Progress in Organic Coatings 111 (2017) 240–247

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Progress in Organic Coatings

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A study on corrosion protection of different polyaniline coatings for mild MARK

steel
⁎ ⁎
Yingjun Zhanga,b,c, , Yawei Shaob, , Xiaoling Liud, Chao Shib, Yanqiu Wangb, Guozhe Mengb,
Xianguang Zenga,c, Yan Yanga,c
a
College of Materials Science and Engineering, Sichuan University of Science and Engineering, Zigong, 643000, PR China
b
Materials Science & Chemical Engineering College, Harbin Engineering University, Nantong ST 145, Harbin, 150001, PR China
c
Sichuan Province Key Laboratory for Corrosion and Protection of Materials, Sichuan University of Science and Engineering, Zigong, 643000, PR China
d
Institution of Materials Science and Engineering, Ocean University of China, Qingdao, 266100, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: The emeraldine base and salt (hydrofluoric acid and camphorsulfonic acid doped) forms of polyaniline (PANI)
Corrosion protection were synthesized and added to be epoxy coating. The corrosion protection of different PANI coatings was studied
EIS by EIS. Results indicated that different PANI coatings could offer the corrosion resistance of mild steel. However,
Mild steel the camphorsulfonic acid-doped PANI coating had the best performance in corrosion protection among the four
PANI coating
systems under investigation. The corrosion product layer was analyzed by SEM and XPS, indicating that PANI
XPS
changed the morphology and component of the corrosion product layer. Moreover, the protective mechanism
imparted by PANI was discussed.

1. Introduction
PANI has been widely studied for a variety of applications in an-
ticorrosion coatings for the past three decades since DeBerry showed in
1984 that the electrochemically deposited polyaniline (PANI) protected
stainless steel by anodic protection [1–6]. Until to the present time, two
forms of PANI have been the most thoroughly investigated in antic-
orrosion coatings: these are the non conducting emeraldine base (EB,
half-oxidized form) and the conducting emeraldine salt (ES, half-
oxidizedand protonated form) respectively. Different results of protec-
tion were obtained, and different mechanisms were proposed, de-
pending on the metal used, the method of synthesis, the corrosion
environments, and the preparation method of coating.
Some findings indicated that the EB form of PANI had an effective
protection for steel in NaCl and NaOH solutions. The positive protection
effects of the EB form of PANI was possibly due to its good adhesive
property toward the metal substrate and the oxidation-reduction
(redox) catalytic property [7–11]. However, other studies showed that
the EB form of PANI, even with an epoxy topcoat, did not protect steel
from the Na2SO4 solution because of poor barrier property and adhe-
sion [12]. Many studies concluded that the EB form of PANI coating
provided better protection from corrosion for steel substrates than the
ES form of PANI coating [13]. Nevertheless, an increasing number of
researchers revealed that the ES form of PANI coating could provide
protection for different metals [14–17]. Our previous work found that
the ES form of PANI coating had better corrosion protection on the
surface of magnesium alloy than that of the EB form of PANI coating
[18]. In addition, other reports found that the corrosion protection
provided by the ES form of PANI coating was strongly influenced by the
type of dopant [19].
Moreover, different protection mechanisms of PANI coating, such as
anodic protection, barrier protection, corrosion inhibitors, and shift of
electrochemical interface, have been proposed [20,21]. The anodic
protection of PANI coating is evidenced by the widely observed shift in
the corrosion potential to the passive region and increase in the po-
larization resistance for metal [22,23]. Evidence suggests the formation
of a thin oxide layer at the interface between the metal and the coating,
offering further protection for metal [24–26]. Some works also reported
that PANI/epoxy coating works as a better barrier against the diffusion
of the electrolyte and aggressive ions than epoxy coating alone [15].
The study about dopants or counter-ions suggested that PANI can re-
lease anions when damage occurs to the coating, forming a second
physical barrier that counteracts penetration of aggressive ions [27].
The work suggested that the active corrosion protection action of a
conductive PANI form due to shift of electrochemical interface and
separation of partial cathodic and anodic corrosion processes [28].
The abovementioned divergent research results and complex me-
chanism of PANI coating are complicated by many factors that possibly

⁎
Corresponding authors at: Materials Science & Chemical Engineering College, Harbin Engineering University, Nantong ST 145, Harbin, 150001, PR China.
E-mail addresses: zhangyingjun425@163.com, zhangyingjun@hrbeu.edu.cn (Y. Zhang), shaoyawei@hrbeu.edu.cn (Y. Shao).

