
passivation and the role of PANI
According to the Pourbaix diagram as shown schemat-
ically in Fig. 1, passivation of steel is possible when its
surface potential and the pH of an aqueous medium
are sufciently high.
1
PANI coating due to its redox
nature could create such a passivation condition at the
paintsteel interface. The paint potential shifts the
steel surface potential toward the noble direction. The
hydroxide ions, which either penetrate through the
paint coating from the aqueous medium or are
liberated by anion exchange would raise the pH at
the interface.
Schauer et al.
103
proposed a passivation model using
a paint system containing epoxy as a topcoat and
conducting PANI as a primer. Lee and coworkers
104
explained excellent corrosion protection properties of
conducting PANI based on its redox properties and
passivation. Sathiyanarayanan et al. argued that passiv-
ation due to iron oxide was responsible for corrosion
protection of steel in basic medium and passivation of
pinholes or defects occurred due to ESLeucoemeral-
dine salt transformation in acidic medium. Passivation
model described in this work is shown in Fig. 3.
105
In another investigation, Sathiyanarayanan et al.
observed that coatings containing 1% and 3% phos-
phate-doped PANI and 3% chloride-doped PANI
were highly corrosion resistant. In this work, the
higher corrosion protection ability of phosphate-doped
PANI was assigned to the redox property of PANI
along with the formation of iron polyaniline complex
and secondary layer of iron phosphate on steel.
106
Controlled inhibitor release mechanism
Doping of CPs can be employed in different ways to
control the electrolytic environment adjacent to the
metal surface when a scratch is formed. When a scratch
exists on the CP-coated metal, there is a galvanic
coupling between the metal and the CP (Fig. 4). The
Steel
Electrons
Electrons
Fe
2+
Fe
2
O
3
OH
,

O
2
ES PANI
(Acid medium)
O
2
+ 2H
2
O
PANI-based paint
40H
-
(Neutral medium)
O
2
+ 2H
2
O 40H
-
(Neutral medium)
PANI based paint
LS PANI
ES PANI
(Acid medium)
LS PANI
Fig. 3: Passivation of steel by conducting PANI-based
paint coating
481
cathodic reaction involves the reduction of the CP
associated with the release of the doping anions
whereas the anodic reaction involves the oxidation of
the metal. On the other hand, the O
2
reduction occurs
simultaneously on both the CP coating and metal
surfaces leading to the CP reoxidation and the
production of OH
, respectively. A self-healing pro-

cess might be initiated depending on the nature of the
metal and doping anions. In several metals (i.e., steels,
aluminum, copper), oxide formation is initiated (ano-
dic protection mechanism) or the doping anions act as
inhibitors (i.e., phosphonic acid derivatives, molyb-
dates). Several investigations have shown this effect in
the case of PANI
90,107
and PPy layers.
93,108
Furthermore, when the anion is released during the
reduction of CP, an anion-exchange process may occur
if the electrolyte contains chlorides and the CP is
doped by small-size anions. By this process, chlorides
may reach the metal surface and induce pitting
corrosion. The transport of chlorides into the CP can
be slowed down by using bulky doping anions. In this
way the transport of H
2
O into the CP should also be
eliminated. Using the electrochemical quartz crystal
microbalance (EQCM) to study the transport of ion
through the PPy layer, Weidlich et al.
109
found that
during the oxidation-reduction transition of the PPy,
the insertion or the expulsion of the doping ions
depends on the size, mobility, and valence of anions
and cations involved in redox processes. Indeed, it was
shown that Naon-PANI composite lms deposited by
a two-step process on stainless-steel 304 completely
inhibit the transport of chlorides through the lm in
comparison with the simple electrodeposited PANI
lms.
110112
It seems that the sulfonate groups in
Naon act as inner doping anions excluding an anion-
exchange process between the composite lm and the
chloride-containing solution.
Other properties related to doping ions are the thick-
ness, porosity, delamination, and hydrophobicity of the
CP layer. Thus, while optimizing the inhibitor release
process and the use of CPs as intelligent coatings a
number of effects might betakenintoaccount for effective
corrosion protection. For instance, it was observed that
the electrochemical reduction of PPy doped with various
anions does not involve anion expulsion exclusively but
cation incorporation is also possible. This may occur
especially whenlargedefects exist inthe coating andsmall
cations are present in the electrolyte. Using Scanning
Kelvin Probe (SKP) microscopy for the study of articial
defects it was shown that delamination of the PPy is
facilitated in the presence of small cations in the electro-
lyte since cation insertion becomes possible during the
reduction of PPy.
113
Cation injection and hence delami-
nation becomes much slower when large cations such as
tetrabutylammonium cations are present during the
electrochemical reduction. It was suggested that incorpo-
rated cations neutralized some negative charge in the
polymer, which will be immobilized. Then, cation trans-
port within the polymer occurs through hopping resulting
in the reduction of the PPy and hence increasing the
mobility of cations. A similar mechanism was found for
PANI-basedcomposite coatings andit is postulatedthat it
is of a general validity for coatings where CP functions as
an active pigment.
