Received: 22 November 2016

DOI: 10.1002/maco.201609363
| Accepted: 21 August 2017

ARTICLE

Epoxy-based PANI/zinc oxide/glass fiber nanocomposite coating

for corrosion protection of carbon steel

Ahmad Rouhollahi | Mohammad Hamed Barzegar Khaleghi

Department of Chemistry, K. N. Toosi

University of Technology, Tehran In this work, a nanocomposite based on conductive polyaniline (PANI) was
1541849611, Iran polymerized, via reverse microemulsion polymerization, in the presence of
phosphoric acid and dodecylbenzenesulfonic acid. Applied simultaneously, these
Correspondence
Ahmad Rouhollahi, Department of acids act as dopants, increasing the solubility of PANI in organic solvents. They
Chemistry, K. N. Toosi University of further improve the corrosion protection performance of PANI by forming
Technology, Tehran 1541849611, Iran.
Email: [email protected]
phosphate-metal complex on metal surface. Zinc oxide nanoparticles were added
to the PANI mixture before introducing ammonium persulfate. The final product of
polymerization was added to an epoxy resin which served as the matrix for the
coating. In order to improve coating elasticity, which can enhance coating resistance
against impacts, E-glass fiber (GF) was added to the coating formulation. It was
observed that, with an optimized w/w%, the PANI/zinc oxide/GF composite
improved the coating characteristics. Coatings were further subjected to stress-strain
and DC polarization tests, and their cross-sections were investigated at break point by
means of SEM. DC polarization plots revealed that the addition of zinc oxide can also
shift the corrosion potential of steel toward positive potentials.

KEYWORDS
epoxy resin, glass fiber, microemulsion polymerization, nano zinc oxide, polyaniline

1 | INTRODUCTION Epoxy resin is commonly used as a matrix in fiber

reinforced coatings due to its outstanding characteristics such
Natural or synthetic fibers are commonly used in composites as good mechanical stability, easy processing, excellent
to improve the strength and rigidity of composite coatings.[1] chemical resistance, and good adhesion to different materi-
Different filaments such as carbon fibers and glass fibers (GF) als.[6] Numerous materials can be added to epoxy resin to
are widely used to reinforce natural or synthetic matrices.[2] enhance its characteristics. These materials may improve the
These fibers must endure external loads when the coating is impact and crack resistance, tensile strength, shear strength,
under stress.[3] In order to effectively prevent damage, these and adhesion properties of epoxy resin.[7–10] Of all available
coatings must provide strong adhesion between reinforcing materials, GFs have high modules and high toughness despite
fibers and the composite matrix. Indeed, the most important their relatively light weight, which makes them a popular
issue concerning adhesion is the interfacial region between choice for improving epoxy resin via formation of the epoxy-
the fibers and the matrix,[4] where good bonding is required so glass fiber composite.[11]
as to spread stress across the coating, thereby preventing Extensive research on the corrosion protection of metals
severe damage to specific areas.[5] using conductive polymer composites in a suitable resin

Materials and Corrosion. 2017;1–9. www.matcorr.com © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim | 1
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| ROUHOLLAHI AND BARZEGAR KHALEGHI