http://dx.doi.org/10.1016/j.porgcoat.2017.06.015
Received 13 October 2016; Received in revised form 17 January 2017; Accepted 6 June 2017
0300-9440/ © 2017 Elsevier B.V. All rights reserved.
Y. Zhang et al.
influence occurrence of the processes. These results of existing research
inspired us to further investigate the corrosion performance and pro-
tection mechanism of PANI coating in more detail. Our previous work
found that a hydrofluoric acid-doped form of PANI coating exhibited
enhanced corrosion protection for magnesium alloy [18]; however,
whether it has the same protection for steel is still unknown. Dopants in
PANI can play an important role in corrosion protection because of the
formation of a metal-dopant interface [15]. José et al. [29] reported
that iron cations form a passivating complex with the PANI doping-
anion (camphorsulfonate) that acts as a second physical barrier to avoid
penetrating aggressive ions in sulfuric acid solutions with or without
chloride ions. The question is if Fe-sulfonate could form and have an
important role for steel in 3.5 wt.%. Therefore, the EB and ES (hydro-
fluoric acid and camphorsulfonic acid doped) forms of PANI were se-
lected in this study. Epoxy coatings containing different forms of PANI
powders were prepared on the surface of mild steel. The corrosion
performances of the prepared PANI coatings in 3.5 wt.% NaCl were
then investigated. The protective mechanism of the coatings was also
discussed.
2. Experimental
2.1. Sample preparation
The coating substrate materials were mild steel plates, which were
cut into the size of 50 mm × 50 mm × 5 mm. The elemental compo-
sitions of these materials are displayed in Table 1. The samples were
ground to 400-grit finish, degreased in acetone and ethanol, and dried
in air before the experiment.
The EB, hydrofluoric acid-doped, and camphorsulfonic acid-doped
form of PANI powders were synthesized by chemical oxidative poly-
merization in the laboratory as described in our previous study [18].
Briefly, some anilines dissolved in hydrochloric acid (or hydrofluoric or
camphorsulfonic acid) solution were oxidized and polymerized through
dropwise addition of ammonium persulfate solution with constant
stirring. After complete polymerization, the dark-green colored
polymer powders were filtered and washed with distilled water. The
hydrofluoric acid-doped camphorsulfonic acid-doped forms of PANI
powders were obtained after further vacuum drying. Especially, the
obtained hydrochloric acid-doped powders were dedoped by stirring in
aqueous ammonia solution. After the dedoping procedure, the EB form
of PANI powders was filtered and washed repeatedly with distilled
water and dried in a vacuum. The size of the powder was approximately
5–10 μm.
The different PANI coatings were obtained by dispersing the EB,
hydrofluoric acid-doped, and camphorsulfonic acid-doped forms of
PANI powders in epoxy resin (E44) using a ball grinding mill. The
powder concentration was 10 mass%. Polyamide (651) was used as the
curing agent. Epoxy resin and polyamide were obtained from Blue Star
Company (China). The coatings were cured at room temperature for
24 h, and then at 60 °C for another 24 h. The thickness of the dry
coatings was 100 ± 5 μm, as determined with a PosiTector 6000
coating thickness gauge (DeFelsko Corporation, USA). Epoxy resin
without any additions (varnish coating) was used as reference speci-
mens. In this study, EP, EB, HF, and CSA coatings were used to express
the varnish and epoxy coating containing EB, hydrofluoric acid-doped,
and camphorsulfonic acid-doped form of PANI powders.
Table 1
Elemental composition (wt.%) of mild steel.
C Mn Si S P Fe
0.14–0.22 0.30–0.65 ≤0.3 ≤0.05 ≤0.045 Bal
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Progress in Organic Coatings 111 (2017) 240–247
2.2. Measurements
The fourier transformation infrared (FTIR) spectroscopy (Nicolet
IR200, USA) using KBr pellets was conducted to characterize the syn-
thesized composite powders.
Electrochemical impedance spectroscopy (EIS) measurements were
performed at the 100 kHz to 10 mHz frequency range and an the AC
amplitude of 20 mV using an Autolab PGSTAT302 potentiostat
(Netherlands). A 3.5 wt.% NaCl solution was used as the electrolyte.
The coated mild steel, which had an exposed area of 9.8 cm2, was used
as the working electrode. Pt and a saturated Ag/AgCl (saturated KCl)
electrode were used as the counter and reference electrodes, respec-
tively. The experimental data were analyzed using the @ZsimpWin
commercial software (Princeton Applied Research, TN, USA).
After immersion measurement, the coatings on the surface of mild
steel were removed. The corrosion morphology of mild steel was
characterized with a camera and SEM (JSM-6480).
The surface composition of mild steel was characterized by XPS
which was performed with a PHI 5700 ESCA spectrometer using the Al
Kα X-ray source. The calibration of the binding energy of the spectra
was performed with the C 1s (284.6 eV) peak.
The glass transition (Tg) of the coatings was obtained by DSC using
TA Q200 (USA). The coatings were heated from ambient temperature to
150 °C at a constant speed (10 °C/min).
3. Result
3.1. Characterization of the PANI powders
The FTIR spectra of EB, hydrofluoric acid, and camphorsulfonic-acid
doped form of PANI powders are illustrated in Fig. 1. For the FTIR
absorption spectroscopy of the EB forms of PANI, the vibration at
1584 cm−1 was for the quinoid rings, with peaks at 1493 cm−1 at-
tributed to benzenoid ring units [30–32]; the peaks at 1298 cm−1
correspond to the CeN stretching of a secondary aromatic amine; the
peaks at 1159 cm−1 are assigned to vibrations associated with the CeH
of N]Q]N (Q was the quinoid rings). These results showed that the
synthesized powder was PANI in emeraldine state [33,34].
The FTIR spectra of hydrofluoric acid or camphorsulfonic acid-
doped form of PANI powders show that the characteristic peaks of the
EB form of PANI were found to shift to lower wavenumber side because
of the addition of hydrofluoric or camphorsulfonic acid. For example,
the corresponding peaks of quinoid ring structures were shifted from
1584 and 1159 cm−1 to 1558 and 1110 cm−1 (hydrofluoric acid
PANI-CSA
1556
1473
1291
1107
PANI-HF
1558
1472
1290
1110
PANI-EB
1159
1298
1584
1493
2500 2000 1500 1000 500
-1
Wavenumber/cm
Fig. 1. FT-IR spectra of synthesized polyaniline.
Y. Zhang et al. Progress in Organic Coatings 111 (2017) 240–247