10
These ndings suggest that CP-based
coatings with an extended percolation network will fail to
provideprotectionwhenrelativelylargedefects exist since
a fast breakdown of the whole coating is possible by rapid
reduction of the CP induced by cation transport. To
optimizethecontrolledreleasemechanism, acompromise
is needed to the extension of the CP percolation network
and the amount of the CP that should insure a sufcient
electric conduct with the metal substrate at the defect site.
According to the above brief survey regarding the
controlled inhibitor release mechanism, the main
suggested strategies aiming to take advantage of
doping anions or to eliminate their unfavorable effects
use: (i) anodic or cathodic inhibitor do-
pants,
16,90,93,107,108,114
(ii) dopants controlling the anio-
nic-exchange property of the coating,
110112,115
(iii)
dopants that favor the coating hydrophobicity.
116,117
For example, a better barrier effect was found when a
more hydrophobic surface was achieved in the pre-
sence of diisopropylsalicylates than salicylates for the
PPy electrodeposition on steel.
118
Recent developments
Several strategies have been followed to increase the
anticorrosion performance of CPs. For instance, the
Cl
O
2
Metal-dopant (MA
n
) complex
A
PANI
Metal oxide
M
n+
ES EM
ne
EM ES
PANI
Metal oxide
M
n+
M
n+
Fig. 4: Controlled inhibitor release mechanism for a metal,
M coated by a CP layer such as PANI doped with an ion, A
2
,
which acts as a corrosion inhibitor
482
use of CPs in epoxy or acrylic blends as well as an
appropriate pretreatment of the substrate metal sur-
face before CPs deposition is considered necessary in
most cases and especially in chloride-containing solu-
tions in order to prevent localized corrosion of the
metal substrate. Furthermore, other specic strategies
have been used depending on the metal and the
corrosive environment, such as (i) copolymerization,
(ii) use of multilayers of CPs, (iii) various dopants, (iv)
nanostructured CPs, (v) composites and nanocompos-
ites of CPs.
Copolymers of CPs
Copolymers of CPs have been attempted for the
corrosion protection of metals and their alloys. Struc-
tural modication of the CP backbone by copolymer-
ization inuences various properties of the polymer
such as conductivity, porosity, adherence to the
substrate and stability. In particular, in the case of
PPy the water uptaking property is one of the main
drawbacks in the use of PPy as protective coating.
Therefore, the anticorrosion performance of several
PPy-based copolymers was investigated in corrosive
media. Poly(N-methyl pyrrole) and its copolymer with
pyrrole showed improved protective properties for
mild steel protection.
119
A series of poly(pyrrole-co-N-
methyl pyrrole) copolymers containing different ratios
of monomers electrodeposited on Cu showed an
optimum protective performance in 3.5% NaCl for
8:2 ratio of pyrrole:N-methyl pyrrole monomers.
120
The improved anticorrosion efciency of this coating
was attributed to the highest interaction between the
copolymer and the Cu substrate. This was supported by
theoretical calculations indicating that for the 8:2 ratio
the copolymer has the most linear structure and hence
the best interaction with the Cu. Interacting with the
Cu surface, the oxidizing form of the copolymer acts as
electron donor.
In a different approach, pyrrole was copolymerized
with substituted anilines. For instance, ter-polymer
poly(pyrrole-co-o-anisidine-co-toluidine) was electro-
chemically deposited on the surface of low-carbon
steel.
121
This ter-polymer exhibited improved resis-
tance to water permeation. The copolymer poly(pyr-
role-co-o-toluidine) was synthesized electrochemically
on mild steel only at low temperatures exhibiting the
best protective efciency in 3.5% NaCl for a pyrrole-o-
toluidine feed 8:2 ratio.
122
PPy and poly(pyrrole-co-o-
anisidine) were electrochemically synthesized on the
surface of 3102 aluminum alloy.
123
This copolymer
contained a hydrophobic methoxy group which was
responsible for lower water permeation than pure PPy
coatings and hence demonstrated better corrosion
protection.
Moreover, copolymers of aniline with its derivatives
containing sulfonic, carboxylic, and methoxy groups
were found to show also improved protection efciency
due to the modication of polymer backbone that
affects adherence, compactness, porosity or the doping/
dedoping process of the coating. Poly(aniline-co-
amino-naphthol-sulfonic acid) nanowires coating was
synthesized electrochemically on the surface of iron.
