J Mater Sci

Metals &Ccorrosion
METALS & ORROSION

Corrosion performance of polypyrrole-bilayer coating

on carbon steel
Liu Yao Cho1,* , Luciano Grande Guiotti1, and Andrea Santos Liu2

1
Research and Development Institute – IP&D, UNIVAP, São José Dos Campos, SP 12244-000, Brazil
2
Federal Institute of Sao Paulo – IFSP, 145Km Dutra Highway, São José dos Campos, SP, Brazil

Received: 9 October 2022 ABSTRACT

Accepted: 14 December 2022
Ó The Author(s), under
exclusive licence to Springer
Science+Business Media, LLC,
part of Springer Nature 2022
Polypyrrole doped with phosphoric acid was electrochemically synthesized on
carbon steel from acetonitrile medium, and then a coating of polypyrrole doped
with a long carbon chain acid, dodecylbenzenesulfonic acid or lauric acid, was
electrodeposited to form a bilayer. The more protective performance of the
bilayers in relation to monolayers was explained in terms of adherence and low
porous, as confirmed by scanning electron microscopy. The corrosion perfor-
mance was also confirmed by electrochemical measurements of open-circuit
potential, potentiodynamic polarization curves and electrochemical impedance
spectroscopy in chloride solution. The polarization experiments indicated that
the corrosion potential values for polypyrrole-bilayer-coated steel were shifted
to the positive direction in relation to uncoated carbon steel, indicating anodic
protection. Tafel plots also indicated that the anodic current densities were
smaller for steel coated by polypyrrole-bilayer. In addition, the electrochemical
impedance data showed that the charge transfer resistance values are associated
with the resistance to electron exchange between the metal and the coating, and
depend on the type of long carbon chain dopant used in the outer-layer. Thus,
the suggested mechanism to explain the protection of carbon steel surfaces
against corrosion was associated to the passivation and barrier effect of the
polypyrrole-bilayer.

Handling Editor: Catalin Croitoru.