Fig. 2. Bode plots of EP coating (a), EB coating (b), HF coating (c) and CSA coating (d) after different immersion time.

doped) or 1556 and 1107 cm−1 (camphorsulfonic acid doped). The

structure of benzene in the 1493 cm−1 shifted to 1472 cm−1 (hydro-
fluoric acid doped) or 1473 cm−1 (camphorsulfonic acid doped).

3.2. EIS measurements

In Fig. 2, the EIS of the EP, EB, HF, and CSA coatings was performed
based on the Bode plot with various exposure times. According to the
literature, the impedance modulus at low frequency (|Z|0.01 Hz) was an
appropriate parameter for characterizing the protective properties of
the coatings [9,35–37]. A coating with good anticorrosion performance
should show the values of |Z|0.01 Hz above 108 Ω cm2, whereas a poor or
failed coating shows the values of |Z|0.01 Hz less than 106 Ω cm2 [38].
The plots of |Z|0.01 Hz against the immersion time for the EP, EB, HF,
and CSA coatings are presented in Fig. 3. The Bode plot for the EP
coating showed a high |Z|0.01Hz value (approximately 1.6 × 1010 Ω
cm2) at the onset of immersion, indicating that this coating exhibited
good barrier property against corrosive ions. When immersion time Fig. 3. Evolution of |Z|0.01 Hz of EP coating, EB coating, HF coating and CSA coating with
increased, the |Z|0.01 Hz of EP coating decreased rapidly to 1.1 × 107 Ω immersion time in 3.5 wt.% NaCl solution.
cm2 in 4 days, and then decreased slowly. After 82 days of immersion,
the |Z|0.01Hz value was 5.5 × 105 Ω cm2 (less than 106 Ω cm2), in- coating. The HF coating showed |Z|0.01Hz 5.8 × 1010 Ω cm2 initially,
dicating failure of protection of the coating. For the EB coating, the then decreased to 3.2 × 108 Ω cm2 after 11 days, and then remained
value of |Z|0.01Hz decreased rapidly from 1.0 × 1011 Ω cm2 to relatively stable. After immersion 175 days, the value of |Z|0.01Hz was
3.2 × 107 Ω cm2 after 10 days of immersion, and then fluctuated 8.9 × 107 Ω cm2, indicating efficient protection of the HF coating. The
smoothly in some ranges. After 175 days of immersion, the value of value of |Z|0.01Hz of the CSA coating was 5.1 × 1010 Ω cm2 at the
|Z|0.01Hz was 1.3 × 107 Ω cm2, indicating an efficient protection of the