matrix has proven that conductive polymers can constitute a work inside a composite coating where the intrinsically
viable option when it comes to the enhancement of the conductive polymer (ICP) is distributed inside a non-
characteristics of coatings. Among these polymers, polyani- conducting matrix. Pure ICP coatings will eventually fail
line (PANI) has received more attention owing to its excellent under practical conditions. However, not all of the
physical and chemical stability, relatively inexpensive composite coatings may succeed to achieve sufficient
synthesis, and nontoxicity. PANI and PANI composites can corrosion protection performance under experimental
effectively protect metal substrates under special conditions situations. In some cases, it was reported that PANI can
through different protection mechanisms such as reversible act as an oxidizing agent that is not able to protect the
redox reaction whereby forming a passive oxide layer, release metal but just increases the corrosion currents. In other
of inhibitor dopants and barrier effect.[12–18] Bulk polymeri- cases, despite initial protection, as soon as the conduct-
zation of PANI usually results in a product which is insoluble ing polymer failed to provide active protection, fast
in usual organic solvents; this severely limits the product's and total reduction of the whole ICP film lead to total
potential application due to reduced processability.[19] failure. These reports show how close positive and
According to the existing literature, one way of overcoming negative effects can be when ICPs are utilized as
this problem is to use emulsion/microemulsion polymeriza- coatings.[38–41]
tion in the presence of suitable surface active agents. During In the present study, an anticorrosive composite was
emulsion polymerization, acting as dopants, surfactants prepared using PANI doped with both phosphoric acid
drastically improve PANI solubility in organic solvents.[20] (PA) and dodecylbenzenesulfonic acid (DBSA), via
Emulsion polymerization is usually performed in an acidic emulsion polymerization in the presence of zinc oxide
medium containing strong inorganic or weak organic acids nanoparticles, so as to enhance the corrosion protection
which serve as dopants and affect PANI properties. As performance of the coating. Milled E-glass fibers were
mentioned in the literature, acids such as H3PO4 enhance the introduced into the reaction vessel to form a fiber-
corrosion protection properties of PANI via forming a reinforced coating with superior physical properties
phosphate-metal complex on metal surface.[21] Recently, (Table 1). Finally, the composite was mixed with epoxy
conductive polymer composites containing metals and metal resin (serving as an adhesive matrix) before being applied
oxides have drawn much attention owing to the wide range on carbon steel specimens.
of their potential applications.[22] Hybrid composites
such as PANI/TiO2,[23] PPY/titanium dioxide,[24] PANI/
2 | MATERIALS AND METHODS
zinc oxide,[25] PANI/copper (II) oxide,[26] PANI/cadmium
(II) oxide,[27] PANI/bismuth (III) oxide,[28] and PANI/
2.1 | Reagents and materials
aluminum oxide[29] can be prepared following the procedures
described in the literature. Aniline (99%), DBSA (97%), phosphoric acid (85%), zinc
The performance of PANI can be improved by adding nitrate hexahydrate (98%), and sodium hydroxide (98%) were
metal oxides as they play a significant role in obtaining purchased from Sigma–Aldrich (USA). Ammonium persul-
PANI nanostructures with good surface morphological fate (APS) (98%) was procured from PanReac Química
properties and high conductivity. Zinc oxide is an n-type (Spain). Chloroform, epoxy resin (EP-400) and epoxy
semiconductor with a wide bond gap (3.37 eV) at room hardener (Ep-100-86) were obtained from local manufac-
temperature and good photocatalytic properties.[30] Nano turers (Amertat Co. and Pars Pamchal Chemical Co., both in
zinc oxide has garnered much interest due to its unique Iran). Double distilled water was used for preparing all
electrical properties, nontoxicity, and high stability. The solutions.
literature shows that zinc-polymer composites provide
highly effective anticorrosive coatings.[31–33] However,
2.2 | Synthesis of zinc oxide nanoparticles
conductive polymer composites suffer from one major
drawback, which is their poor adhesion to various Zinc oxide nanoparticles were prepared adopting the
substrates; this limits their application severely. Because procedure explained in the literature. [42] In doing so,
of their mechanical stability and chemical inertness, epoxy proper amounts of zinc nitrate and sodium hydroxide
resins are widely used as an adhesive matrix for anticorro- were dissolved in deionized water to form a solution of
sive coatings.[34] In a large number of previously reported Zn2+ and OH−. While sodium hydroxide solution was
studies, epoxy-PANI composites were used to overcome the being vigorously stirred, the zinc nitrate solution was
drawbacks of PANI coatings by applying epoxy as a major added to it dropwise. After 2 h of reaction time, a white
part of the coating matrix phase or a top coat.[35–37] precipitate deposited, which was washed with ethanol
Based on prior reports, this must be kept in mind that and distilled water before being centrifuged. Finally, the
corrosion protection by conducting polymers will only paste-like zinc oxide was dried in oven at 80 °C for 12 h.
ROUHOLLAHI AND BARZEGAR KHALEGHI
| 3

