Progress in Organic Coatings xxx (xxxx) xxxx

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Progress in Organic Coatings

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

Anticorrosion behavior of DBSA doped polyaniline nanoparticles/epoxy

ester coating on carbon steel in saline-alkaline solution
Mohsen Rayati, Reza Arefinia*
Chemical Engineering Department, Faculty of Engineering, Ferdowsi University of Mashhad, Mashhad, Iran

ARTICLE INFO ABSTRACT

Keywords: Anticorrosion coatings based on epoxy ester containing different concentrations of dodecyl benzene sulfonic acid
Polyaniline nanoparticles doped polyaniline nanoparticles (nPAni(DBSA)) were prepared and applied on the carbon steel surface. The
Corrosion corrosion behavior of this system in saline-alkaline solution (3.5% NaCl and pH 9) was studied using electro-
Active inhibition chemical impedance spectroscopy (EIS) during 100 days immersion. At the end of immersion, the metal/coating
Carbon steel
interface was analyzed using scanning electron microscopy (SEM) and Raman spectroscopy. The obtained results
EIS
showed that nPAni(DBSA) particles could efficiently improve the anticorrosion performance of the epoxy ester
coating through both the barrier and the active mechanisms where the best corrosion inhibition of carbon steel
was attained at 1.5% of nPAni(DBSA). The active inhibition of nPAni(DBSA) is attributed to the formation of a
secondary passive layer at the metal/coating interface.

1. Introduction polyaniline (transformation of ES to EB) because of the basic medium of

Since three past decades, conductive polymers (CPs) such as poly-
aniline (PAni), polythiophene and polypyrrole (PPy) have been used in
various applications such as solar cell [1], fuel cell [2], rechargeable
batteries [3], drug industry [4] and anticorrosion coatings [5]. The
specific properties of CPs are mainly attributed to their electrically
conductive nature [6–8]. Among the CPs, PAni has attracted a great
deal of attention owing to its low cost, easy synthesis, good adhesion
and environmental stability [9–12].
PAni could be used in different structural forms depending on its
oxidation and protonation level. These forms can be converted to each
other by change in the chemical composition of environment or under
applying a potential. Emeraldine base (EB) and emeraldine salt (ES) are
two most promising forms of PAni, used in the empirical applications
[13–15]. It is known that PAni-EB can be easily transformed to PAni-ES
by the doping process at which PAni-EB is subjected to an organic or an
inorganic acidic solution [5,14,16]. Various acids such as camphor
sulfonic acid [8,17], phosphoric acid [9,16], lingo sulfonic acid [14],
dodecyl benzene sulfonic acid (DBSA) [18–20] have been used in the
doping process of polyaniline.
In the coating applications, PAni in either ES or EB form has been
commonly blended with the other polymer matrixes to compensate the
low mechanical properties of polyaniline. Nevertheless, blending of
PAni-ES with some resins e.g. epoxy [8,13] causes the deprotonation of
these coatings [21,22]. However, some other resins such as epoxy ester
[21,23], alkyd [24] and acrylic [25] have no side effect on the con-
ductive property of PAni-ES.
According to the literature, addition of PAni within a coating im-
proves its barrier property either in alkaline or acidic solutions; how-
ever, the corrosion resistance is lower in acidic solutions because of the
higher deterioration effect [8,10,13]. Besides the physical barrier, PAni
may act through an active inhibition mechanism by the formation of a
passive layer at the metal/coating interface. Researchers have ex-
pressed two main opinions about the nature of this layer: (a) a metal
oxide/hydroxide layer based on the redox capability of PAni [6,16,26]
and (b) a metal salt layer formed by the reaction between the metal
cations dopant anions [1,16,21,25,27]. The early view has been re-
ported for the protection behavior of both PAni-EB and PAni-ES [13]
while the latter has been particularly proposed for PAni-ES [16,21].
Moreover, a few authors claimed that the protection mechanism of PAni
is ascribed to the existence of an electric field at the polymer/metal
interface, blocking the electron transfer [19].
Many studies have been performed on the anticorrosion behavior of
PAni-EB and PAni-ES in the various corrosive environments. In this
regard, some authors believed that both ES and EB forms could protect
metals at different environments [14,27,28]. However, some others
claimed that PAni-EB provides a better protection in alkaline and
neutral solutions, while in the acidic media, PAni-ES reveals a better