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Y. Zhang et al.
beginning of immersion, rapidly decreased to 1.1 × 109 Ω cm2 after
10 days, and then decreased slightly to 7.5 × 108 Ω cm2 after 175 days
of immersion, indicating further efficient coating protection. The EIS
result indicated that the protective effect of the coating for steel was:
CSA > HF > EB > EP.
3.3. Morphologies of the corroded surface beneath the coatings
The morphologies of the mild steel beneath the EP, EB, HF, and CSA
coatings after immersion in 3.5 wt.% NaCl solution are depicted in
Fig. 4. The surface beneath the EP coating showed severe corrosion
with numerous corrosion products [Fig. 4(a)] after 100 days of im-
mersion. After 400 days of immersion, some pitting and filiform cor-
rosions were distributed on the surface of the steel beneath the EB
coating [Fig. 4(b)]. However, compared with the EP coating, only some
filiform corrosions were observed on the surface of the steel beneath the
HF and the CSA coatings after 400 days of immersion [Fig. 4(c) and
(d)].
The corrosion morphology of the mild steel beneath the different
coatings after immersion measurement was further investigated by SEM
(Fig. 5). Serious corrosion and loose corrosion product were observed
on the surface of the mild steel beneath the EP coating [Fig. 5(a)].
Compact but discontinuous corrosion product was observed on the
surface of the mild steel beneath the EB coating [Fig. 5(b)], while very
compact and continuous product layers were found on the surface of
the steel beneath HF and CSA coatings [Fig. 5(c) and (d)].
3.4. XPS analysis of corroded surface
The surfaces of the mild steel beneath the EP, EB, and CSA coatings
after immersion in 3.5 wt.% NaCl solution were analyzed using XPS.
From the analysis of the XPS spectra, the compositions of the surface of
the steel beneath the three coatings are calculated and listed in Table 2.
The results showed that the compositions of the steel beneath the EP
coating included C, O, Fe, N, and Cl; those beneath the EB coating
consisted of C, O, Fe, N and Na; and those beneath the CSA coating
comprised C, O, Fe, N, and some S. The results of the photoelectron
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Progress in Organic Coatings 111 (2017) 240–247
Fig. 4. Surface morphologies of EP coating (a) after 100 days immersion
and EB coating (b), HF coating (c) and CSA coating (d) after 400 days
immersion.
signals after background subtraction and the curve fitting of O (1s) are
illustrated in Fig. 6. The O (1s) core-level spectrum beneath the EP
coating (Fig. 6(a)) was composed of Fe2O3 at 529.57 eV [39], Fe3O4 at
530.71 eV [40], and FeOOH at 531.86 eV [41]. The O (1s) core-level
spectrum beneath EB coating (Fig. 6(b)) had four components, namely,
O/(-C6H5-N-H-)n at 532.67 eV [42], which had been attributed to PANI;
Fe3O4 at 530.64 eV [40]; Fe2O3 at 529.53 eV [39]; and FeOOH at
531.57 eV [41]. However, beneath the CSA coating (Fig. 6(c)), the O
(1s) core-level spectrum was not only composed of Fe3O4 at 530.34 eV
[40]; Fe2O3 at 529.36 eV [39]; FeOOH at 531.07 eV [41]; and O/
(-C6H5-N-H-)n at 531.95 eV [42] but also of R-SO3 at 532.01 eV [43].
Fig. 7(a) and (b) showed Fe 2p spectra of the corresponding surfaces
of the mild steel beneath the EB and CSA coatings. Three peaks, namely,
Fe3O4 at 709.58 eV [44], Fe2O3 at 709.58 eV [45], and FeOOH at
712.01 eV [41], were observed on the alloy surface beneath the EB
coating (Fig. 7(a)). However, besides a peak of Fe3O4 at 709.71 eV [44],
Fe2O3 at 710.74 eV [45], and FeOOH at 711.71 eV [41] on the surface
alloy beneath the CSA coating (Fig. 7(b)), a peak at 712.82 eV was
observed, which was attributed to the presence of sulfonate ligand of
Fe.
4. Discussion
An organic coating offers corrosion protection for a metal substrate
immersed in an electrolyte in two ways. First, the coating acts as a
barrier to oxygen, water, and ions. Second, the coating can serve as a
reservoir for corrosion inhibitors, which aid the surface in resisting
attack [46–48]. Therefore, the corrosion protection of the different
PANI coatings for mild steel was discussed from two aspects.
4.1. Influence of the different forms of PANI on the barrier effect of coating
The electrical equivalent circuits in Fig. 8 were used for EIS data
fitting to obtain additional more information about coating. In the
circuits, Rs, Qc, Rpore, Qdl, and Rt are the solution resistance, coating
capacitance, coating pore resistance, double-layer capacitance, and
charge-transfer resistance, respectively. The change in Rpore and Rt was
Y. Zhang et al. Progress in Organic Coatings 111 (2017) 240–247