Address correspondence to E-mail: liu@univap.br

https://doi.org/10.1007/s10853-022-08094-8

GRAPHICAL ABSTRACT
Mechanism to corrosion protection of PPy-bilayer coated carbon steel.
Introduction
Corrosion of metals is an electrochemical process
whereby metal releases electrons to an oxidizing
species at the interface between metal and corrosive
media, resulting in the deterioration of the metal.
Among metal alloys, carbon steel is commonly used
in several industries and engineering structures due
to its excellent mechanical properties and low cost.
However, it is susceptible to corrosion in aggressive
media resulting in enormous economic loss [1–3].
In the last years, conducting polymers (CP) have
been studied for corrosion protection of many
metallic materials, such as aluminum, copper, nickel,
lead and carbon steel [1, 4–9]. Conducting polymers
are composed of conjugated chains containing p-
electrons delocalized along the polymer backbone
and combine physico-electrochemical properties that
make them a unique class of organic materials [5].
Among the CP, polypyrrole (PPy) is an attractive
material due to its properties such as good stability of
the oxidized form, high electrical conductivity and
ease synthesis by chemical or electrochemical method
[4].
Electrochemical method allows the control of
coating thickness and morphologies, by the opti-
mization of polymerization conditions to obtain pore-
free and adhesive coatings [1, 6, 10–14]. Moreover,
the electrodeposition of CP can promote the anodic
J Mater Sci
passivation of the metal followed by the formation of
polymer on the substrate [3, 10].
CP may protect metal surfaces by the barrier effect,
which inhibits the penetration of aggressive species
and protects the steel against corrosion. Moreover, if
the polymer is in the oxidized form, the anodic pro-
tection mechanism through which protective oxide
layers are formed on the metal surface might prevent
metal corrosion [4, 15, 16]. Furthermore, the media-
tion of oxygen reduction; cathodic protection and
controlled inhibitor release are other proposed pro-
tection mechanisms. Additionally, it has also been
reported that self-healing is promoted by CP, in
which the polymer can repair small defects sponta-
neously and form a passive state film on the surface
of metal substrate to inhibit the corrosion [7, 17–21].
In addition, PPy can provide corrosion protection
by using it as an additive, blended with conventional
polymers, resulting in a composite coating. Studies
have shown that even with low concentrations of CP
on epoxy coating, can promote higher barrier for
protection carbon steel against corrosion [22, 23].
The type of solvent and the dopant nature play an
important role in the coating performance of PPy for
corrosion protection. Although organic solvents are
less common, it enables the use of a range of water-
immiscible dopants. Tuken and collaborators have
reported that the film synthesized from acetonitrile
medium had a higher stability and less porous
structure than that prepared from an aqueous oxalic
J Mater Sci
acid solution, and therefore, the PPy deposited in
organic medium presented better corrosion perfor-
mance for steel surfaces [24]. Furthermore, the
selection of less nucleophilic solvents than water,
such as acetonitrile, affects the electrical conductivity
of the polymer. Yan and collaborators reported that
the stronger nucleophilicity the solvent has, the
shorter life of cationic free radicals, and the shorter of
the obtained conjugate chains, which results in the
lower conductivity and mechanical strength of the
PPy films [10].
Dopants can be incorporated into the PPy coatings
simultaneously during the synthesis, and corrosive
ions attack could be restricted. If the barrier effect
fails due to defects in the coatings, a dopant anion
could be attractive in the repair process since it is able
to passivate the metal surface within the defect.
During oxidation–reduction, small dopant anions
may be released from the conducting polymer and
form a passive layer at the metal surface [1, 7, 25].
Thus, a coating that contains a dopant which may
produce a barrier effect and another dopant capable
of inducing passivation could be interesting. Hien
and collaborators investigated a PPy-bilayer coating
that was electrochemically synthesized on an iron
surface. The inner-layer was doped with oxalate and
the outer-layer was doped with dodecylsulfate. Cor-
rosion protection experiments have indicated that the
bilayer coating performed significantly better when
compared to the coating doped only with dodecyl-
sulfate [26]. Vera et al. have also reported that when a
redox reaction occurs in matrix polymeric in the
presence of large carbon chain dopants, such as
dodecylbenzenesulfate, the cations instead of the
anions in the corrosive media diffuse through the
polymer structure [27]. Hung et al. have reported that
the joint doping of molybdate and camphorsulfonate
in PPy films deposited on carbon steel increased the
thermal stability and redox properties of the coating
[15]. The authors affirmed that the corrosion resis-
tance of this coating was better than the doped
coatings only with molybdate or only with cam-
phorsulfonate. Menkuer and Ozkazanc have shown
that the use of oxalate and dodecylbenzosulfonate as
dopants of PPy films presented good results for cor-
rosion protection of copper surfaces [28].
The corrosion performance of bilayer conducting
polymer electrodeposited from organic media has
been scarcely reported in the literature. In this work,
we present new results on the employment of PPy-
bilayers for steel protection as well as the role of large
molecules as dopant anions in conducting polymer
matrix, which are able to trap aggressive ions from
solution and decrease the corrosion attack to the
carbon steel surface. These coatings were electrode-
posited galvanostatically from acetonitrile medium
on carbon steel surfaces: an inner-layer was doped
with phosphoric acid and an outer-layer was doped
with a long carbon chain acid, dodecylbenzenesul-
fonic acid (DBSA) or lauric acid (LA). Coatings
morphology was analyzed by scanning electron
microscopy (SEM). Corrosion protection was evalu-
ated using electrochemical analysis (open-circuit
potential, potentiodynamic polarization and electro-
chemical impedance spectroscopy) in a saline
solution.
Experimental
Chemicals
The following reagents were used in the electro-
chemical synthesis of polypyrrole coatings: pyrrole
(Merk), acetonitrile (Merk), phosphoric acid
(Dynamica), lauric acid (Exodo Scientific) and dode-
cylbenzenesulfonic acid (Dynamica). Pyrrole was
distilled prior to use and the acid reagents were used
as received. Sodium chloride (Synth) was used in
corrosion experiments.
Electrochemical synthesis of polypyrrole
The electrochemical experiments were carried out at
room temperature (25 °C) in a single compartment
cell containing three electrodes. The working elec-
trode was a carbon steel (diameter: 2.0 cm and
thickness: 0.2 cm) with the composition (wt%): 0.19%
C, 0.46% Mn, 0.01% P, 0.005% S, 0.13% Si and Fe
balance. The electrodes were abraded using silicon
carbide papers with 320, 800 and 1200 grit, rinsed in
water and degreased with acetone before use. The
reference electrode was a saturated Ag/AgCl elec-
trode, and the auxiliary electrode was a platinum
wire. The experiments were carried out by a
Metrohm Autolab Potentiostat/Galvanostat model
PGSTAT302N.
Electrosynthesis of PPy coatings on carbon steel
electrodes was carried out by galvanostatic tech-
nique. The PPy coatings were deposited from