⁎
Corresponding author.
E-mail address: arefinia@um.ac.ir (R. Arefinia).

https://doi.org/10.1016/j.porgcoat.2019.105451
Received 9 February 2019; Received in revised form 12 November 2019; Accepted 19 November 2019
0300-9440/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Mohsen Rayati and Reza Arefinia, Progress in Organic Coatings, https://doi.org/10.1016/j.porgcoat.2019.105451
M. Rayati and R. Arefinia
performance [8,10,29]. According to the best of our knowledge, no
investigation has been performed to study the corrosion inhibition be-
havior of a PAni-ES blended coating in alkaline solution.
In the present work, the epoxy ester coatings blended with dodecyl
benzene sulfonic acid doped polyaniline nanoparticles (nPAni(DBSA))
were prepared and applied on the carbon steel surface. The inhibition
effect of nPAni(DBSA) at different concentrations on the protection
behavior of prepared coatings for 100 days immersion in saline-alkaline
solution (3.5% NaCl and pH 9) was investigated using electrochemical
impedance spectroscopy (EIS) and the surface analysis methods of
scanning electron microscopy (SEM) and Raman spectroscopy.
2. Experimental
2.1. Preparation of coatings
Dodecyl benzene sulfonic acid doped polyaniline nanoparticles
(nPAni(DBSA)) were synthesized through the inverse microemulsion
polymerization method according to previous work [21]. Briefly, DBSA
as both surfactant and doping agent was mixed with hexane (Merck, 99
%) as the solvent then 0.1 M aniline monomers (Merck, 99.5% distilled
under reduced pressure) was added drop wise to solution and mixed 30
min until reaches a homogenous milky solution. At the end, ammonium
peroxydisulfate (APS) (Merck, extra pure) as oxidant agent was in-
troduced to initiate the oxidative polymerization. The reaction tem-
perature was kept at 0 °C during all steps. The green color mixture
indicated the conductive form of DBSA doped PAni and the products
were washed three times by ethanol, methanol, and distilled water and
then dried at 40 °C for 24 h. According to previous works, the synthe-
sized powder of polyaniline has a spherical shape with an average
particle size of about 30 nm [21,30].
The coating systems were prepared by the addition of different
concentrations (0, 0.5, 1.5, 3 and 5% w/w) of nPAni (DBSA) in a sol-
vent based epoxy ester (35 wt% of resin in the solution) (Saman Chem.
Co.) as binder and the blend was continuously mixed during 15 min.
Before application of coatings, the carbon steel plates were sand blasted
with a profile of about 30 μm and then degreased with acetone. The
coatings were applied to the carbon steel plates (SAE 1020) of size 5 cm
× 5 cm where the average thickness of coatings after completely drying
at room temperature (25 ± 2 °C) for 10 days was 50 ± 5 μm. The
coating systems containing different concentrations of nPAni(DBSA) are
named in Table 1.
2.2. EIS measurements
To manufacture the electrochemical cell, a glass tube with 2.25 cm
diameter was firmly attached to the coated steel plate by means of a
silicone adhesive where the isolated surface of coating was about 4.52
cm2. The EIS measurements were carried out with an Autolab po-
tentiostat/galvanostat model 302 N in a three-electrode cell including
an isolated surface of coating as working electrode, a saturated calomel
electrode (SCE) as reference electrode and a graphite rod as counter
electrode in 80 ml saline-alkaline (3.5 % NaCl and pH 9) electrolyte
named as "SA" solution. The solution pH was adjusted to 9 by addition
of aqueous NaOH.
Table 1
The coating systems with different concentrations of nPAni(DBSA).
nPAni(DBSA) concentration Coating name
(% w/w)
0.0 EPE
0.5 EPE/nPAni-0.5