Fig. 5. SEM images of corrosion morphology of mild

steel beneath coatings after immersion measurement
beneath EP coating (a), EB coating (b), HF coating
(c) and CSA coating (d).

Table 2 different coatings. The result showed an increase of Tg in the different

Atom content of component on the surface of mild steel beneath EP coating, EB coating PANI coatings compared with that in the EP coating; the HF and CSA
and CSA coating from XPS spectra results. coatings had higher Tg than the EB coating. These results also indicated
Element
that the ES forms of PANI coating had higher barrier capability than the
EB forms.
Coating O Fe C N Na Cl S

EP coating 34.67 11.52 51.01 1.09 / 1.71 /

EB coating 26.56 4.68 66.33 2.18 0.25 / /
4.2. Influence of the different forms of PANI on the corrosion of mild steel
CSA coating 31.43 7.23 59.32 1.80 / / 0.22 substrate

Rt value is a measure of the resistance of the electron transfer across

determined by EIS data fitting.
The coating pore resistance Rpore generally reflects the barrier ability
of a coating to an electrolyte solution. Thus, Rpore is an important
parameter for evaluating the corrosion resistance of a coating [49,50].
The immersion time dependences of the coating pore resistances Rpore,
for EP, EB, HF, and CSA coatings are illustrated in Fig. 9. The Rpore
values for all the coatings significantly decreased in the beginning of
immersion time, then slowly decreased, and then remained stable in a
relative range after a certain period. After 100 days of immersion, the
Rpore values of the EP, EB, HF, and CSA coatings were 6.2 × 104,
1.8 × 106, 2.0 × 108, and 2.4 × 108 Ω cm2, respectively. The Rpore
value of the HF and CSA coatings were nearly four orders of magnitude
higher than that of the EP coating and two orders of magnitude higher
than that of the EB coating. After 175 days of immersion, the Rpore
values of the EB, HF, and CSA coatings were 2.6 × 106, 8.1 × 107, and
4.7 × 108 Ω cm2, respectively. This result indicated that the different
PANI coatings (EB, HF, and CSA coatings) had better barrier properties
than those of the EP coating. However, the HF and CSA coatings ex-
hibited higher Rpore values than those of the EB coating, which indicated
that the ES forms of PANI coating had higher barrier capability against
the electrolyte and better corrosion protective properties on the surface
of the mild steel.
Crosslink density is also a crucial parameter for revealing the barrier
properties of coatings. Higher crosslink density leads to a low diffusion
of ions and a good barrier property [51,52]. The extent of crosslink can
be determined from the glass transition (Tg) using DSC. The different
curves in Fig. 10 correspond to the glass transitions obtained for the
the metal surface; it is inversely proportional to the corrosion rate of
carbon steel [53]. Therefore, high Rt values result in difficult occur-
rence of corrosion reaction and low corrosion rate. The plot of charge
transfer resistances, Rt, against the immersion time for the EP, EB, HF,
and CSA coatings are presented in Fig. 11. The variation of the Rt values
of the EP and EB coatings had the same trend during immersion. The Rt
values of the EP and EB coatings decreased rapidly at initial immersion
and then decreased slowly. After 100 days of immersion, the Rt values
of the EP and EB coatings decreased to 3.3 × 105 and 3.3 × 107 Ω cm2,
respectively. The Rt values of the EB coating were two orders of mag-
nitude higher than those of the EP coating. When immersion time was
increased to 175 days, the Rt values of the EB coating decreased to
7.6 × 106 Ω cm2. The Rt value for the HF coating decreased in the
earlier stage and fluctuated within a certain range with the increase of
immersion time. After 175 days of immersion, the Rt value of the HF
coating was 2.6 × 107 Ω cm2. The values of the CSA coating gradually
decreased at the onset of immersion and then remained constant. After
immersion for 175 days, this Rt value was 2.8 × 108 Ω cm2, which was
an order of magnitude higher than that of that HF coating. The analysis
result of the Rt indicated that the corrosion process of mild steel under
the different forms of PANI coatings was more difficult than that of the
EP coating. Moreover, the CSA coating had the best protective prop-
erties among the three forms of PANI coating. The above corrosion
morphological observations have indicated that the different forms of
PANI coatings made the corrosion product layer more compact than
that of the EP coating (Fig. 4).