124
Increased corrosion resistance in comparison with a
PANI coating was attributed to the strong adherence
of the copolymer due to the interaction of side groups
to the iron substrate as well as its superior adsorption
to the iron substrate. Poly(aniline-co-4-amino-3-hydro-
xy-naphthalene-1-sulfonic acid) was synthesized by
chemical oxidative polymerization. In this synthesis,
4-amino-3-hydroxy-naphthalene-1-sulfonic acid was a
dopant. The corrosion-inhibiting properties of the
copolymer were studied on an iron substrate in 1 M
HCl. It was found that as the concentration of the
inhibitor dopant increased in the monomer feed, the
corrosion inhibition efciency also increased.
125
Elec-
trochemical synthesis of poly(aniline-co-o-anisidine)
thin lms on copper by cyclic potential sweep deposi-
tion at low and high scan rates was homogeneous and
strongly adherent on the substrate exhibiting good
corrosion resistance.
126,127
In an attempt to investigate
the effect of a hydrophilic group attached to the PANI
chain on the anticorrosive performance of PANI-based
coatings, poly(aniline-co-metanilic) copolymers were
prepared chemically and deposited on carbon steel.
128
Though the copolymers provide less protection of the
coated carbon steel in 1 M H
2
SO
4
than the PANI
itself, it seems that the lower the sulfur content in
copolymer the better is the protective ability. This
behavior is attributed to the hydrophilic character of
the sulfonic group that does not favor the anticorrosion
performance of the coating. In another study, poly(ani-
line-co-m-amino benzoic acid) was electropolymerized
on the surface of steel.
129
It was found that the
improved corrosion protection ability of the synthe-
sized copolymer was attributed to the better compact-
ness of the resulting lms.
Multilayers of CPs
Multilayer coatings of CPs have been reported for
corrosion protection of metals and their alloys. This
approach has been used in the case of aniline
electropolymerization on zinc and mild steel from
aqueous media and is a two-step process.
91,130,131
A
thin PPy lm was rst deposited on the metal substrate
from a neutral salicylate medium. The thin PPy layer
behaves as a noble metal layer slowing down the
substrate corrosion rate. Then in a second step, the
PANI was electrodeposited on the metal|PPy substrate
from an acidic medium. The PPy/PANI bilayers as well
as the composites PPy/PANI electrodeposited in a one-
step process
132,133
indicate superior anticorrosion per-
formance in sodium chloride solutions than the plain
PANI or PPy layers. A nding that points to the
mechanism by which the protection efciency of the
PPy/PANI bilayer is greatly improved is that when
PANI was rst deposited on steel, instead of PPy, the
483
resulting PANI/PPy has a lesser protective ability than
the PPy/PANI bilayer.
91
This shows that the underly-
ing PPy lm provides a better barrier effect and
sufcient adherence to the top PANI-layer. It is
suggested that the strip-shaped PANI layer formed
within the matrix of PPy lowered the permeability of
the PPy/PANI coating and therefore the transport of
electrolyte, O
2
, and H
2
O through the coating. The
complex PPy/PANI can be characterized as composite
or bilayer since the PPy is rst formed either in the
one- or two-step (layer-by-layer) process as the oxida-
tion potential of pyrrole is lower than that of aniline.
Bilayers of PANI and poly(N-methylaniline)
(PNMA) were synthesized electrochemically on a mild
steel surface in layer-by-layer manner. The galvanic
interaction of CP bilayers was responsible for better
corrosion resistance than the respective homopolymers
on the mild steel substrate.
134
On similar lines, bilayer
coatings of PPy and PNMA were obtained on mild
steel by electrochemical polymerization.
135
In this case,
PPy was doped with the dodecylsulfate ion. The
PNMA/PPy coating exhibited the best anticorrosion
performance among PNMA/PPy coating, PPy homo-
polymer coating, and the PPy/PNMA coating. The
reduction in anionic permeability due to the presence
of the dodecylsulfate ion was found to be the cause of
improved corrosion resistance performance. In another
attempt, multilayer thin lms of poly(vinylsulfonic
acid, sodium salt) (PVSS) and PANI were synthesized
using a layer-by-layer technique on the surface of AA
2024.
136
Several layers of PVSS/PANI were synthe-
sized and were tested against corrosion. It was found
that optimum anticorrosion performance was obtained
at eight layers of PVSS/PANI on the surface of AA
2024 in the chloride media. PPy and PANI bilayers
were electrochemically synthesized on carbon steel as
well as stainless steel 304.
137,138
Multilayers of CPs can result in improved corrosion
protection. PPy electropolymerized on the surface of a
copper layer deposited on aluminum imparted greater
corrosion resistance than just copper-deposited alumi-
num and PPy-deposited aluminum.
139
This improve-
ment was found to be due to the enhanced barrier
protection from the presence of various multilayers of
CPs and metal.
Doped CPs for corrosion protection
As discussed earlier, different corrosion-inhibiting
dopants can be incorporated in the CPs. Both electro-
chemical polymerization and chemical oxidative poly-
merization can be employed for the synthesis of doped
CPs. Doping anions may also form complexes or
products that slow down corrosion rate by acting as
physical or chemical barriers.