1.5 EPE/nPAni-1.5
3.0 EPE/nPAni-3
5.0 EPE/nPAni-5
2
Progress in Organic Coatings xxx (xxxx) xxxx
The EIS spectra were recorded at an amplitude perturbation of 10
mV versus open circuit potential (OCP) over the frequency range of 100
kHz to 10 mHz. Prior to EIS measurements, the OCP values were re-
gistered for at least 100 min to assure the steady condition of the
coating system.
2.3. Surface analyses
The top surface of coatings was analyzed using the scanning elec-
tron microscope (SEM, LEO 1450VP) before and after the immersion in
SA solution. Ex-situ Raman spectroscopy technique was used to study
the corrosion product at the metal/coating interface. Raman spectro-
scopy was carried out by an AvaRaman-785 TEC with a 785 nm laser
wavelength, exposure time 15 s and laser power 500 mW.
3. Results and discussion
3.1. SEM analysis of coating surface before immersion
The surface of coatings containing different concentrations (blank,
0.5, 1.5, 3 and 5% by weight) of nPAni(DBSA) was studied using SEM
and the taken images are shown in Fig. 1. As can be seen, the surface of
EPE coating is smooth and uniform while in the presence of nPAni
(DBSA), some white regions are observed on the surface of coatings
which is as an indication of agglomeration of PAni nanoparticles.
Moreover, the density and size of these regions are increased by an
increase in the concentration of nPAni(DBSA). For the EPE/nPAni-5
coating (see Fig. 1e), the white regions cover throughout the coating
surface; additionally, the rough and wavy shape of surface are probably
arisen from the high level of agglomeration of nPAni(DBSA) where was
reported before [14].
3.2. OCP measurement
Fig. 2 shows variations of open circuit potential (OCP) versus the
immersion time for different concentrations of nPAni(DBSA) blended
epoxy ester in SA solution. It is apparent that the OCP values for EPE
and EPE/nPAni-0.5 coatings intensively decrease during about 21 days
immersion and do not change considerably for the longer time of im-
mersion. The OCP values for EPE/nPAni-1.5 and EPE/nPAni-3 coatings
shift to the more positive values for about 28 and 10 days of immersion,
respectively and then steadily decrease up to the end of immersion. In
the case of EPE/nPAni-5 coating, a different trend of variation can be
identified (Fig. 2) i.e. OCP values are sharply decreased by the im-
mersion over 21 days and then shift to the noble direction up to the end
of immersion.
A continues decrease of recorded OCP values for a conventional
coating, subjected to a corrosive environment, will be expected due to
the deterioration of coating and corrosion development process. Despite
this, increasing the OCP values for coatings with 1.5, 3 and 5% nPAni
(DBSA) is likely arisen from the active protection mechanism of nPAni
(DBSA) which has been addressed by some researchers [8,14,26,27]
and will be further discussed in the next sections. Moreover, Fig. 2
shows that the coatings containing nPAni(DBSA) have higher values of
OCP compared with the EPE coating, which indicates the hypothesis
that nPAni(DBSA) acts as an anodic inhibitor in SA solution.
3.3. EIS measurements
3.3.1. Evaluation of coating performance using EIS curves
The EIS curves for the coatings containing different concentrations
(0, 5, 1.5, 3 and 5% by weight) of nPAni(DBSA) at different interval
times over 100 days immersion in SA solution were recorded and the
obtained data in the form of Nyquist and Bode plots for EPE and EPE/
nPAni-0.5 coatings are shown in Fig. 3. These plots for EPE/nPAni-1.5,
EPE/nPAni-3 and EPE/nPAni-5 coatings are displayed in Fig. 4. As
M. Rayati and R. Arefinia Progress in Organic Coatings xxx (xxxx) xxxx