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Y. Zhang et al. Progress in Organic Coatings 111 (2017) 240–247

6000
(a)
FeOOH
Fe2O3
5500

Intensity/cps
Fe3O4
5000

4500

723 720 717 714 711 708 705 702 699

Binding Energy/eV

(b)
FeOOH
5500 Fe-CSA
Fe2O3

Intensity/cps
5000
Fe3O4
4500

4000

723 720 717 714 711 708 705 702 699

Binding Energy/eV
Fig. 7. XPS patterns of Fe 2p of mild steel beneath EB coating (a) and CSA coating (b).

Fig. 6. XPS patterns of O1s of mild steel beneath EP coating (a), EB coating (b) and CSA
coating (c).

4.3. Mechanism of corrosion resistance of the different forms of PANI

coatings

All of the above analytical results indicated that the different forms
of PANI coatings could provide protection for the mild steel in 3.5 wt.%
NaCl solution. The PANI coating can protect the metals from several
kinds of possible mechanisms, such as barrier protection, corrosion
inhibition, anodic protection, and formation of an insoluble counter-
anion salt, and the inhibitory properties of the counter-anion etc.
[21,23,25,54,55]. The mechanism of the corrosion resistance of dif-
ferent forms of PANI coatings for mild steel was discussed as follows.
4.3.1. EB form of PANI coating
According to the above EIS result, the EB coating not only had
higher impedance value (Fig. 3) but also had the higher Rpore values
than those of the EP coating (Fig. 9). The diffusion process of the
Fig. 8. Equivalent electrical circuit used to fit the EIS data different coatings with (a) one
capacitive loop (b) two capacitive loop.
electrolyte into the EB coating would be more difficult than the EP
coating. The EB coating could offer further effective protection for mild
steel in 3.5 wt.% NaCl solution. Therefore, barrier protection was one of
the mechanisms of the corrosion resistance of the EB form of PANI.
The higher Rt values of the EB coating indicated that the corrosion
process of mild steel under the coating was more difficult than that of
the EP coating (Fig. 11). The corrosion product layer of the mild steel