PANI doped with tungstate was prepared via
chemical oxidative polymerization and was dispersed
in primer containing vinyl resin as a binder.
140
This
coating was applied on a steel substrate and its
anticorrosion performance was evaluated using salt
spray and EIS. The EIS measurements were carried
out in 3% NaCl solution. The OCP values were in the
noble direction, which indicated the passivation pro-
vided by PANI doped with tungstate coating. An iron-
tungstate complex was also observed on the surface of
the iron substrate signifying more resistance to corro-
sion. In the same manner, sulfonate-doped PANI was
prepared by chemical oxidative polymerization and
was incorporated in a vinyl resin-based coating.
141
The
anticorrosion performance of the coating on an iron
substrate in 0.1 N HCl and 3% NaCl was monitored
via EIS. The coating containing sulfonate-doped PANI
exhibited very high impedance after 100 days exposure
to acid and neutral media whereas coatings without
sulfonate-doped PANI showed anticorrosion perfor-
mance up to 50 days in acidic media and 100 days in
neutral media. The increased ability to protect against
corrosion was attributed to the formation of a passive
oxide lm of PANI-iron-sulfonate complex. Moreover,
phosphate and chloride-doped PANI, synthesized
chemically, were used in epoxy-coal tar coatings for
the corrosion protection of steel.
106
From EIS studies,
it has been found that the resistance of coatings
containing 1% and 3% phosphate-doped and 3%
chloride-doped PANI was kept high for 90 days in
3% NaCl solution. The resistance of these pigmented
coatings was higher by two orders of magnitude
compared to that of conventional coal tar epoxy
coatings. The anticorrosive efciency of the coatings
containing phosphate-doped PANI was higher. X-ray
photoelectron spectroscopy has shown that beneath
the coating the complex PANI-Fe along with the iron
oxide was formed resulting in the enhancement of the
steel protection against localized corrosion.
Comparing the protective performance of several
epoxy resin (EP)-based coatings containing either
PANI as EB, ES, sulfonated and bers or zinc
phosphate and zinc chromate on mild steel in 3.5%
NaCl shows that the addition of PANI results in
improved corrosion protection of steel. Only the
coating containing PANI-EB showed a lower efciency
than the other PANI-containing coatings.
142
CR-con-
taining PANI showed improved protective properties
as compared with a simple CR-based coating against
the corrosion of mild steel in 3.5% NaCl.
143
In another study, PANI was electropolymerized on
the surface of 430 stainless steel in nitric acid
solution.
144
Its performance against corrosion was
evaluated in 3% NaCl solution by EIS and anodic
polarization. The catalytic effect of PANI was respon-
sible for the formation of a dense oxide layer at the
polymer metal interface. Dense oxide lm and PANI
were responsible for the improved corrosion protec-
tion of the coating on the 430 stainless steel substrate.
In same way, PANI-molybdate coating was prepared
by electrochemical synthesis on a steel substrate via
cyclic voltammetry.
145
Potentiodynamic polarization
and EIS were employed for monitoring the corrosion
protection ability of the PANI-molybdate coating in
484
1% NaCl solution. The passivating nature of PANI
and the formation of an iron-molybdate complex were
responsible for the improved corrosion performance
of the PANI-molybdate coating on the surface of
steel.
PANI doped with hydrouoric acid was synthesized
by chemical oxidative polymerization.
146
This pigment
was incorporated into an epoxy primer, which was
applied to AZ91D magnesium alloy. X-ray photoelec-
tron spectroscopy results displayed the formation of
magnesium uoride (MgF
2
) underneath the coating as
it was exposed to 3.5% sodium chloride solution. It was
found that the insoluble MgF
2
was responsible for the
improved corrosion resistance by uoride-doped PANI
on AZ91D magnesium alloy substrate. On similar
lines, methane sulfonic acid (MeSA)-doped PANI was
synthesized by chemical oxidative polymerization.
147
PANI-MeSA was used as an anticorrosive pigment in
ultraviolet light curable polyester acrylate matrix and
was applied on the surface of galvanized steel. OCP
measurements in 3% sodium chloride solution indi-
cated a shift in positive direction due to the anodic
ennoblement of the substrate giving long-term corro-
sion protection.
PANI doped with benzene-sulfonate (BS) and ligno-
sulfonate (LS) was synthesized by chemical oxidative
polymerization and was incorporated into a CR binder
in varying weight proportions.
148
The coatings were
applied on mild steel and the corrosion performance
behavior was monitored by EIS with salt spray expo-
sure and immersion in sodium chloride solution. Below
1% concentration of BS-doped PANI and 3% concen-
tration of LS-doped PANI showed improved corrosion
performance. In this study, it was observed that LS was
not covalently bonded to PANI, which was responsible
for the different behavior than that of BS-doped PANI.