Table 1 PPy-bilayer electrosynthesis parameters
Sample Inner-layer
Dopant Applied current density
(mA.cm- 2)
PPy-PA|PPy- PA 0.20 mol 5.0
DBSA L-1
PPy-PA|PPy-LA PA 0.20 mol 5.0
L-1
acetonitrile solutions containing 0.20 mol L-1 pyrrole
and 0.20 mol L-1 of each analytical grade acid.
The applied current density and initial concentra-
tion of dopants for PPy-bilayers on carbon steel are
shown in Table 1. The time of deposition for each
PPy-layer was 3600 s. The bilayer-coated samples
were rinsed thoroughly with distilled water and
dried in a vacuum.
Characterization of the polypyrrole films
The morphology of carbon steel surfaces coated with
PPy films was analyzed using a Zeiss Scanning
Electron Microscope (SEM), model EVO MA 10. The
micrographs were obtained using a 20 keV electron
beam and images were taken at a magnification of
2000x. The PPy thickness was also estimated from
SEM images of the film cross section.
Element analysis of the coatings was investigated
by using EDX (INCA Oxford Instruments)
measurements.
The PPy-bilayer films composition was evaluated
by Fourier transform infrared (FTIR) and analyses
were conducted on a Frontier FTIR PerkinElmer
spectrometer, Spectrum One model, from 3500 to
450 cm-1 spectral range, with a resolution of
4 cm-1 and 16 scans. The spectra were obtained in
the reflection mode by the use of a universal total
attenuated reflection (UATR) accessory with a Zn-Se
crystal and applied pressure of 90 N over a previ-
ously ground sample.
An adhesive scotch tape (3 MÒ) was used for
testing adherence of PPy coatings following the pro-
cedure mentioned in ASTM D3359 standard.
J Mater Sci
Outer-layer
Dopant Applied current density
(mA.cm- 2)
DBSA 0.20 mol 5.0
L-1
LA 0.20 mol L-1 5.0
Electrochemical analysis
The corrosion performance of the PPy coatings was
evaluated by electrochemical experiments in 0.1 mol
L-1 NaCl solution.
Potentiodynamic polarization curves were
obtained by shifting the electrode potential from -
1.0 V to ? 0.1 V at a scan rate of 1.0 mV s-1, after
2 h immersion in the electrolyte. The corrosion
potential (Ecorr) and the corrosion current density
(jcorr) were obtained from the Tafel plots. The Ecorr is
the potential at which the current density is zero. The
jcorr was determined by extrapolation, to Ecorr, from
linear parts of the anodic and cathodic branches of
the Tafel plots.
Electrochemical impedance spectroscopy (EIS)
measurements were performed at a frequency range
from 100 kHz to 2 mHz with an amplitude of 10 mV,
after 8, 24 and 48 h immersion in the electrolyte.
Experimental data were analyzed by using the EC-
LAB v10.40 software.
Results and Discussion
Electrodeposition of PPy coatings on carbon
steel
The electrodeposition of PPy-monolayers on carbon
steel surfaces in acetonitrile medium was successfully
performed, applying a current density of
5.0 mA cm-2 for 3600 s, and maintaining the same
deposition charge (1.8 9 105 C m- 2).
In concordance with our results, Rahman and col-
laborators have reported by salt spray experiments
that PPy coating did not work well when the thick-
ness of the coating is small. The authors have shown
that at the deposition time of 3600 s, the behavior of
PPy coating is similar to commercial primer [29].
J Mater Sci
In addition, the PPy-bilayer coatings were also
successfully electrosynthesized on carbon steel sur-
faces from organic solvent acetonitrile (potential–