TABLE 1 Main chemical composition of GF

SiO2 Al2O3 CaO + MgO B2O3 Na2O + K2O
54 w% 14 w% 22 w% 10 w% >2 w%

FIGURE 1 Anilinium-DBSA complex

2.3 | Synthesis of PANI/zinc oxide/GF
composite
Suitable amounts of DBSA (0.2–0.5 ml) were added to 50 ml
A three-electrode cell was prepared for electrochemical
of chloroform, and a proper amount of distilled aniline
procedures. The setup consisted of an Ag/AgCl (filled with
(according to stoichiometric ratios) was added to this solution
3 M KCl solution) reference electrode, a platinum disk
to form a cloudy mixture. Under vigorous stirring, different
counter electrode (with a surface area of 2 cm2), and a carbon
amounts of zinc oxide nanoparticles and GF (Table 2) were
steel working electrode (with a surface area of 1 cm2). All
added to the above-said solution and APS (An/APS = 4/5),
working electrodes were cut and prepared from API 5L X52
and 1 M PA solutions were slowly introduced into this
oil pipes before being polished using different sizes (220, 400,
mixture. Stirring was continued for 1 h at room temperature
600, 800, 1200, and 2000) of emery paper and ultrasonically
until the dark green solution of PANI was formed. The
degreased in a solution containing acetone and methanol. A
emulsion was broken by adding methanol (with respect to the
double-jacketed cell was used in electrochemical experiments
phase diagram of the chloroform–methanol–water mixture).
to ensure steady temperature.
At this stage, PANI/zinc oxide/GF was separated from the
emulsion using a separatory funnel and dried in a rotary
evaporator. The resulting green paste was then washed 3 | RESULTS AND DISCUSSION
thoroughly with the ethanol/water (2:5 v/v) solution to
remove oligomers and unreacted reagents. Once the paste 3.1 | Formation of PANI doped with
dried in an oven at 50 °C overnight, the PANI/zinc oxide/GF PA-DBSA
green powder was obtained.
The importance of anionic dopants in the polymerization of
aniline is very well understood, and their impact on the
2.4 | Formation of the PANI/zinc oxide/GF conductivity, stability, and solubility of PANI has been
coating thoroughly investigated.[43] The present work focuses on both
processability and corrosion protection performance of PANI
A total of 0.5 g of the PANI/zinc oxide/GF nanocomposite
using PA and DBSA as dopants. During bulk polymerization
was dissolved in 2 ml of xylene under vigorous stirring for
of aniline, undesirable branching reactions and ortho-
60 min. This solution was then filtered to remove undispersed
coupling reaction may result in non-dispersible PANI.[44]
particles. At this point, 1 ml of the solution was added to
In order to prevent this, the polymerization of aniline was
3 ml of epoxy resin and 1 ml of hardener (following the
performed in a heterogeneous medium containing chloroform
manufacturer's recommendation) and homogenized for
and water. In this reaction, DBSA serves as both a surfactant
another 20 min to form the final paint formulation. Epoxy
paint was subsequently dip-coated on polished carbon steel
plates and allowed to dry for 2 days at room temperature.

2.5 | Electrochemical setup

Electrochemical analysis was carried out using a Metrohm
Autolab PGSTAT30 licensed for the NOVA 1.10.4 software.

TABLE 2 Values of w/w% of added zinc oxide and GF to the coating

formulation
Zinc oxide w/w% GF w/w%
0 0
0.5 2
1 5
FIGURE 2 The micelle formed during polymerization of aniline
2 10
in heterogeneous polymerization
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| ROUHOLLAHI AND BARZEGAR KHALEGHI

PANI emeraldine salt. The end product of polymerization is

PANI-PA-DBSA together with some sulfate anionic dopants
due to the presence of APS.

3.2 | Formation of PANI on zinc oxide

nanoparticles
FIGURE 3 Formation of conductive PANI on nano zinc oxide Formation of PANI on GF surface via in situ polymerization
surface via chemical oxidation of aniline for corrosion protection of steel has already been reported by
Liu et al.,[49] who tightly bonded PANI to GF surface and used
this composite to form an anticorrosive coating. In the present
and a dopant, resulting in an organic dispersible PANI by work, an attempt was made to change the PANI/GF
favoring para-coupling of monomers and preventing unnec- composite to the PANI/zinc oxide/GF nanocomposite. As
essary branching reactions.[45] mentioned previously, nano-sized metal oxides such as zinc
The polymerization of aniline is done through the oxide can enhance corrosion protection performance of PANI
formation of anilinium-DBSA complex (Figure 1). Formed coatings. As it was mentioned earlier by Mostafavi,
in the organic phase, these structures have Krafft points polymerization of PANI in the presence of zinc oxide will
similar to those of ionic surfactants.[46] Hence, they can act as result in structures shown in Figure 3. Due to the rich
surfactants and form micelles at the critical micelle hydroxyl groups existing on the surface of the ZnO
concentration (CMC).[47] At this point, it became obvious nanoparticles, the water wettability of ZnO nanoparticles
that the formation of the milky solution prior to the addition of was stronger than their oil wettability. The ZnO nanoparticles
the oxidant/acid solution has been due to the formation of spontaneously assembled in anilinium-DBSA reverse mi-
anilinium-DBSA reverse micelles. celles, forming anilinium-DBSA/ZnO structures. Aniline in
As is illustrated in Figure 2, when the aqueous phase the anilinium-DBSA micelles polymerized under the oxida-
containing APS and PA is added to the aforementioned tion of APS to yield PANI. PANI covered the ZnO
solution, water and water soluble agents are trapped inside the nanoparticles, forming PANI-ZnO nanocomposites.[50–52]
reversed micelles. Polymerization of aniline is initiated
through the formation of anilinium cation while being
3.3 | Formation of the PANI/zinc oxide/GF
attacked by initiators. This cation is polymerized to form
nanocomposite
PANI; at this stage, DBSA serves as an acidic dopant.[48]
During polymerization, the milky white solution turns into a According to the SEM images presented in Figure 4, when
dark green solution, indicating the formation of conductive polymerized on the surface of nano zinc oxide, PANI can

FIGURE 4 SEM image and EDX analysis of PANI/zinc oxide/GF composite

ROUHOLLAHI AND BARZEGAR KHALEGHI
| 5

The formation of PANI/zinc oxide on GF surface was also

proven via EDX graphs.