Fig. 1. SEM images taken from the top surface of coatings containing different concentrations of nPAni(DBSA): a) EPE, b) EPE/nPAni-0.5, c) EPE/nPAni-1.5, d) EPE/
nPAni-3 and e) EPE/nPAni-5, before immersion.

seen, the shape of Nyquist plots for EPE, EPE/nPAni-0.5 (in Fig. 3a and
c) and EPE/nPAni-5 (in Fig. 4e) coatings is composed of two distinct
depressed loops or one loop with a large diameter as a result of the
combination of two small loops. These observations mean that the
electrolyte molecules could pass the coating structure and reach to the
metal surface, causing the initiation of corrosion process immediately
after a short time of exposure to the corrosive environment. In this si-
tuation, the coatings without and with 0.5 and 5% nPAni(DBSA) behave
as a "defected coating", arisen from their low barrier properties [21].
In the case of EPE/nPAni-1.5 and EPE/nPAni-3 coatings (see Fig. 4a
and b), the shape of Nyquist plots is composed of one incomplete loop
over the all times of immersion. This indicats the superior protetion of
these coatings against the corrosion development and their function is
as an "intact coating". Although, the change in the diameter of capaci-
tive loop is influenced by change in the protective charactreistic of
coating which will be further discussed using the variations of

Fig. 2. Variations of OCP values for the coatings containing different concentrations of nPAni(DBSA) in SA solution during 100 days immersion.