time curves shown in Supplementary Information—
Fig. 1S). An inner-layer of phosphoric acid-doped
polypyrrole was easily obtained at the applied cur-
rent. The phosphoric acid system was selected as it
gives a stable pre-layer of polymer that was used to
deposit the PPy-DBSA or PPy-LA outer-layer.
The obtained PPy films were thin, smooth, black
and homogeneous. The adherence of the coatings
was estimated at 75 and 100% leading to a normal-
ized tape test.
The inner-layer (doped with phosphoric acid –
PPy-PA) reached a potential for polymerization,
approximately 1.0 V vs Ag/AgCl, after about 890 s
reaction. This time may be associated with elec-
trodissolution of carbon steel and metal surface pas-
sivation [5]. The outer-layer of the PPy-PA|PPy-
DBSA coating exhibited a lower monomer oxidation
potential (? 0.3 V vs Ag/AgCl) than PPy-PA|PPy-
LA sample (? 3.1 V vs Ag/AgCl). Hydrogen bond-
ing between the SO3H group in DBSA and the NH
group in PPy could affect the formation rate of the
doped PPy [15].
The long carbon chain dopants in the outer-layer
were chosen for this study because of their contri-
bution in doping the conducting polymers and their
use as corrosion inhibitors [30].
Figure 1 FTIR spectra of a Undoped-PPy, b PPy-PA|PPy-LA
and c PPy-PA|PPy-DBSA.
Characterization of the PPy films
FTIR
FTIR spectroscopy was used to analyze the PPy
composition. Figure 1a shows the spectrum of
undoped polypyrrole and spectra of polypyrrole-bi-
layer are shown in Fig. 1b (PPy-PA|PPy-LA) and
Fig. 1c (PPy-PA|PPy-DBSA).
Bands at 1030–1040 cm-1 and 1520–1560 cm-1
were observed in all spectra and were attributed to
the N–H bending deformation and C=C stretching
pyrrole ring, characteristic of polypyrrole coatings
[31]. Bands at 3000–2840 cm-1 were observed for
doped coatings and were not observed for the
undoped coating. These bands were attributed to C–
H sp3 stretching vibrations [32], characteristic of the
long carbon chain acids used as dopants. A band at
960 cm-1 was detected in doped coating spectra,
corresponding to the P-O bending vibration [33],
which suggests the phosphoric acid doping. Fur-
thermore, a band at 1150 cm-1 for PPy-PA|PPy-
DBSA was attributed to S=O symmetric stretching
[32], characteristic of the sulfonic group in DBSA.
Table 2 shows the main FTIR bands observed
(Fig. 1) for PPy coatings samples, as well as the
expected (from the literature) bands.
SEM and EDX analysis
Figure 2 shows SEM images of PPy-monolayers on
carbon steel surfaces. The morphology was changed
by the different dopants. Typical morphology of
granular PPy can be seen in coatings electrodeposited
from phosphoric acid (Fig. 2a) and DBSA (Fig. 2b).
These structures were not observed in PPy electro-
formed in lauric acid (Fig. 2c). Additionally, Fig. 2d
shows the micrograph for undoped PPy synthesized
in the dopant absence.
An adhesive tape test was performed to verify the
adherence of PPy-monolayer coatings on the metal
surface and it showed that the phosphoric acid con-
taining layer was more adherent than others.
According Fig. 2a, the coating from phosphoric
acid dopant presents higher compactness and uni-
formity. In addition, Hosseini and collaborators have
shown that with phosphate anions, greater globular
growth of the polymer is obtained. Also, the authors
have reported that the compaction of the coating is
enhanced in phosphate dopant [34].
 J Mater Sci