3.4 | Role of GF in the PANI/zinc oxide/GF

nanocomposite
Many studies have reported improved mechanical character-
istics for epoxy matrices to which GF had been added because
of the reinforcement caused by GF.[53–55] In order to
investigate the mechanical properties of the PANI/zinc
oxide/GF nanocomposite in an epoxy matrix, stress–strain
FIGURE 5 Stress–strain curves of PANI/zinc oxide/GF curves were obtained using a Shimadzu Autograph AG-G
nanocomposite with different GF contents expressed in GF percent in Series universal testing machine. Figure 5 shows the curve of
epoxy matrix tensile stress as a function of tensile strain for the cured neat
epoxy and PANI/zinc oxide/GF nanocomposites containing
different GF w/w%.
TABLE 3 Young's modules of neat epoxy and PANI/zinc oxide/GF As it is obvious from Figure 5, adding PANI/zinc oxide/
nanocomposites containing different GF w/w% GF can be an effective way of enhancing the mechanical
GF w/w% of PANI/zinc strength of the coating. The tensile strength of neat epoxy
oxide/GF Young's modules (GPa) coating is 47.8 MPa. When PANI/zinc oxide/GF is added to
0 (neat epoxy) 1.8 epoxy resin tensile strength is improved up to 63.5 MPa in the
2 2.3 case of 5 w/w%. However, the tensile strength of 10 w/w%
PANI/zinc oxide/GF nanocomposites was decreased to
5 3.1
57.93 MPa, which is induced by the agglomeration of the
10 2.6
PANI/zinc oxide/GF nanocomposite. Therefore, it can be
argued that if GF content is too low, small strengthening
effect may occur and that if it is too high, the epoxy matrix
effectively cling to GF surface. This attachment seems to be may fail to effectively surround fibers.
more than a simple physical interaction, as indicated by the The Young's modulus is the slope of the stress–strain
uniform dispersion of PANI/zinc oxide and the good stability curve at elastic portion. Young's modulus is a measure of the
of the attached particles during corrosion performance tests. ability of a material to withstand changes in length when

FIGURE 6 SEM images of different break points across sample cross-sections

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| ROUHOLLAHI AND BARZEGAR KHALEGHI

PANI and PANI/zinc oxide/GF-coated samples showed

higher positive potentials, implying that samples containing
zinc oxide nanoparticles had better corrosion protection
capabilities. Among these samples, 1 w/w% zinc oxide
seemed to be the best alternative. It was reported that, in
the presence of ZnO nanoparticles, Zn2+ is released, even
small amounts of which can inhibit the corrosion of the
substrate. Moreover, this phenomenon can be attributed to the
blocking of the free iron surface for the cathodic oxygen
reduction reaction and decreasing of the overall corrosion
rate.[52,56]
As it was reported in literature, PANI/zinc oxide/GF
FIGURE 7 DC polarization plots of different samples in NaCl nanocomposite acts as a physical barrier preventing corrosive
3.5% solution with potential scan rate of 5 mV s−1 ions from diffusing across the coating; the barrier effect is
improved due to the presence of PANI nanocomposite in
epoxy matrix. In addition, it passivates the metal surface by
under lengthwise tension or compression. The Young's forming or even improving iron (III) oxide passive film on the
modulus of neat epoxy and PANI/zinc oxide/GF nano- surface of iron (Figure 8). As previously reported, PANI can
composites are summarized in Table 3. be re-oxidized by molecular oxygen from the environmental
In order to investigate breaking patterns, SEM images air while the oxidation of iron to its oxides takes place on the
were taken from different sample cross-sections (Figure 6). exposed iron surface at pinhole areas and under the film. This
It is clear from the results that the addition of GF to the re-oxidation depends very much on the conditions of the
PANI/zinc oxide composite can enhance the elasticity of the experiment and may not occur under all conditions. As soon
obtained composite as indicated by the fact that the breaking as the conducting polymer is no longer able to provide active
points of the GF-added sample are not as sharp as those of the protection total failure reduction of PANI film occurs. It was
sample without GF. No obvious breaking edge was observed also reported that, in highly corrosive environments (e.g., in
in the composite containing 5% of GF, implying the superior chloride-containing environments), the required passivation
elasticity of this coating. current density in active defects causes accordingly high
reduction rates of the PANI. In such cases, the re-oxidation
rate by oxygen may not suffice for keeping the PANI active
3.5 | