Progress in Organic Coatings 64 (2009) 383–386

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Epoxy powder coatings containing polyaniline for

enhanced corrosion protection
S. Radhakrishnan ∗ , Narendra Sonawane, C.R. Siju
Polymer Science and Engineering, National Chemical Laboratory, Pune 411008, India

a r t i c l e i n f o a b s t r a c t

Article history: Incorporation of polyaniline (PANI) in epoxy type powder coating formulations has not been attempted
Received 12 March 2008 earlier. Using specific grade of PANI with low doping, it can be incorporated in epoxy powder coating for-
Accepted 29 July 2008 mulations by twin screw extrusion process. The powder formulations were deposited on steel substrates
by electrostatic spray coating at −60 kV and baked at 140 ◦ C for 20 min. These were extensively tested for
Keywords: corrosion resistance by exposure to hot saline conditions followed by electrochemical impedance spec-
Epoxy
troscopy and also salt spray testing. PANI incorporated coatings showed no deterioration even after 1400 h
Powder coating
of hot (65 ◦ C) saline treatment. The coatings intentionally scratched also exhibited self healing property
Polyaniline
Corrosion resistance
and there was no rust formation even after prolonged exposure to hot saline conditions. These results
could be explained on the basis of additional crosslinking due to PANI, as confirmed by DSC results, which
gave rise to improved barrier property and self healing was associated with the scavenging of ions by PANI
which prevented corrosion of the underlying substrate.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction sizing the polyaniline played an important role in obtaining good

Conducting polymers have been studied in great details for past
two decades for a variety of applications in electrical/electronic
industry such EMI shielding, ESD protection, etc. [1–3]. Amongst
these, polyaniline (PANI) has been found to be important con-
stituent in different types of coatings and recently that it has
drawn attention as an effective material for corrosion protection
[4–7]. PANI based “smart” coatings can prevent corrosion even in
scratched areas where bare steel surface is exposed to the aggres-
sive environment [8,9]. The anti-corrosive coatings can be prepared
either from chemically synthesized PANI or it may be directly
deposited on metal by electrochemical method [10,11]. Chemically
synthesized PANI by conventional route is difficult to process in
common organic solvents and hence its applicability depends on
forming stable dispersions. Epoxy powder coatings are known to
be superior in many respects to regular paints due their scratch
hardness, adhesion, etc. [12,13]. However, even these coatings are
known to fail under harsh environmental conditions over pro-
longed exposure. Incorporation of PANI in these type of powder
coating formulations has not been attempted earlier. During our
attempts for the incorporation of PANI in epoxy formulations it
was observed that the extent of doping and the method of synthe-
∗ Corresponding author. Fax: +91 20 25902615.
E-mail address: s.radhakrishnan@ncl.res.in (S. Radhakrishnan).
epoxy formulations. This arises due to two reasons: PANI being con-
ducting when prepared under normal conditions renders the epoxy
powder with less electrical charge and also the curing of epoxy
becomes too rapid due to the amine terminal groups in polyani-
line. These drawbacks have been overcome by using appropriate
method of synthesis for PANI which has been successfully incor-
porated in epoxy powder coating formulations. The present paper
describes results of our studies on these aspects and the improved
corrosion resistance obtained for the coatings.
2. Experimental
The lightly doped PANI was prepared according to our patented
procedure [14] which essentially consists in polymerization of ani-
line (1 M) in aqueous medium containing 1:1.5 M mixed oxidizing
and doping agent such as ammonium peroxidisulfate (APS) and
ferric chloride (FeCl3 ) being kept at 5 ◦ C for 8 h under constant
stirring, precipitating the product using charge neutralizing agent,
centrifuging filtering and drying the polymer. Very fine and uniform
PANI powder was obtained (200 mesh size) after crushing which
was blended with epoxy formulation in various proportions rang-
ing from 0% to 7%. For powder coating, the following compositions
have been used: epoxy resin (bisphenol A, Huntsman 7004) (93%),
hardener (B31) (6.2%), flow agents or leveling agent (BYK 368P)
(0.5%), degassing agent (benzoin) (0.3%) and polyaniline powder
added as 1%, 3%, 5%, 7% of total (phr), respectively. All ingredients

0300-9440/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2008.07.024
384 S. Radhakrishnan et al. / Progress in Organic Coatings 64 (2009) 383–386
Table 1
Gloss values of PANI–epoxy powder coatings on steel
Samples Gloss value
Viewing angle
60◦
Pure epoxy 108.9
1% PANI 100.4
3% PANI 94.4
5% PANI 96.1
7% PANI 95.8
were homogenously mixed in high speed mixer and extruded by
lab model twin screw extruder at 100–105 ◦ C followed by cool-
ing, grinding and sieving for obtaining the final powder for coating
(100 mesh size). Steel substrates (5 cm × 1 cm × 0.1 cm) which were
polished with fine emery paper and rounded edges were used for
coating. Electrostatic spray gun used for deposition of powder coat-
ing which was held at 60 kV potential with respect to the substrate
(grounded). After obtaining uniform coverage of the powder, the
coated plates were placed in air drying oven for curing at 140 ◦ C
for 20 min. The coupons were then cooled and the various proper-
ties of the coatings such as gloss, scratch hardness, etc. were noted
by standard methods. The coating thickness was in the range of
100–110 ␮m. The gloss was measured by BYK-Gardner Tri-angle
gloss-o-meter (20◦ , 60◦ , 85◦ ). The samples were then subjected for
measurement of corrosion inhibition properties by electrochemical
impedance measurement and salt spray techniques. Cyclic voltam-
mogram, Tafel plot and impedance measurements were carried
out in 3.5% NaCl solution. All measurements were performed on
computerized electrochemical analyzer (supplied by CH instru-
ments, USA). Stainless steel plate coated with composites, Pt and
SCE were used as working, counter and reference electrode, respec-
tively. The voltammograms were measured between +1 and −1 V
at a scan rate of 50 mV/s. Tafel plots was recorded at a scan rate of
2 mV/s. After initial measurements all the coupons were immersed
in hot 3.5% NaCl solution (65 ◦ C and 75 ◦ C) for a period extending
to 1500 h so as to accelerate the corrosion testing which otherwise
took several months. The coupons were subjected to electrochem-
ical measurements at different intervals and then placed back in
hot saline condition and this procedure was continued for 60 days.
In one set of experiments, the samples were intentionally marked
with an indenter to create a defect. The hard pin was used with
0.1 mm radial diameter with applied load of 2 kg to mark the inden-
tation on the coating. These were tested for corrosion protection
in the same manner as described above and elsewhere [15]. The
cross marked/scratched samples were tested for corrosion resis-
tance using salt spray technique following ASTM standard (B117).
3. Results and discussion
The initial trials on mixing PANI synthesized by conventional
route using hydrochloric acid [16] with commercial epoxy formu-
lation (obtained from Dr. Beck/Schenectady Ltd., Electrocoat Pvt.
Ltd. and others) did not yield good product and led to very rapid
curing and hardening with the reaction being exothermic. Hence,
alternate route for synthesis of PANI was adopted which did not
contain any free acid as such [14]. The product obtained from the
reaction was characterized by UV spectroscopy and it exhibited the
conventional bipolaronic band at 850 nm. The room temperature
electrical conductivity was found to be in range of 5 to 7 × 10−2 S/cm
which suggests that it is moderately doped as against the highly
doped PANI obtained in acidic media. The epoxy powder coatings
appeared dark green with high gloss value (see Table 1) and good
scratch hardness. The high gloss value clearly indicates that PANI
85◦
98.5
95
90
91.5
91.41
Fig. 1. Impedance of the epoxy–PANI powder coatings on steel after prolonged cor-
rosion testing in hot saline conditions. The data was recorded at room temperature
in 3.5% NaCl solution using electrochemical impedance spectroscopy. It is shown as
Bode plots recorded after each exposure time.
was uniformly dispersed in the powder formulation and it did not
lead to adverse effects on powder spraying or the curing behaviour
nor was there any aggregate formation which would have given
defects.
These coatings exhibited excellent corrosion resistance to saline
environment: so much so that there was no change observed in the
Tafel plot or cyclic voltammogram even after exposure to hot saline
(65 ◦ C as well as 75 ◦ C) for 45 days. The corrosion currents were also
very low and the open circuit potential (OCP) was +200 mV (SCE).
Fig. 1 indicates the Bode plot of the coatings after prolonged testing
in hot saline conditions. It is seen that there is hardly any change
even after 1500 h. The OCP values determined from the Tafel plots
after different times of exposure are shown in Fig. 2. Here too there
is practically no change in the OCP value which remains on the
anodic side with respect to steel. Hence, in another set of experi-
ments the samples were intentionally damaged using an indenter
leading to small pin hole (0.1 mm dia). These samples showed most
interesting behaviour of self healing and passivation after contin-
uous exposure to hot saline solution. Fig. 3 shows the typical Tafel
plots obtained for the intentionally scratched coatings containing
different concentrations of PANI. The coating without PANI exhibits
the Tafel plot which is similar to that of bare steel and this is not
surprising since an artificial defect was created by indentation. The
most dramatic result is obtained in the PANI–epoxy coatings. In
spite of the presence of the defect there is considerable shift in
the OCP towards anodic side when PANI is incorporated in the
coating. Corrosion resistance behaviour was tracked by monitor-
ing the OCP values with respect to time of exposure to corrosive
atmosphere. Fig. 4 shows the variation of OCP with exposure time
for coatings containing different concentrations of PANI and which
have been artificially indented. It is observed that initially there is
Fig. 2. The change in OCP values obtained from Tafel plots recorded for epoxy–PANI
powder coatings after prolonged corrosion testing in hot saline conditions.
 S. Radhakrishnan et al. / Progress in Organic Coatings 64 (2009) 383–386 385

