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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.
⁎
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 Progress in Organic Coatings xxx (xxxx) xxxx
performance [8,10,29]. According to the best of our knowledge, no The EIS spectra were recorded at an amplitude perturbation of 10
investigation has been performed to study the corrosion inhibition be- mV versus open circuit potential (OCP) over the frequency range of 100
havior of a PAni-ES blended coating in alkaline solution. kHz to 10 mHz. Prior to EIS measurements, the OCP values were re-
In the present work, the epoxy ester coatings blended with dodecyl gistered for at least 100 min to assure the steady condition of the
benzene sulfonic acid doped polyaniline nanoparticles (nPAni(DBSA)) coating system.
were prepared and applied on the carbon steel surface. The inhibition
effect of nPAni(DBSA) at different concentrations on the protection 2.3. Surface analyses
behavior of prepared coatings for 100 days immersion in saline-alkaline
solution (3.5% NaCl and pH 9) was investigated using electrochemical The top surface of coatings was analyzed using the scanning elec-
impedance spectroscopy (EIS) and the surface analysis methods of tron microscope (SEM, LEO 1450VP) before and after the immersion in
scanning electron microscopy (SEM) and Raman spectroscopy. SA solution. Ex-situ Raman spectroscopy technique was used to study
the corrosion product at the metal/coating interface. Raman spectro-
2. Experimental scopy was carried out by an AvaRaman-785 TEC with a 785 nm laser
wavelength, exposure time 15 s and laser power 500 mW.
2.1. Preparation of coatings
3. Results and discussion
Dodecyl benzene sulfonic acid doped polyaniline nanoparticles
(nPAni(DBSA)) were synthesized through the inverse microemulsion 3.1. SEM analysis of coating surface before immersion
polymerization method according to previous work [21]. Briefly, DBSA
as both surfactant and doping agent was mixed with hexane (Merck, 99 The surface of coatings containing different concentrations (blank,
%) as the solvent then 0.1 M aniline monomers (Merck, 99.5% distilled 0.5, 1.5, 3 and 5% by weight) of nPAni(DBSA) was studied using SEM
under reduced pressure) was added drop wise to solution and mixed 30 and the taken images are shown in Fig. 1. As can be seen, the surface of
min until reaches a homogenous milky solution. At the end, ammonium EPE coating is smooth and uniform while in the presence of nPAni
peroxydisulfate (APS) (Merck, extra pure) as oxidant agent was in- (DBSA), some white regions are observed on the surface of coatings
troduced to initiate the oxidative polymerization. The reaction tem- which is as an indication of agglomeration of PAni nanoparticles.
perature was kept at 0 °C during all steps. The green color mixture Moreover, the density and size of these regions are increased by an
indicated the conductive form of DBSA doped PAni and the products increase in the concentration of nPAni(DBSA). For the EPE/nPAni-5
were washed three times by ethanol, methanol, and distilled water and coating (see Fig. 1e), the white regions cover throughout the coating
then dried at 40 °C for 24 h. According to previous works, the synthe- surface; additionally, the rough and wavy shape of surface are probably
sized powder of polyaniline has a spherical shape with an average arisen from the high level of agglomeration of nPAni(DBSA) where was
particle size of about 30 nm [21,30]. reported before [14].
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- 3.2. OCP measurement
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. Fig. 2 shows variations of open circuit potential (OCP) versus the
Before application of coatings, the carbon steel plates were sand blasted immersion time for different concentrations of nPAni(DBSA) blended
with a profile of about 30 μm and then degreased with acetone. The epoxy ester in SA solution. It is apparent that the OCP values for EPE
coatings were applied to the carbon steel plates (SAE 1020) of size 5 cm and EPE/nPAni-0.5 coatings intensively decrease during about 21 days
× 5 cm where the average thickness of coatings after completely drying immersion and do not change considerably for the longer time of im-
at room temperature (25 ± 2 °C) for 10 days was 50 ± 5 μm. The mersion. The OCP values for EPE/nPAni-1.5 and EPE/nPAni-3 coatings
coating systems containing different concentrations of nPAni(DBSA) are shift to the more positive values for about 28 and 10 days of immersion,
named in Table 1. 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
2.2. EIS measurements 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
To manufacture the electrochemical cell, a glass tube with 2.25 cm of immersion.