PANI-LS/epoxy coatings were also employed for
corrosion protection of AA2024-T3.
149
The perfor-
mance of PANI-LS/epoxy blends was investigated in
0.6 M NaCl during 30 days for different loadings in
PANI-LS. A better protection efciency was found for
an optimum amount of PANI-LS (5 wt%) in epoxy
blends. It appears that at these optimized concentra-
tions of PANI-LS, a uniform distribution of PANI
particles results in a decrease of the permeability of
H
2
O and O
2
. The improved corrosion protection is
explained in terms of the anodic protection mechanism
and the controlled inhibitor release mechanism. A
thickened oxide lm is formed due to the active redox
role of PANI whereas the release of dopant (LS) at the
defect site prevents active dissolution of the substrate
by the formation of an aluminum-sulfonate complex.
Moreover, dodecylbenzenesulfonic acid-doped PANI
nanoparticles (1 wt%) blended epoxy ester (EPE)
showed better corrosion protection of the carbon steel
substrate in 3.5% NaCl compared to the simple EPE
coating.
150
This behavior was also attributed to the
released dopant anions that with the iron cations
provide a secondary barrier layer, which passivates the
carbon steel.
In the case of benzoate-PANI coatings, galvanostat-
ically synthesized on mild steel, it was suggested that
the protection effect can be described by the switch-
ing zone mechanism.
151
According to this mechanism
during an initial period, the corrosion potential shifts to
more negative values determined cathodically by the
dedoping process of PANI-benzoate along with the
oxygen reduction and anodically by the iron dissolu-
tion. As most of the benzoates were released the PANI
conductivity decreases. During a medium period, the
corrosion potential shifts to less negative values deter-
mined by the cathodic oxygen reduction at the bare
metal in the bottom of the PANI pores and the anodic
partial doping of PANI by chlorides and the initial
period is repeated. It is suggested that during a
prolonged period a thin oxide layer is formed near
the PANI and thus the oxygen reduction is catalyzed.
PPy doped with corrosion-inhibiting ions have been
studied for the corrosion protection of metals and their
alloys. Molybdate and nitrate doped PPy were elec-
tropolymerized on the surface of 316L SS in neutral
and alkaline media.
152
It was found that the pitting
potential of the substrate was reduced. Improved
corrosion protection was attributed to the electro-
chemical activity of PPy, the formation of a passive
oxide layer, and the nature of dopants used in the
electrochemical synthesis of PPy on the substrate. In
another study, electrochemical polymerization of PPy
was carried out on AA 2024-T3 substrate using various
dopants, such as camphor sulfonic acid, phenylphos-
phonic acid, para-toluene sulfonic acid, oxalic acid, and
cerium nitrate salt. Different morphologies and varying
corrosion behaviors of the PPy were observed as a
function of dopant anion.
153
Nanostructured CPs
The application of nanotechnology in metal anticorro-
sion technology has attracted a great interest recently,
although it is still in its infancy. Nanostructured CPs
such as nanoparticle, nanober, nanowire, nanorod,
nanotube can be prepared by different meth-
ods.
17,154158
They are characterized by specic phys-
icochemical properties that are found to enhance the
performance of CP-based materials when used in
several applications.
159161
Among new properties are
specic light absorption, quantum tunneling effects,
hydrophobicity, stability, catalytic, and magnetic prop-
erties.
154,162,163
In particular, nanostructured CPs also
seem to be promising materials in preparation of
protective coatings against metal corrosion.
17,50,164,165
It is suggested that the anticorrosion property is
improved through either the enhancement of the
adhesion of CP-based coatings to the metal substrate
by using bifunctional compounds or the increase of the
CP-coating hydrophobicity. Nanostructured CPs result
in compact passive layers at the metal substrate,
increasing protection efciency. Nanotechnology is
expected to have a great potential for corrosion control
485
in the case of either simple CP layers or CP composites
where various compounds might be incorporated to
obtain multifunctionalized nanocomposites.
166
PANI nanostructures synthesized chemically
164,165
or electrochemically
50
indicate improvement of the
anticorrosion performance of PANI-based coatings.
Yao et al.
164
studied the anticorrosion properties of
PANI nanobers synthesized by interfacial polymeri-
zation and applied to carbon steel as a suspension in
ethanol in comparison with the anticorrosion perfor-
mance of aggregated PANI-coated carbon steel in 5%
NaCl aqueous solution. On the basis of potentiody-
namic polarization, measurements show that the PANI
nanobers have better corrosion protection to carbon
steel than the aggregated PANI. Raman spectroscopy
shows that PANI nanobers induce the formation of
better passive oxide layers on carbon steel. This is
attributed to the better dispersion stability of PANI
nanobers in ethanol, which results in the formation of
a more compact coating layer on carbon steel surface.
Yang et al.
165
synthesized different one-dimensional
PANI nanostructures in sulfuric acid solutions using
different polymerization methods, namely conven-
tional polymerization, interfacial polymerization, and
direct mixed reaction. The PANI products were
applied to the mild steel surface as a suspension in
N-methyl-2-pyrrolidinone (NMP) and their anticorro-
sion properties were investigated in 3.5% NaCl solu-
tion by potentiodynamic polarization curves.
Comparative studies revealed that PANI nanobers
synthesized by direct mixed reaction have greater
uniform morphology and better protective properties
than the PANI synthesized by other methods.
Moreover, PANI nanobers were prepared by direct
mixed reaction in four different inorganic acids,
namely HCl, H
2
SO
4
, HNO
3
, H
3
PO
4
, and use in
composite coatings of PANI-epoxy resin by mechan-
ical grinding.
167
The type of inorganic acid inuences
the morphology of PANI nanobers. The effect of the
PANIs content on the anticorrosion property of the
epoxy composite coatings mixed with different PANI
nanobers doped by four different acids was investi-
gated for Q235 steel in 3.5% NaCl solution. The best
protective performance was obtained when the amount
of PANI was around 0.5% and doped with H
3
PO
4
. The
effect of the doping anions on the protective ability was
varied in the order H
3
PO
4
> H
2
SO
4
> HNO
3
> HCl.
The superior protection in the case of H
3
PO
4
was
explained considering the controlled inhibitor release
mechanism
15,16
by which the release of phosphates
induces the formation of an excellent passive lm on
the steel substrate.
47
In the case of the composite
coatings mixed with H
2
SO
4
, HNO
3
-doped PANI better
protection was attributed to the PANI excellent ber
morphology and network structure.
In another situation, by employing a miniemulsion
polymerization technique, conducting polymer nano-
particles (CPNs) of polyanisidine, polytoluidine, and
their copolymers (CCPNs) were synthesized.
168
Barrier
properties along with ability of conducting polymers to
act as an oxidant to underneath steel surface improved
the corrosion protection provided by coatings based on
CPNs and CCPNs.
Composites and nanocomposites of CPs
Many researchers have exploited the possibility of
using composite materials based on CPs as anticorro-
sive coatings. Composites combine the functional
properties of diverse materials imparting improved
properties for corrosion protection of metals and their
alloys. A number of different metal, metalloid, metal
oxide particles or nanoparticles as well as carbon
nanomaterials such as carbon nanotubes and graphene
can be encapsulated into the matrix of a PANI to
produce PANI-based composite materials.
29
To dem-
onstrate the improved protection ability of composites
of PANI, on a mild steel substrate, coatings based on a
PANI matrix lled with zinc and zinc nanoparticles
were obtained on iron by solution mixing method.
169
The presence of nanoparticles of Zn in PANI
improved its conductivity and anticorrosion properties
in comparison to the microsized particles of Zn in
PANI composite coatings. This study showed the
impact of ller particles, their loadings, nature, mor-
phology, and size on the nal anticorrosion properties.
Further investigation was done by in situ synthesis of
PANI, in the presence of zinc nanoparticles.
170
Chem-
ical oxidative polymerization was used for PANI-Zn
nanocomposite synthesis. This nanocomposite was
then applied to an iron substrate by the solution
casting method. The maximum conductivity of the
PANI-Zn nanocomposite coating was obtained at
5% w/w zinc loading. The conductivity was found to
be the function of the amount of zinc present in the
composite. Zinc protects iron cathodically by sacricial
protection. The corrosion products of Zn can ll the
pores in the CPs resulting in more barrier protection
along with the added electrochemical activity of CPs.
OCP measurements displayed a positive shift indicat-
ing better anticorrosion performance for PANI-Zn
nanocomposite coating against just PANI coating.
Moreover, recently the chemical oxidation of aniline
monomer with ammonium peroxydisulfate was used in
the presence of camphosulfonic (CSA) acid for the
preparation of PANI nanocomposites containing ZnO
nanorods.
171
TGA results showed that the decomposi-
tion of the nanocomposite was less than that of pure
PANI indicating its potential application in anticorro-
sive paints. The doping effect of ZnO nanorods was
observed in PANI-ZnO nanocomposites. The interac-
tion between PANI and ZnO nanorods is based on the
formation of hydrogen bonding and electrostatic
interaction between CSA-capped ZnO nanorods.
SiO
2
is among the promising nanoparticles em-
ployed in metal anticorrosion coatings. Hydrophobic
PANI-SiO
2
composites nanocomposites (HPSC) syn-
thesized chemically and deposited on mild steel exhibit
improved protective efciency as compared with
486
PANI. This was explained by considering that the
HPSC results in the formation of a passive oxide lm
on mild steel and simultaneously prevents the chloride
ion penetration into the coating due to the hydropho-
bic character of the composite. The HPSC coating acts
as a barrier between the metal and the corrosive
environment. Moreover, the presence of SiO
2
nano-
particles leads to the reinforcement of PANI and hence
diminution of its degradation.
18
The synergistic effect
of the PANI redox catalytic ability and hydrophobicity
properties leading to advanced anticorrosion coatings
was also observed in the case of composites prepared
from uoro-substituted PANI incorporated with sils-
esquioxane spheres.
172
Casting of the as-prepared
composite material onto a CRS electrode results in a
coated-CRS with enhanced corrosion resistance in
saline conditions.
Composites of PANI with multiwall carbon nano-
tubes (MWCNT) used as paints on low-carbon steel
were found to have promising anticorrosion proper-
ties.
173
It seems that the PANI-MWCNT-based paints
signicantly decrease the corrosion rate of the steel in
3.5% NaCl aqueous solution.
PPy and nanocomposites of PPy and zinc oxide
(PPy-ZnO) were electrodeposited.
174
The anticorro-
sion performance of the coatings in 3.5% NaCl solution
was monitored by Tafel polarization and EIS. The PPy-
ZnO nanocomposite coating showed improved corro-
sion resistance in comparison with the PPy coating.
This improved performance of PPy-ZnO nanocompos-
ite coating over the PPy coating was attributed to the
ZnO morphology. ZnO was in the form of nanorods in
the PPy-ZnO nanocomposite coating. So the morphol-
ogy of the contributing element in nanocomposite of
CPs also affects the nal corrosion performance
properties of composite coatings.
In the presence of TiO
2
nanoparticles, poly(N-
methyl pyrrole) coating was synthesized on the surface
of steel.
175
This synthesis was carried out in the
presence of dodecyl benzene sulfonic acid and oxalic
acid. The presence of TiO
2
nanoparticles in the
poly(N-methyl pyrrole) coating improved the interac-
tive surface area of poly(N-methyl pyrrole) with the
ions involved in the corrosion reaction. This resulted in
the decreased water uptake by the composite coating
as well as the increase in the pore resistance of the
resultant coating. Along the same lines, PPy/Sn-doped
TiO
2
nanocomposites were used as anticorrosive pig-
ment in epoxy primer on steel substrate.
176
Sn doping
of TiO
2
nanoparticles improved the anticorrosion
ability of PPy/Sn-doped TiO
2
nanocomposites in com-
parison with PPy/TiO
2
nanocomposites. In this re-
search, it was observed that Sn doping increases the
band gap of TiO
2
in turn decreasing the charge transfer
in the nal coating based on PPy/Sn-doped TiO
2
nanocomposites. PPy/Ni-doped TiO
2
nanocomposites
were also synthesized for the corrosion protection of
steel.
177
An increase in the surface area due to the
presence of nanoparticles resulted in increased inter-
action between the particles and the ions involved in
the corrosion reaction. Ni doping also decreased the
size of the nal PPy/Ni-doped TiO
2
nanoparticles in
comparison with PPy/TiO
2
nanoparticles, which fur-
ther improved the corrosion resistance.
PPy/carboxylic acid functionalized single-walled
carbon nanotubes (CNT-CA), and PPy/poly-amino-
benzene sulfonic acid functionalized single-walled
carbon nanotubes (CNT-PABS) were electrochemi-
cally prepared.
178
In this synthesis, CNT served as the
dopant. Their anticorrosion performance on carbon
steel in 3.5% NaCl solution and their mechanical
properties were compared with pure PPy. It was found
that the PPy/CNT-CA and PPy/CNT-PABS composite
coatings showed more anodic potential and lower
corrosion current against uncoated steel and improved
mechanical reinforcement. Besides CNT-CA, multi-
walled carbon nanotubes (MWCNT) also served as
dopants in poly(3,4-ethylenedioxythiophene) nano-
spheres (PEDOT-NSP/MWCNT) changing the intrin-
sic anion-transport selectivity of PEDOT to a cation-
transport selectivity.
179
The PEDOT-NSP/MWCNT
was synthesized using microemulsion polymerization
and investigated as a corrosion inhibitor for aluminum
in LiPF
6
. The anticorrosion effectiveness of PEDOT-
NSP/MWCNT was attributed to a synergistic effect
that involves the cation exchange PEDOT and the
anion-repulsive pristine MWCNT surface. Due to this
cooperative action, the transport of the PF
6
anions
toward the aluminum surface is blocked and hence
pitting corrosion induced by PF
6
anions is prevented.
Composites and nanocomposites of CPs can be
prepared by the inclusion of layered materials. The
plate-like shape of these materials lengthens the path
of corrosive ions toward the substrate resulting in delay
in the onset of corrosion process. The ake structure
can reduce the permeability of the solute by a factor of
10 after their inclusion in the coating.