Fig. 3. Tafel plots for intentionally scratched epoxy powder coating and exposed to
hot saline conditions.
a shift of the OCP to cathodic side which goes to almost that of bare
steel (−600 mV) [17]. For the coatings without any PANI this value
remains in the high negative region but for the coatings contain-
ing PANI, the OCP shifts progressively to more anodic side which
indicates that corrosion is getting prevented, i.e. there is self heal-
ing process present. Interestingly, this process continues for long
time and also depends on the PANI content in the coating. Thus,
the presence of PANI leads to corrosion prevention even if there is
a defect like a scratch/pin hole formed in the coating.
Fig. 4. The OCP values for intentionally damaged epoxy-powder coatings on steel
and exposed to hot saline conditions.
The results of the salt spray tests on these coatings show more
clearly that the corrosion is indeed prevented in PANI–epoxy coat-
ings. The appearance of the samples after salt spray test for 700 h is
depicted in Fig. 5. The epoxy coatings without PANI show fast degra-
dation with rust formation (see A) while those with PANI show no
rust formation in the scratched region. These findings are in keeping
with the above observations made in electrochemical tests.
The corrosion resistance of an organic coating without defects,
depends on mainly its barrier properties, i.e. how it reduces the
diffusion of moisture and corrosive ions through the film [18].
Amongst the parameters which contribute to barrier properties

Fig. 5. Photographs of surface of epoxy coatings subjected to salt spray tests after 700 h.

Fig. 6. DSC thermograms of the epoxy–PANI powder coating formulation recorded after second heating. First heating was carried out up to 160 ◦ C. Heating rate 10 ◦ C/min,
nitrogen atmosphere.
386 S. Radhakrishnan et al. / Progress in Organic Coatings 64 (2009) 383–386
Table 2
Glass transition in epoxy powder + PANI
PANI in epoxy (%) Tg a (◦ C)
0 103.65
1 105.65
3 106.32
5 108.30
a
Second heating cycle 10◦ /min.
Fig. 7. Reaction scheme indicating the self healing process for coatings containing
PANI which goes through doping and undoping cycle during exposure to corroding
ions.
of the polymer, crosslink density is very important [19]: higher
the crosslink density, lower is the diffusion of ions and better is
the barrier property. The extent of crosslinking can be determined
from the glass transition (Tg ) using DSC. Fig. 6 indicates the thermo-
grams of the epoxy powder coating samples in the second heating
cycle, i.e. the samples were subjected to first heating cycle during
which curing took place. The different curves in the figure corre-
spond to the glass transition obtained for cured samples containing
PANI content of 0, 1, 3 and 5% PANI, respectively. The values of Tg
derived from these thermograms are compiled in Table 2 shown
as the inset. There is considerable increase of Tg in epoxy contain-
ing PANI as compared with virgin powder which indicates higher
crosslink density. The shift of Tg is related to crosslink density
through following equation [20]:
5 [9] W.K. Lu, R.L. Elsenbaumer, B. Wessling, Synth. Met. 71 (1995) 2163.
Tg = Tg − Tg (0) =
(Mc /M) × Nrot
where Tg (0) is the glass transition for uncrosslinked sample, Mc
is the molecular weight between crosslink, M is molecular weight
of the whole linear chain and Nrot is degree of freedom for rota-
tion of the group between crosslinks which in the present case is
assumed to be three. A shift of 5 degrees in Tg implies increase
of 3 crosslinks per chain as derived from (Mc /M) for coatings with
5% PANI. In the present case, PANI provides additional crosslink-
ing over and above the usual epoxy + hardner system. This leads to
better barrier properties in epoxy–PANI giving excellent corrosion
resistance behaviour as compared to epoxy alone. In addition to the
above factors, PANI gives the self healing effect in the intentionally
damaged samples. This is due to the redox characteristics of PANI
which prevents the corrosion reaction to progress. It may be termed
“ion scavenging” since it gets doped by these ions and prevents the
attack of the underlying metal substrate. Also, the conducting PANI
liberates the dopant near the bare area which creates a passivating
layer on the substrate thus preventing further corrosion [21,22].
This can be depicted by the reaction scheme given in Fig. 7. It may
be pointed out here that PANI used in the present case is not fully
doped which is usually obtained by conventional route [23] since
it is synthesized by proprietary non-acidic route. Hence, it can cap-
ture the ions (possibly Cl− ) easily to form the doped polymer as
depicted in Fig. 7. Thus, PANI in the present case provides better
corrosion resistance than normal epoxy powder coatings by two
mechanisms: (1) it helps in better curing giving higher crosslink
density and improves barrier properties and (2) it also acts as a self
healing additive in the coating.
4. Conclusions
Polyaniline has been successfully incorporated in epoxy powder
coating formulation without adverse effects of rapid crosslink-
ing or deterioration of powder properties. These electrostatic
spray coated powder coatings on steel were tested for corrosion
under severe conditions of hot saline media (65 ◦ C and 75 ◦ C) for
extended periods of 1000 h. It was found that coatings as such could
withstand these conditions even after intentionally damaged by
scratching/indentation. The outstanding corrosion resistant prop-
erties of these coatings arise from the two fold action of PANI, i.e. it
leads to higher crosslink density after curing giving improved bar-
rier and it imparts self healing behaviour to the coatings even after
scratch is formed.
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