diameter was firmly attached to the coated steel plate by means of a A continues decrease of recorded OCP values for a conventional
silicone adhesive where the isolated surface of coating was about 4.52 coating, subjected to a corrosive environment, will be expected due to
cm2. The EIS measurements were carried out with an Autolab po- the deterioration of coating and corrosion development process. Despite
tentiostat/galvanostat model 302 N in a three-electrode cell including this, increasing the OCP values for coatings with 1.5, 3 and 5% nPAni
an isolated surface of coating as working electrode, a saturated calomel (DBSA) is likely arisen from the active protection mechanism of nPAni
electrode (SCE) as reference electrode and a graphite rod as counter (DBSA) which has been addressed by some researchers [8,14,26,27]
electrode in 80 ml saline-alkaline (3.5 % NaCl and pH 9) electrolyte and will be further discussed in the next sections. Moreover, Fig. 2
named as "SA" solution. The solution pH was adjusted to 9 by addition shows that the coatings containing nPAni(DBSA) have higher values of
of aqueous NaOH. OCP compared with the EPE coating, which indicates the hypothesis
that nPAni(DBSA) acts as an anodic inhibitor in SA solution.
Table 1
The coating systems with different concentrations of nPAni(DBSA). 3.3. EIS measurements
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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 as a "defected coating", arisen from their low barrier properties [21].
c) and EPE/nPAni-5 (in Fig. 4e) coatings is composed of two distinct In the case of EPE/nPAni-1.5 and EPE/nPAni-3 coatings (see Fig. 4a
depressed loops or one loop with a large diameter as a result of the and b), the shape of Nyquist plots is composed of one incomplete loop
combination of two small loops. These observations mean that the over the all times of immersion. This indicats the superior protetion of
electrolyte molecules could pass the coating structure and reach to the these coatings against the corrosion development and their function is
metal surface, causing the initiation of corrosion process immediately as an "intact coating". Although, the change in the diameter of capaci-
after a short time of exposure to the corrosive environment. In this si- tive loop is influenced by change in the protective charactreistic of
tuation, the coatings without and with 0.5 and 5% nPAni(DBSA) behave 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.
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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. (
Cc = Yc /R cnc -1)1/n c
(2)
where parameters nc and Yc are the CPE exponent and constant for a
3.3.2. Simulation of coting behavior using ECMs
coating, respectively. In the case of the double layer, the surface dis-
The impedance data were analyzed using the equivalent circuit
tribution of time constants is more appropriate and hence the value of
models (ECMs) shown in Fig. 5. The ECM with one time constant
double layer capacitance (Cdl) was calculated by the Brug formula as
(Fig. 5a) and with two time constants (Fig. 5b) correspond to the cor-
follows [33]:
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 Rs Rct
(1-ndl )/n dl
the case of the ECM with two-time constats (Fig. 5b), the outer and inner Cdl=Ydl1/ndl
Rs + R ct (3)
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, where ndl and Ydl are the CPE exponent and constant for the double
was used to characterize the coating properties. The inner circle of ECM layer, respectively. Based on these concepts, the EIS spectra were well
with two-time constants (Fig. 5b), represents the characteristics of the fitted to the proposed equivalent circuit using Zview software and the
double layer formed at the coating/metal interface. impedance parameters were estimated.
In these equivalent circuits, the elements Rs, Rc, and Rct define the
resistance of solution, coating and charge transfer, respectively. The 3.3.3. Variations of impedance parameters of coating
CPE (constant phase element) is substitute for an ideal capacitance Variation of impedance parameters including Rc, Cc and nc for the
element when the capacitive loop, in the Nyquist curve, has a depressed coatings without and with different concentrations of nPAni(DBSA) in
shape, originated from the surface inhomogeneity or porosity. The SA solution during 100 days of immersion are shown in Fig. 6. As seen
impedance relation of the CPE element is defined as the following re- in Fig. 6a, in the case of EPE coating, Rc decreases sharply during the
lation: 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
1
ZCPE= coating and hence it is unable to handle the coating task (failed coating)
Y (j ) n (1)
[13]; in this situation, the EIS measurement was not continued after 28
where Y is the CPE constant with a dimension of Ω−1 sn cm-2, ω is the days. Furthermore, the EPE coating has the lowest value of coating
angular frequency (rad/s), n is the CPE exponent as a measure of the resistance (Rc), while the value of Rc for the other coatings, containing
surface inhomogeneity or porosity level and j is the imaginary number different concentrations of nPAni(DBSA), is greater than 1 × 108 Ω cm2
( 1 ). all over the immersion time. The sequence of Rc as a function of nPAni
The value of ideal capacitance can be estimated using the CPE (DBSA) concentration is as following:
parameters. In this regard, the value of coating capacitance (Cc) was
EPE/nPAni-1.5 > EPE/nPAni-3 > > EPE/nPAni-5 > EPE/nPAni-
calculated using Hsu and Mansfeld formula (Eq. (2)) based on the
0.5 > > EPE
normal distribution of time constants as follows [31,32]:
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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 14 days immersion and then increases up to the end of immersion. Si-
of PAni nanoparticles concentration on the barrier properties of coat- milar behavior for the epoxy ester coating containing polyaniline na-
ings. Indeed, an increase in the amounts of nPAni(DBSA) within the noparticles in 3.5% NaCl solution has been reported [21]. This interest
coating structure causes a balance between two main effects: (a) a behavior can be attributed to the self-healing function of nPAni(DBSA)
higher adhesion between polyaniline particles and epoxy ester, pro- at the coating defects, where causes to reduce the penetration of elec-
viding a positive influence on the physical resistance against the pe- trolyte species; additionally it may decrease the chloride contamination
netration of electrolyte molecules which has been reported before [28]; of solution within the coating pores through the ion scavengering
and (b) an increment in the coating porosity due to the agglomeration nature of polyaniline particles.