180
CP/MMT
clays composites and nanocomposite have been used
for the corrosion protection of metals and their
alloys.
181185
PANI/MMT nanocomposites were pre-
pared by blending PANI and MMT in epoxy resin.
181
The specic morphology of the nanocomposite re-
sulted in improved corrosion protection of Al 5000.
In another attempt, PANI/clay nanocomposite was
prepared by chemical oxidative polymerization meth-
od.
182
This nanocomposite was then incorporated in a
zinc-rich ethyl silicate resin. EIS measurements were
carried out in 3.5% NaCl solution and OCP was
monitored for the corrosion evaluation. The barrier
protection and the passivation of the substrate due to
presence of the composite pigment resulted in im-
proved corrosion resistance of the coating containing
PANI/clay nanocomposite in comparison with the
pristine coating. Along similar lines, PANI/MMT
nanocomposite coatings were prepared on aluminum
alloy (AA 3004) by galvanostatic method.
183
The
corrosion performance properties of these coatings
were monitored in 3.5% NaCl solution by impedance
and potentiodynamic measurements. With the nano-
composite on the surface of AA 3004, the corrosion
487
current was found to be decreasing. The anticorrosion
performance of the PANI/MMT nanocomposite was
attributed to the barrier nature of MMT and redox
catalytic nature of PANI. Molybdate-doped PPy/MMT
nanocomposites were also found to improve the
steel.
186
The protection was attributed to the increased
barrier protection due to the MMT and dopant release
from PPy.
Conducting polymer-containing composite coatings
(CPCC) is a new class of materials, which can resolve
processibility issues related to CPs along with their
bulk synthesis. PPy/aluminum (Al) ake composite
coatings have been found to protect aluminum alloy
(AA 2024-T3) against corrosion.
187189
The presence of
PPy in intimate contact with aluminum akes activates
them toward anodic activity resulting in galvanic
coupling between composite and the substrate. The
effect of PPy morphology formed on the surface of Al
ake was studied for the corrosion protection of AA
2024-T3.
190
It was found that wire PPy formed on the
surface of Al ake resulted in PPy/Al ake composite
which in turn provided sacricial corrosion protection
to the underlying AA 2024-T3 substrate. Phosphate
and nitrate doped PPy/Al ake composite pigment-
based coatings were applied on the surface of AA
2024-T3.
191
Dopant release mechanism combined with
galvanic coupling helps to protect underlying substrate.
PPy/micaceous iron oxide (MIOX) composite pig-
ments were synthesized by chemical oxidative poly-
merization.
192
Redox properties of PPy combined with
barrier properties of MIOX provided prolonged cor-
rosion protection.
Conclusions
CPs can be used in various forms for corrosion
protection of metals and metal alloys. They can be
used as pigments, multilayers, and composites. Corro-
sion-inhibitive dopants can be incorporated on the
backbone of CPs which can be released when CPs are
reduced under particular conditions. Bulk synthesis of
CPs is possible by chemical oxidative polymerization
method. Electrochemical deposition of CP layers
directly on the oxidizable surfaces of metals and alloys
using appropriate electrolytes in polymerization solu-
tions is also possible. Anodic protection occurs as far as
the OCP of the M|CP system is kept within the
passivation state of the metal substrate. However, a
simple CP coating seems unable to provide protection
for a long period in aggressive environments where
localized breakdown of the CP coating usually occurs.
Using suitable doping ions and an optimized amount of
CP in protective coatings, a self-healing process oper-
ates as far as the CP is in its electroactive state. The
morphology of CPs inuences the anticorrosion prop-
erties of the CP-based coatings. Future investigations
exerting more control over the synthetic paths of
nanostructured CPs are expected to lead to improved
protective CP-based materials with a better perfor-
mance. Numerous studies in recent times show the
tremendous potential of CPs for the corrosion protec-
tion of metals and their alloys, which is yet to be fully
explored.
Acknowledgments The corresponding author would
like to thank Prof. S.T. Vagge, Head, Department of
Metallurgy and Material Science, College of
Engineering, Pune 411005 (MH) India for providing
facilities, and Prof. Anil Sahasrabudhe, Director,
College of Engineering, Pune 411005 (MH), India for
his constant encouragement along with support from
Alumni Association of COEP for granting ADFF
Meta Fellowship, AICTE and UGC, New Delhi India
and ISRO, Bangalore. Authors from North Dakota
State University (NDSU) gratefully acknowledge the
support from US Army Research Laboratory under
Grant No. W911NF-09-2-0014, W911NF-10-2-0082,
and W911NF-11-2-0027.
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Conducting polymers for corrosion protection: a review

Pravin P. Deshpande, Niteen G. Jadhav,

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zylmaz, AT, Erbil, M, Yazc, B, The Electrochemical

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