3
M. Rayati and R. Arefinia
Fig. 3. Nyquist and Bode module plots for the coatings: (a and b) EPE; (c and d) EPE/nPAni-0.5 in SA solution during 100 days immersion.
impedance parametres.
3.3.2. Simulation of coting behavior using ECMs
The impedance data were analyzed using the equivalent circuit
models (ECMs) shown in Fig. 5. The ECM with one time constant
(Fig. 5a) and with two time constants (Fig. 5b) correspond to the cor-
rosion state of an intact and a defected coating, respectively [1] as de-
scribed on the basis of Nyquist plots in the previous section. Therefore, in
the case of the ECM with two-time constats (Fig. 5b), the outer and inner
circles correspond to the high and low frequency loops, respectively.
Indeed, the outer circle of this ECM as well as the ECM shown in Fig. 5a,
was used to characterize the coating properties. The inner circle of ECM
with two-time constants (Fig. 5b), represents the characteristics of the
double layer formed at the coating/metal interface.
In these equivalent circuits, the elements Rs, Rc, and Rct define the
resistance of solution, coating and charge transfer, respectively. The
CPE (constant phase element) is substitute for an ideal capacitance
element when the capacitive loop, in the Nyquist curve, has a depressed
shape, originated from the surface inhomogeneity or porosity. The
impedance relation of the CPE element is defined as the following re-
lation:
1
ZCPE=
Y (j ) n
where Y is the CPE constant with a dimension of Ω−1 sn cm-2, ω is the
angular frequency (rad/s), n is the CPE exponent as a measure of the
surface inhomogeneity or porosity level and j is the imaginary number
( 1 ).
The value of ideal capacitance can be estimated using the CPE
parameters. In this regard, the value of coating capacitance (Cc) was
calculated using Hsu and Mansfeld formula (Eq. (2)) based on the
normal distribution of time constants as follows [31,32]:
Progress in Organic Coatings xxx (xxxx) xxxx
(
Cc = Yc /R cnc -1)1/n c
(2)
where parameters nc and Yc are the CPE exponent and constant for a
coating, respectively. In the case of the double layer, the surface dis-
tribution of time constants is more appropriate and hence the value of
double layer capacitance (Cdl) was calculated by the Brug formula as
follows [33]:
Rs Rct
(1-ndl )/n dl
Cdl=Ydl1/ndl
Rs + R ct (3)
where ndl and Ydl are the CPE exponent and constant for the double
layer, respectively. Based on these concepts, the EIS spectra were well
fitted to the proposed equivalent circuit using Zview software and the
impedance parameters were estimated.
3.3.3. Variations of impedance parameters of coating
Variation of impedance parameters including Rc, Cc and nc for the
coatings without and with different concentrations of nPAni(DBSA) in
SA solution during 100 days of immersion are shown in Fig. 6. As seen
in Fig. 6a, in the case of EPE coating, Rc decreases sharply during the
early period of immersion and after 28 days, it reaches to the steady
value of about 1 × 106 Ω cm2. This indicates the serious defects of EPE
coating and hence it is unable to handle the coating task (failed coating)
(1)
[13]; in this situation, the EIS measurement was not continued after 28
days. Furthermore, the EPE coating has the lowest value of coating
resistance (Rc), while the value of Rc for the other coatings, containing
different concentrations of nPAni(DBSA), is greater than 1 × 108 Ω cm2
all over the immersion time. The sequence of Rc as a function of nPAni
(DBSA) concentration is as following:
EPE/nPAni-1.5 > EPE/nPAni-3 > > EPE/nPAni-5 > EPE/nPAni-
0.5 > > EPE
4
M. Rayati and R. Arefinia
Fig. 4. Nyquist and Bode module plots for coating systems: (a and b) EPE/nPAni-1.5, (c and d) EPE/nPAni-3, (e and f) EPE/nPAni-5 in SA solution during 100 days
immersion.
This trend of variations can be mainly interpreted by the influence
of PAni nanoparticles concentration on the barrier properties of coat-
ings. Indeed, an increase in the amounts of nPAni(DBSA) within the
coating structure causes a balance between two main effects: (a) a
higher adhesion between polyaniline particles and epoxy ester, pro-
viding a positive influence on the physical resistance against the pe-
netration of electrolyte molecules which has been reported before [28];
and (b) an increment in the coating porosity due to the agglomeration
phenomenon of nanoparticles which was observed by the SEM images
(Fig. 1). Therefore, it can be stated that for the nPAni(DBSA) con-
centration less than 1.5%, the first effect is predominant, while for the
higher concentrations, the second is the major effect. Consequently, at
the end of immersion, the EPE/nPAni-1.5 coating has the highest bar-
rier resistance (Rc is from the order of 1011 Ω cm2) in SA solution.
Detailed inspection in Fig. 6a reveals that for the coatings con-
taining 1.5, 3 and 5% of nPAni(DBSA), Rc decreases gradually during
5
Progress in Organic Coatings xxx (xxxx) xxxx
14 days immersion and then increases up to the end of immersion. Si-
milar behavior for the epoxy ester coating containing polyaniline na-
noparticles in 3.5% NaCl solution has been reported [21]. This interest
behavior can be attributed to the self-healing function of nPAni(DBSA)
at the coating defects, where causes to reduce the penetration of elec-
trolyte species; additionally it may decrease the chloride contamination
of solution within the coating pores through the ion scavengering
nature of polyaniline particles.
Fig. 6b shows the variations of coating capacitance (Cc) with time at
different concentrations of nPAni(DBSA) in SA solution. It is apparent
that at the beginning of immersion, the higher concentration of nPAni
(DBSA) is associated with the greater value of Cc likely due to the in-
crease of dielectric constant (ε) which can be related to coating capa-
citance, Cc using the following equation:
Cc= 0 A/d (4)
where ε0 is the permittivity of free space which is equal to 8.85 ×
M. Rayati and R. Arefinia Progress in Organic Coatings xxx (xxxx) xxxx