phenomenon of nanoparticles which was observed by the SEM images Fig. 6b shows the variations of coating capacitance (Cc) with time at
(Fig. 1). Therefore, it can be stated that for the nPAni(DBSA) con- different concentrations of nPAni(DBSA) in SA solution. It is apparent
centration less than 1.5%, the first effect is predominant, while for the that at the beginning of immersion, the higher concentration of nPAni
higher concentrations, the second is the major effect. Consequently, at (DBSA) is associated with the greater value of Cc likely due to the in-
the end of immersion, the EPE/nPAni-1.5 coating has the highest bar- crease of dielectric constant (ε) which can be related to coating capa-
rier resistance (Rc is from the order of 1011 Ω cm2) in SA solution. citance, Cc using the following equation:
Detailed inspection in Fig. 6a reveals that for the coatings con-
Cc= 0 A/d (4)
taining 1.5, 3 and 5% of nPAni(DBSA), Rc decreases gradually during
where ε0 is the permittivity of free space which is equal to 8.85 ×
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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.
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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
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M. Rayati and R. Arefinia Progress in Organic Coatings xxx (xxxx) xxxx
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 be attributed to both the barrier and active mechanism. In the case of
sufficiently weak to conclude the presence of negligible corrosion barrier mechanism, the coatings act as a physical barrier against the
products at the metal surface due to the anticorrosion effect of nPAni diffusion of electrolyte molecules; additionally, it protects from the
(DBSA). However, the nature of the thin layer, formed at the metal/ nPAni(DBSA) particles against the deprotonation process in an alkaline
coating interface, was characterized using the Raman spectrum where environment. In this regard, using the optimum concentration (1.5% by
both goethite (at bands 302 and 480 cm−1) and maghemite (at bands weight) of nPAni(DBSA) has a vital role to attain the best barrier
358, 422 and 726 cm−1) are identified [39,40]. Although, it is evident properties [28].
that the contribution of the stable iron oxide of maghemite (γ-Fe2O3) is The active inhibition mechanism of nPAni(DBSA) is mainly related
much greater than that for EPE coating, resulting the formation of a to the formation a passive layer at the metal/coating interface.
robust passive layer. Moreover, bands at 615, 1138 and 1165 cm−1 are Moreover, the shift of OCP values to the noble direction suggests that
assigned to the δa(SO3), CeH stretching and S]O out of plane bending, the nPAni(DBSA) acts as an anodic inhibitor [13,42]. According to the
respectively [41], confirming the contribution of dodecyl benzene sul- literature, the opinions about the formation of a passive film at the
fonic anion in the structure of the passive layer. However, the results metal/coating interface can be categorized into two main groups: the
obtained in the present work, advice that this thin layer cannot be first is that the corrosion process provides a driving force to release the
explored only using the EIS method when the coating impedance is high dopant anions at the defected points of the coating followed by the
enough like that resulted in the case of coatings containing 1.5 and 3% reaction of metal cations with the anion dopants to form an iron(do-
nPAni(DBSA). 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
3.5. Protection mechanism of nPAni(DBSA) [6,26,43].
In the present work, Raman spectroscopy results demonstrate the
The corrosion inhibition of carbon steel using epoxy ester coating formation of both the stable iron oxide (γ-Fe2O3) along with the iron/
containing different concentrations of nPAni(DBSA) in SA solution can
8
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.
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 Progress in Organic Coatings xxx (xxxx) xxxx
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