Table 2 FTIR band

assignments for bilayer Sample Band position (cm-1) Assignment Reference
coatings and undoped PPy
PPy-PA|PPy-DBSA 2941, 2905 and 2860 C–H sp3 stretching vibrations [32]
1530 C=C stretching pyrrole ring [31]
1150 S=O symmetric stretching [32]
1032 N–H bending deformation [31]
960 P–O bending vibration [33]
780 C–H out-of-plane vibrations [31]
PPy-PA|PPy-LA 2905 and 2860 C–H sp3 stretching vibrations [32]
1562 C=C stretching pyrrole ring [31]
1037 N–H bending deformation [31]
964 P–O bending vibration [33]
772 C–H out-of-plane vibrations [31]
Undoped PPy 1522 C=C stretching pyrrole ring [31]
1037 N–H bending deformation [31]
780 C-H out-of-plane vibrations [31]

Figure 2 SEM images of PPy-monolayer obtained from different dopants: a phosphoric acid; b DBSA; c lauric acid and d undoped PPy
film.

Moreover, the micrograph for undoped PPy pre-
sented a more porous fiber structure and no spherical
grains were observed.
Figure 3 shows the SEM micrographs of the steel
surfaces coated by polypyrrole-bilayer: PPy-PA|PPy-
LA and PPy-PA|PPy-DBSA.
The morphology of the PPy-PA|PPy-DBSA sample
(Fig. 3a) exhibits a structure similar to microspherical
cauliflower and a more compact and adherent film
[35]. According to Bazzaoui and collaborators, this
cauliflower structure is related to the intercalation of
the disordered polymer chain [36]. The PPy-PA|PPy-
LA coating (Fig. 3b) showed a compact morphology
J Mater Sci

Figure 3 SEM images at different magnifications of bilayer coating: a PPy-PA|PPy-DBSA and b PPy-PA|PPy-LA.

Table 3 EDX result of carbon

steel samples coated by PPy Sample C N O Fe Mn P S
coatings (% wt)
PPy 58.50 0.91 19.44 21.16 – – –
PPy-PO 35.68 12.76 34.96 2.77 – 12.76 –
PPy-DBSA 54.53 – 26.07 11.77 – – 7.64
PPy-LA 11.27 – 10.19 78.17 0.37 – –
PPy-PA|PPy-DBSA 70.90 – 18.93 1.48 – 0.64 8.06
PPy-PA|PPy-LA 53.99 6.73 26.98 2.96 – 9.34 –

with larger diameter microspheres (about 6 lm). The
denser the cauliflower structure of the coating is, the
better the corrosion protection performance [15].
These results can contribute to explain the effective-
ness of the corrosion protection achieved by PPy-bi-
layer coatings, as will be discussed in results of
electrochemical analysis.
Table 3 shows the EDX results obtained for the PPy
coatings. The sulfur and phosphor content in PPy
electrodeposited from dodecylbenzenesulfonic and
phosphoric acids indicated that sulfonic and phos-
phoric groups should be incorporated into the poly-
meric chain.
Figure 4 shows the morphology of uncoated car-
bon steel, PPy-PA|PPy-DBSA and PPy-PA|PPy-LA-
coated steel after potentiodynamic polarization
experiments. For the uncoated metal (Fig. 4a), it was
observed that the surface morphology was corroded
and covered by rust. On the other hand, coated car-
bon steel exhibited a compact surface without cracks
after polarization in chloride medium. In addition,
the PPy-PA|PPy-DBSA coating (Fig. 4b) did not
change significantly from its original morphology as
observed in Fig. 3a. In the case of PPy-PA|PPy-LA
(Fig. 4c), it was found that the microspheres had a
reduction in diameter and exhibited an overlap with
each other with the presence of small voids.
Furthermore, the average thickness of the PPy films
was estimated by SEM images of the film cross sec-
tion. The thickness of the monolayer deposited from
 J Mater Sci

Figure 4 SEM images of a uncoated steel surface and PPy-bilayers coating: b PPy-PA|PPy-DBSA and c PPy-PA|PPy-LA, after
potentiodynamic polarization experiment.

phosphoric acid (PPy-PA) was around 41 lm,
whereas PPy-bilayers coating electrodeposited from
lauric acid (PPy-PA|PPy-LA) and from dodecylben-
zenesulfonic acid (PPy-PA|PPy-DBSA) was around
85 lm and 82 lm, respectively.
Electrochemical analysis
The performance of PPy-bilayer coatings for corro-
sion inhibition of carbon steel was evaluated by OCP,
potentiodynamic polarization and EIS measurements
in chloride medium (NaCl 0.1 mol L-1).
more negative in relation to uncoated surface after
about 860 s. This result is related to smaller adher-
ence of such coating onto steel surface, which allows
the penetration of aggressive species and promotes
metal corrosion [7, 37] (Supplementary Information—
Fig. 2S).
The literature shows that phosphoric acid has been
used as a relevant dopant for PPy coatings, since

Evolution of the open-circuit potential

OCP measurements were recorded during two hours

for the carbon steel surfaces coated by PPy. The initial
potential of the uncoated carbon steel was - 559 mV,
decreasing over time to a steady state with a value
of - 653 mV. Besides, the initial potential values of
carbon steel coated by PPy are comparatively higher
than the potential of uncoated carbon steel. However,
Figure 5 Open-circuit potential recorded as a function of in
the OCP values for coated surfaces decreased with
0.1 mol L-1 NaCl solution for a uncoated carbon steel and coated
immersion time and the PPy-LA presented OCP by PPy-bilayers: b PPy-PA|PPy-LA and c PPy-PA|PPy-DBSA.
J Mater Sci
phosphate ions can form a passivation layer in which
PPy electrodeposition occurs. A release of phosphate
from the conducting polymer could repassivate the
metal surface if the protective layer is harmed
[34, 38, 39].
Figure 5 shows the OCP data for carbon steel
coated with PPy-bilayer. According to Fig. 5, OCP
values of carbon steel coated by bilayers were shifted
in the positive direction compared to uncoated car-
bon steel, which indicates corrosion protection
[35, 40–42]. In the case of PPy-bilayer-coated carbon
steel (PPy-PA|PPy-DBSA) the initial potential is ?
140 mV, this value is more anodic than the OCP of
uncoated steel, which attains during the time a value
around - 270 mV. Moreover, PPy-bilayer-coated
carbon steel (PPy-PA|PPy-LA) the initial potential is
-136 mV and reaches –576 mV after 2 h. Thus, with
increase in immersion time, the potential decreases
until a steady potential is obtained. However, the
final potential for PPy-bilayer is still more positive if
compared to the potential of uncoated carbon steel.
Linear polarization measurements
Potentiodynamic polarization experiments of steel
surfaces uncoated and coated with PPy-monolayers
and PPy-bilayers were carried out in 0.1 mol L-1
NaCl. The Tafel curves are shown in Fig. 6 and 7.
Analyzing Fig. 7, it was observed that uncoated
steel showed higher anodic currents in relation to the
substrate coated with PPy-bilayers, indicating more
oxidation of Fe to Fe?2 for uncoated carbon steel.
Figure 6 Tafel curves obtained from potentiodynamic
polarization in 0.1 mol L-1 NaCl solution for carbon steel
surfaces: a uncoated; b undoped; and PPy-monolayer
electrodeposited from different dopants: c phosphoric acid;
d DBSA; e lauric acid.
Figure 7 Tafel curves obtained from potentiodynamic
polarization in 0.1 mol L-1 NaCl solution for: a uncoated
carbon steel and coated by PPy-bilayer: b PPy-PA|PPy-LA and
c PPy-PA|PPy-DBSA.
Tafel curves also showed that the corrosion
potentials (Ecorr) for PPy-bilayer-coated carbon steel
with different dopants were shifted to a more posi-
tive direction compared to the uncoated surface,
indicating anodic protection [31, 40–43]. In addition,
PPy-PA|PPy-DBSA exhibited higher shift to a more
positive direction compared to PPy-PA|PPy-LA.
Nevertheless, the corrosion performance of PPy-
monolayers was lower as observed in Fig. 6, due to
low adherence and higher porosity of these coatings.
The corrosion parameters from the Tafel plots and
protection efficiency [44] are shown in Table 4.
Low porous films prevent the carbon steel surface
from oxidation. It has been reported that polymer
coatings with lower porosity have a better barrier
effect and reduce the transport of H2O and O2
through the polymer film [35]. In order to avoid
delamination and detachment of the conducting
polymer, it must be compact and adherent to the
substrate [7]. The presence of pores (micrograph in
Fig. 3d) on undoped PPy might explain its low effi-
ciency as indicated by OCP and linear polarization
experiments. Beltran et al. have also reported that
PPy films with more compact morphology showed a
notable improvement against corrosion even in
aggressive media of sulfuric acid [45]
The corrosion protection performance of the PPy-
bilayer coatings, during the immersion in an
aggressive medium, can be explained by: (i) there are
not big cracks or big pores in the coating as confirmed
by SEM micrographs; (ii) the penetration of chloride
ions through the polymer layers is hindered because
both dodecylbenzenesulfonate and laurate are fixed