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Y. Zhang et al.
Fig. 9. The coating pore resistance, Rpore, as a function of the immersion time of EP
coating, EB coating, HF coating and CSA coating in 3.5 wt.% NaCl solution.
Fig. 10. DSC curve of EP coating, EB coating, HF coating and CSA coating.
Fig. 11. The charge transfer resistances Rt as a function of the immersion time of EP
coating, EB coating, HF coating and CSA coating.
beneath the EB coating was compact despite the presence of some
corrosion (Fig. 4(b) and (b)). One type of the proposed corrosion pro-
tection mechanisms of PANI for metal was the passivation effect be-
cause of the redox capability of the EB form of PANI.
First, the corrosion reactions (iron dissolution) of steel would occur
in 3.5 wt.% NaCl when the electrolyte diffused into the surface of the
steel via micropore or defect of the coating. Meanwhile the electron was
released.
Second, the EB form of PANI in the coating was reduced to the re-
ductive PANI (Leuco base (LB)) by capturing the electron (released by
iron dissolution).
Reduction of the EB form of PANI:
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Progress in Organic Coatings 111 (2017) 240–247
EB + e− → LB (1)
Next, the LB form of PANI was oxidized to its original form (EB form
of PANI) through the oxygen reduction reaction occurring on PANI
[56].
LB → EB + e− (2)
O2 + 2H2O + 4e− → 4OH− (3)
The presence of O/(-C6H5-N-H-)n in the result of XPS (Fig. 6) in-
dicated that an oxygen reduction reaction of PANI occurred on the
surface of the mild steel. The surface of the metal was covered with the
compact product layer, which was one of the mechanisms of the cor-
rosion resistance of the EB form of PANI, because of the cyclic reaction
of PANI. Therefore, the better protective corrosion capability of the EB
coating than the EP coating may be attributed to two main reasons.
First, the EB coating improved the barrier effect of the coating and
reduced the number of corrosive ion diffusions to the surface of the
steel; thus, the corrosion occurred slowly. Second, the oxygen reduction
reaction of the EB form of PANI could make the corrosion product layer
extra compact and offer further protection for steel.
4.3.2. ES form of PANI coating
According to the above analysis, the HF and CSA coatings not only
had higher Rpore (Fig. 9) and Rt (Fig. 11) values, but also had more
compact and continuous corrosion product layer (Fig. 5) than those of
the EB coating. Therefore, the HF and CSA coatings have remarkably
barrier properties than the EB coating. Meanwhile, the fitting results of
the O (1s) of XPS are depicted in Fig. 6. The presence of O/(-C6H5-N-H-
)n in the result of XPS (Fig. 6) indicated that an oxygen reduction re-
action of the ES form of PANI occurred on the surface of the mild steel.
Therefore, the barrier protection and formation of compact corrosion
product layer could be the most possible mechanism of the corrosion
resistance of the ES form of PANI coatings.
Moreover, the test result indicated that two kinds of the ES forms of
PANI coatings had different protective effects for mild steel. The CSA
coating had better protective corrosion ability than the HF coating. XPS
results revealed that not only O/(-C6H5-N-H-)n was present on the
surface of the mild steel beneath the CSA coating but also sulfonate
ligand of Fe (Fig. 7). Therefore, the mechanism of the protection of the
CSA coating is not only the barrier protection and the formation of the
passive film because of the redox reaction of PANI as abovementioned
but also the secondary reaction of the formation of dopant Fe complex.
The concomitant redox reaction with PANI salt (camphorsulfonic acid
doped PANI) and the sulfonate ligand anions were released. These
sulfonate ligand anions formed Fe complexes, which had a compact
microstructure and was difficult to dissolve in water, with mild steel.
Therefore, the corrosion product layer also supplied the protective ef-
fect on the surface of the mild steel [57].
In particular, the barrier protection and formation of the compact
corrosion product layer were the mechanisms of the corrosion re-
sistance of the HF coating. However, the CSA coating not only had good
barrier property but also formed the compact corrosion product layer
because of the redox reaction of PANI and also formed the Fe complexes
film because of the sulfonate ligand anions released from the cam-
phorsulfonic acid-doped PANI on the surface of the mild steel.
Therefore, the CSA coating can provide the best corrosion resistance on
mild steel compared with the EP, EB, and HF coatings.
5. Conclusion
The corrosion protection abilities of the EB and ES (hydrofluoric
acid and camphorsulfonic acid-doped) forms of PANI coatings on mild
steel were studied in the present work. The EIS results revealed that the
ES (especially camphorsulfonic acid-doped) forms of PANI coating ex-
hibited higher corrosion resistance, although all forms of the PANI
Y. Zhang et al.
coatings could offer corrosion resistance for mild steel in 3.5 wt.% NaCl
solution. SEM and XPS results indicated that the presence of PANI
changed the chemical structure of the corrosion product layer via the
redox reaction of PANI. Therefore, the mechanism of the corrosion
resistance of the different forms of PANI coatings for mild steel may be
of one or more kinds as follows: 1) barrier property; 2) passivation layer
via the redox reaction of PANI; 3) insoluble counter-anion salt.
Acknowledgements
The authors wish to acknowledge the financial supports of the
Research Foundation for the Introduction of Talent of Sichuan
University of Science and Engineering, China (Grant No. 2016RCL13,
NO. 2014RC30), International S & T Cooperation Project of China
(ISTCP) (2014DFR50560), the Fundamental Research Funds for the
Central Universities (HEUCFZ1502), the Foundation of Material
Corrosion and Protection Key Laboratory of Sichuan Province, China
(Grant No. 2016CL11, 2014CL11).
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