are shown in Fig. 6c. It can be found that at the beginning of immersion,
when the concentration of nPAni(DBSA) particle increases from 0 to
5%, the value of nc decreases approximately from 0.99 to 0.96 probably
due to the enhancement in the surface heterogeneity as observed by the
images of coating surface, taken before the immersion (see Fig. 1).
Fig. 6c shows that generally, the value of nc decreases with the im-
mersion time which can be ascribed to the increase in porosity level of
coating and agrees with the increase of Cc values (Fig. 6b). For the long
time of immersion, the lowest value of nc for EPE/nPAni-5 (Fig. 6c) is
likely due to the highest level of porosity while no significant difference
can be observed for the other coatings.

3.3.4. Variations of impedance parameters of double layer

As mentioned before, the impedance data implicate that for the EPE,
EPE/nPAni-0.5 and EPE/nPAni-5 coatings, electrolyte molecules can
pass through the coating thickness and reach to the metal surface
during the immersion time (see Figs. 3 and 4). In this situation, it is
possible to create a double layer at the metal/coating interface and the
impedance parameters, corresponding to the double layer, were esti-
mated using the fitting procedure and their variations versus the im-
mersion time are presented in Fig. 7.
Fig. 5. ECMs used to analysis the EIS data for coatings in (a) intact and (b) Figs. 7a through c show that for the coating free of nPAni(DBSA)
defected state. particles (EPE), during just 21 days of immersion, the double layer
resistance (Rct) decreases sharply about two orders of magnitude from
about 108 to 106 Ω cm2, the double layer capacitance (Cdl) increases
10−12 F m−1 and A is the area of working electrode, d is the coating
markedly from 10−9 to 10-7 F cm-2 and ndl decreases significantly from
thickness. With respect to Eq. (4), the conductive nature of nPAni
0.90 to 0.65. These variations agree with the intensive decrement of Rc
(DBSA) is responsible for the increase of Cc as a result of the en-
(Fig. 6a), supporting the hypothesis that the barrier resistance is only
hancement of parameter ε. However, the obtained data implies that
mechanism against corrosion development which is considerably wea-
there is no linear relationship between Cc and parameter εε, which
kened by the immersion time. This causes a serious attack of corrosive
implies that the increase of nPAni(DBSA) has no linear effect on the
species at the metal surface and thus the fast deficient of EPE coating in
increment of dielectric constant (ε) of coating.
SA solution.
Fig. 6b shows that during the early period of immersion (until 14
However, addition of 0.5% nPAni(DBSA) within the epoxy ester
days), the trend of variation of Cc with time depends on the con-
produces an approximately high value (about 109 Ω cm2) of Rct over 21
centration of nPAni(DBSA) i.e. at the low concentrations (0.5 and 1.5%)
days immersion (Fig. 7a), indicating that EPE/nPAni-0.5 coating is
of nPAni(DBSA), Cc increases while at the concentrations (3 and 5%), a
capable of efficiently protection of the carbon steel against the corro-
reverse trend of variation is observed. These behaviors can be inter-
sion process in this span time. This result is likely arisen from the in-
preted by the diffusion effect of electrolyte molecules within the
hibition effect of nPAni(DBSA) through an active mechanism which will
coating, where causes two opposite effects on the dielectric constant (ε)
be discussed later. Nevertheless, after 21 days, a significant decrease in
of the coatings: from one hand, the penetration of hydroxyl groups
the values of Rct (reaches to about 107 Ω cm2) can be explained by two
causes the deprotonation of nPAni(DBSA) structure and hence de-
main reasons: the low resistance of coating in term of Rc, facilitating the
creases the coating conductivity in term of ε; on the other hands, the
diffusion of electrolyte species towards the metal surface associated
enhancement of water content within the coating pores results in an
with the lack of nPAni(DBSA) reducing the ability to made an active
increase of ε because of the high dielectric constant of water. With
inhibition for a long time immersion. In this regard, Schauer et al. was
respect to these concepts together with Eq. (4), it can be found that for
reported that the barrier properties of coating affects the durability of
the coatings EPE/nPAni-3 and EPE/nPAni-5, the early effect is pre-
active protection mechanism [22]. Moreover, Fig. 7b and c show a
dominant, resulting the decrease of Cc with immersion time. While the
significant increase of Cdl and a decrease of ndl for the EPE/nPAni-0.5
value of Cc increases with time for the coatings EPE, EPE/nPAni-0.5 and
coating at the early time of immersion probably due to the enhance-
EPE/nPAni-1.5 as a result of the dominant effect of water penetration.
ment in the amounts of corrosion products, resulting an increase in the
After the initial period of immersion, Cc values for approximately all
surface heterogeneity; however, these parameters do not change
the nPAni(DBSA) coatings increase steadily with time (Fig. 6b) which
markedly up to the end of immersion.
can be related to the dominant effect of enhancement of water content
In the case of EPE/nPAni-5 coating, the immersion up to 21 days in
within the coating structure as well reported previously [34,35].
SA solution is associated with the considerably increase of Cdl, decrease
However, this increment is negligible for the EPE/nPAni-1.5 coating.
of both Rct and ndl (see Figs. 7a through c) which can be directly related
Generally, In this span time, the Cc values are as the following order:
to the development of the corrosion process at the metal surface.
EPE/nPAni-1.5 < EPE/nPAni-3 < EPE/nPAni-0.5 < EPE/nPAni-5 However, after 21 days, a reverse behavior is observed i.e. both Rct and
ndl increase and Cdl decreases. In this regard, one may be expected the
This order of variations except for the EPE/nPAni-5 is reverse of that
increase of corrosion rate (decrement of Rct) with the immersion time,
reported for Rc values, suggesting that the increase of coating resistance
while this opposite behavior, observed after 21 days, is probably ori-
creates a higher barrier property against the penetration of electrolyte
ginated from the dominant effect of the active inhibition mechanism
molecules and hence the lowest value of Cc for EPE/nPAni-1.5 coating
relative to the barrier mechanism as a result of the high concentration
is ascribed to its highest Rc value. However, in the case of EPE/nPAni-5,
of nPAni(DBSA). This condition favors the formation of a secondary
the highest conductive nature of coating may be another reason for the
barrier layer at the metal/coating interface where was reported pre-
greatest values of Cc.
viously [21,27]. Moreover, this behavior is consistent with the incre-
Time dependency of parameter nc for the coatings with different
ment of OCP values for EPE/nPAni-5 coating after 21 days [14]. It can
concentrations of nPAni(DBSA) over 100 days immersion in SA solution
be proposed that the corrosion development stimulates nPAni(DBSA) to

6
M. Rayati and R. Arefinia Progress in Organic Coatings xxx (xxxx) xxxx

Fig. 6. Time dependency of impedance parameters of the double layer: (a) Rc, (b) Cc and (c) nc for the coatings containing different concentrations of nPAni(DBSA)
during 100 days immersion in SA solution.