Table 4 Electrochemical parameters from Tafel curves
Sample Corrosion potential, Ecorr Corrosion current density, jcorr (mA
(mV) cm-2)
Uncoated Carbon - 651 0.0295
Steel
Undoped-PPy - 790 0.0208
PPy-PA|PPy-DBSA - 487 0.0072
PPy-PA|PPy-LA - 605 0.0100
PPy-PA - 634 0.0201
PPy-DBSA - 727 0.0250
PPy-LA - 658 0.0160
in the PPy matrix; (iii) the transport through the
bilayer is blocked and the coating can act as an useful
oxidizer to remain the carbon steel in the passive
state [46].
Thus, corrosion performance of PPy-bilayer
depends on the corrosive ion transport through the
bilayers of conducting polymers, which is condi-
tioned by the characteristics of the dopant anions in
both layers. If an outer-layer doped with anions of
limited mobility into the polymer matrix such as
dodecylsulfonate or laurate, the oxidation process of
the inner-layer will be restricted because this process
requires the diffusion of anions through the outer-
layer, which is hindered due the size of its dopant
anion.
Electrochemical impedance spectroscopy
EIS measurements were performed to evaluate the
protection of the coatings for carbon steel in 0.1 mol
L-1 NaCl solution. Figure 8 shows the Nyquist plots
of PPy-bilayer coatings after different immersion
times in saline solution.
The curves were fitted with simple Randles circuit
(Fig. 9a) for uncoated steel and the circuit as shown
in Fig. 9b for coated steel, where RS represented the
solution resistance, RC corresponded to the pore
resistance, RCT represented the charge transfer resis-
tance, CPEDL represented the double layer capaci-
tance and CPEC indicated the coating capacitance. A
constant phase element (CPE) was introduced to
describe the non-ideal capacitive response of the
corrosion system.
Table 5 shows the electrochemical parameters fit-
ted by the equivalent circuit models, where the
polarization resistance (RP) of the bilayer-coated
J Mater Sci
% Protection Rp
efficiency (X.cm2)
– 913.4
29.5 1493.8
75.6 3054.6
66.1 2508.5
31.9 993.5
15.2 885.5
45.8 1583.7
electrode was the sum of RC and RCT values, which
reflected the corrosion resistance of these coatings.
The protection efficiency (g) of the coating was also
calculated as literature [3] and shown in Table 5.
From Fig. 8a, the curves of the uncoated carbon
steel displayed just one capacitive arc. It was
observed that the diameter of the semicircle
decreased over immersion time, which corresponded
to a reduction in corrosion protection for steel, as can
be seen by Nyquist plots (Fig. 8a and Table 4).
According to data, the RCT declined from 1.046 kX at
8 h to 0.969 kX at 48 h. The decrease in RCT over time
may be attributed to the gradual loss of corrosion
products. Furthermore, the values of n decreased
from 0.80 to 0.77 over this time period, which is
related to the formation of an unprotected and
heterogenic film on the surface [47].
The Nyquist diagrams for PPy-bilayer-coated steel
samples consisted of two semicircles, which corre-
spond to two different electrochemical processes: at
high-frequency region is associated to the responses
of the coating/electrolyte, and at low-frequency
region corresponds to the oxidation of the metal
through the polymer at the carbon steel and coating
interface.
At the high-frequency region, the RC parameter
was related to the penetration of the ionic species into
the micropores of the coating. The increasing RC
values over immersion time indicated that the pores
may be blocked by the corrosion products, which
difficult the penetration of corrosive species.
At the low-frequency region, the parameter RCT
represents the resistance to electron exchange
between metal and coating. The higher the RCT is, the
lower the corrosion of the metal [3].
J Mater Sci

Figure 8 Nyquist curves

obtained in 0.1 mol L-1 NaCl
solution for different
immersion times of a uncoated
carbon steel, b PPy-PA|PPy-
DBSA and c PPy-PA|PPy-LA
coatings.
 J Mater Sci

Figure 9 Equivalent circuit

for fitting the impedance data
for a uncoated carbon steel;
b PPy-bilayers coated carbon
steel.