form a passive layer at the anodic sites of the metal surface [16]. remarkable influence of hydroxyl groups on the protonated structure of
PAni nanoparticles. In other words, at this optimum concentration,
nPAni(DBSA) particles have been well protected against the dedoping
3.4. Surface analysis after long term immersion
process in SA solution.
After 100 days immersion, the EPE and EPE/nPAni-1.5 coatings
After 100 days immersion in SA solution, both surface and under-
were peeled from the metal surface and the material analysis of the
neath of EPE and EPE/nPAni-1.5 coatings were inspected using SEM
carbon steel surface was carried out using Raman spectroscopy and the
and the micrographs, taken from top surface of coatings, and are shown
recorded Raman spectra are shown in Fig. 9. In the case of EPE coating
in Fig. 8. It is obvious the formation of big cracks at the surface of EPE
(Fig. 9a), three strong bands at 637, 834 and 1110 cm−1 corresponding
coating while no surface damage is apeared at the surface of EPE/
to aromatic ring vibrations, out of plane bending of aromatic CeH and
nPAni-1.5 coating (Fig. 8a and b). These observations are in good
aromatic CeH stretching, respectively, can be observed where the weak
agreement with the lowest and the highest values of Rc obtained for the
band at 987 cm−1 corresponds to the epoxy group [19]. These data
EPE and EPE/nPAni-1.5 coating, respectively (Fig. 6a). Morover, Fig. 8c
indicate that the deterioration of EPE coating in SA solution causes the
and d shows a higher level of inhomoginity underneath the EPE coating
contamination of metal surface with the resin constituents as obtained
comared to EPE/nPAni-1.5, suggesting the accumulation of corrosion
by the intensive decrease of Rc value during the immersion time (see
products at the metal/coating interface of EPE coating which agrees
Fig. 6a).
with the lowest values of Rct for this coating (Fig. 7). Therefore, the
Furthermore, Fig. 9a shows the presence of corrosion products,
smooth surface of carbon steel for EPE/nPAni-1.5 coating can be at-
composed of a poorly crystallized phase of goethite α-FeOOH (bands at
tributed to the fact that corrosion process has been significantly low-
393, 480 and 1002 cm−1) [36,37] and two weak bands at about 663
ered by the addition of 1.5% nPAni(DBSA) within the epoxy ester
cm-1 and 734 cm-1 corresponding to the magnetite Fe3O4 and maghe-
coating.
mite γ-Fe2O3, respectively [38,39].
The visual inspection showed the green color of the EPE/nPAni-1.5
In contrast, Fig. 9b shows that all over the frequency range of
coating even after 100 days immersion in SA solution, reflecting no

7
M. Rayati and R. Arefinia
Fig. 7. Time dependency of impedance parameters of the double layer: (a) Rct, (b) Cdl and (c) ndl for the coatings containing different concentrations of nPAni(DBSA)
during 100 days immersion in SA solution.
Raman spectrum, the peak bands for the EPE/nPAni-1.5 coating are
sufficiently weak to conclude the presence of negligible corrosion
products at the metal surface due to the anticorrosion effect of nPAni
(DBSA). However, the nature of the thin layer, formed at the metal/
coating interface, was characterized using the Raman spectrum where
both goethite (at bands 302 and 480 cm−1) and maghemite (at bands
358, 422 and 726 cm−1) are identified [39,40]. Although, it is evident
that the contribution of the stable iron oxide of maghemite (γ-Fe2O3) is
much greater than that for EPE coating, resulting the formation of a
robust passive layer. Moreover, bands at 615, 1138 and 1165 cm−1 are
assigned to the δa(SO3), CeH stretching and S]O out of plane bending,
respectively [41], confirming the contribution of dodecyl benzene sul-
fonic anion in the structure of the passive layer. However, the results
obtained in the present work, advice that this thin layer cannot be
explored only using the EIS method when the coating impedance is high
enough like that resulted in the case of coatings containing 1.5 and 3%
nPAni(DBSA).
3.5. Protection mechanism of nPAni(DBSA)
The corrosion inhibition of carbon steel using epoxy ester coating
containing different concentrations of nPAni(DBSA) in SA solution can
8
Progress in Organic Coatings xxx (xxxx) xxxx
be attributed to both the barrier and active mechanism. In the case of
barrier mechanism, the coatings act as a physical barrier against the
diffusion of electrolyte molecules; additionally, it protects from the
nPAni(DBSA) particles against the deprotonation process in an alkaline
environment. In this regard, using the optimum concentration (1.5% by
weight) of nPAni(DBSA) has a vital role to attain the best barrier
properties [28].
The active inhibition mechanism of nPAni(DBSA) is mainly related
to the formation a passive layer at the metal/coating interface.
Moreover, the shift of OCP values to the noble direction suggests that
the nPAni(DBSA) acts as an anodic inhibitor [13,42]. According to the
literature, the opinions about the formation of a passive film at the
metal/coating interface can be categorized into two main groups: the
first is that the corrosion process provides a driving force to release the
dopant anions at the defected points of the coating followed by the
reaction of metal cations with the anion dopants to form an iron(do-
pant) complex [1,16,21,25,27]. The second view is based on the redox
property of polyaniline, yielding the formation of a stable iron oxide
layer e.g. maghemite (γ-Fe2O3) as reported by some researchers
[6,26,43].
In the present work, Raman spectroscopy results demonstrate the
formation of both the stable iron oxide (γ-Fe2O3) along with the iron/
M. Rayati and R. Arefinia Progress in Organic Coatings xxx (xxxx) xxxx