Table 5 EIS parameters fitted by the equivalent circuits proposed

Sample Immersion time RC (kX) CPEC RCT (kX) CPEDL RP (kX) g

Y0 n Y0 n
(F.sn- 1) (F.sn- 1)

Carbon steel 8 h – – – 1.046 6.26 9 10–4 0.80 1.046 –

24 h – – – 0.970 6.49 9 10–4 0.78 0.970 –
48 h – – – 0.969 7.69 9 10– 4 0.77 0.969 –
PPy-PA|PPy-DBSA 8 h 0.027 7.84 9 10– 3
0.62 1.578 4.81 9 10– 2 0.86 1.605 35%
24 h 0.155 5.75 9 10– 3
0.43 30.00 4.47. 9 10– 2 0.82 30.15 97%
48 h 0.246 4.29 9 10– 3
0.41 40.00 4.71 9 10– 2 0.85 40.25 98%
PPy-PA|PPy-LA 8 h 0.563 3.61 9 10– 4
0.55 0.467 4.98 9 10– 2 0.84 1.030 –
24 h 1.164 3.12 9 10– 4
0.64 0.693 6.87 9 10– 2 0.87 1.857 48%
48 h 1.690 3.60 9 10– 4
0.63 0.685 1.35 9 10– 1 0.90 2.375 59%

The literature has reported that the doping–de-
doping process of PPy synthesized in the presence of
voluminous anions (X), which can trapped within the
polymer film and are not interchangeable, occurs by
the exchange of cations (C) in the electrolyte solution,
as described in Eq. 1 [27].
 
PPy0 Xn ½Cn=m PPynþ Xn þ n=mCmþ þ ne ð1Þ
This behavior may be explained by chloride ions in
the corrosive environment being pushed by large
dodecylbenzenesulfonate anions with negative char-
ges trapped within the polymer film due to electro-
static interaction. The polymer matrix may act as
permselective membranes against aggressive species
and avoid the attack of metal surfaces by chloride
[28].
It has been reported that larger doping anions are
less labile to be exchanged with aggressive species,
such as chloride anions, which could increase the
lifetime of the topcoat layer as well as the passive
layer [48].
The suggested mechanism to explain corrosion
performance by PPy-bilayers is shown in Fig. 10.
In this mechanism (Fig. 10) voluminous doping
anions into the conducting polymer are one possi-
bility to increase its ion-barrier properties, while
introducing phosphate anions leads to anti-corrosive
coatings with inhibition capability [7, 46, 48–50].
Thus, the inner-layer could be reduced and conse-
quently dopants could be available as a result of a
galvanic coupling between the conducting polymer
and the corroding metal. The phosphate could pas-
sivate the exposed metal surface due to its release of
the conducting polymer during the reduction process
[34, 38, 39].
In this process, the doped form of PPy captures the
electrons from the metal oxidation reaction and forms
the dedoped form of PPy.
J Mater Sci
Figure 10 Mechanism to corrosion protection of PPy-bilayer-coated carbon steel.
Conclusion
PPy-bilayer coatings were successfully electrosyn-
thesized on carbon steel surfaces from the organic
solvent acetonitrile.
The inner-layer of the PPy coating was electrode-
posited by using phosphoric acid dopant, which
contributed to corrosion performance. The phosphate
ions form a passivation layer in which PPy elec-
trodeposition occurs, and if the protective layer is
damaged, a release of phosphate from the polymer
can repassivate the substrate.
The outer-layer PPy-LA or PPy-DBSA coating was
evaluated for corrosion protection performance and
polarization experiments indicated that the corrosion
potential values of PPy-bilayer coatings were shifted
to the positive direction and the anodic current den-
sities were smaller in relation to uncoated carbon
steel, indicating anodic protection. Moreover, the
impedance data showed that the charge transfer
resistance values associated with the resistance to
electron exchange between metal and coating depend
on the type of long carbon chain dopant used in the
outer-layer.
It was observed that the outer-layer electrode-
posited from DBSA showed better performance to
protect the alloy against corrosion than LA, since this
coating is more compact and uniform, as verified by
SEM images.
On the other hand, electrochemical experiments
indicated that the corrosion performance of PPy-
monolayers is lower due to low adherence and higher
porosity of these coatings.
Funding
The authors received no financial support for the
research, authorship and/or publication of this arti-
cle. The authors are grateful for the infrastructure and
equipment maintained by the FAPESP and CNPq at
the Univap Research and Development Institute.
Declarations
Conflict of interest The authors declare that they
have no known competing financial interests or per-
sonal relationships that could have appeared to
influence the work reported in this paper.
Date availability The data from this study are
available from the corresponding author upon
request.
Ethical approval This article contains no animal or
human studies conducted by any of the authors.
Supplementary Information: The online version
contains supplementary material available at http
s://doi.org/10.1007/s10853-022-08094-8.
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