Fig. 8. SEM images taken from: (a and b) top surface, (c and d) underneath the EPE and EPE/nPAni-1.5 coatings, respectively after 100 days immersion in SA
solution.

dopant complex. At the low concentration of polyaniline, Kalendová 4. Conclusion

et al. [9] proposed that only the polyaniline particles that are in contact
with the metal surface could participate in the active protection me-
chanism which is similar to that observed in the present work at 1.5%
nPAni(DBSA).
Generally, based on the obtained results, it can be found that re-
gardless the concentration effect of nPAni(DBSA) on the barrier me-
chanism, an increase in the content of nPAni(DBSA) within the coating
structure strengthens the active inhibition mechanism. However, as
recommended by Schauer et al., the barrier property of a coating has a
direct influence on the durability of its active inhibition mechanism
[22].
This work describes the concentration effect of DBSA doped poly-
aniline nanoparticle (nPAni(DBSA)) on the anticorrosion behavior of
epoxy ester coating applied on the carbon steel surface during 100 days
immersion in a saline-alkaline solution (3.5% NaCl and pH 9). The most
important results are summarized as following:
- The addition of nPAni(DBSA) improves significantly the antic-
orrosion properties of the epoxy ester coating in comparison with
the coating without nPAni(DBSA). In this regard, an increase in the
content of nPAni(DBSA) up to 1.5% resulted in the enhancement of
the barrier properties of coatings because of the cohesion between

Fig. 9. Raman spectrum of the coating/metal interface for: (a) EPE and (b) EPE/nPAni-1.5 coatings at the end of immersion in SA solution.

9
M. Rayati and R. Arefinia
nPAni(DBSA) and epoxy ester; nevertheless, further addition of
nPAni(DBSA) causes a negative effect due to the enhancement in the
porosity level.
- At the appropriate concentrations (1.5 and 3%) of nPAni(DBSA), the
coatings act as an intact state all over the immersion, i.e. the elec-
trolyte molecules are unable to reach the metal surface because of
the superior inhibition through the barrier mechanism. However, at
both the low (0.5 %) and the high (5%) concentrations of nPAni
(DBSA), the coating performance changes to a defected state only
after a short time of immersion. In this situation, the corrosion
protection of carbon steel is mainly processed through the active
mechanism of nPAni(DBSA). Therefore, for a defected coating, the
greater amounts of nPAni(DBSA) (e.g. 5%) may provide a better
performance of the coating in a long term of immersion. On the
other hand, the barrier property has a great influence on the dur-
ability of the active inhibition.
- The surface analysis of the coatings by Raman spectroscopy de-
monstrated that the active inhibition mechanism of nPAni(DBSA) is
processed by the formation of a passive layer at the metal/coating
interface, where the nature of this layer is mainly composed of both
the stable iron oxide mainly as maghemite, associated with the iron/
dopant complex.
Declaration of Competing Interest
None.
Acknowledgment
We highly appreciate Khorasan Razavi Gas Co. for providing the
laboratory facilities for conducting the experiments in this research.
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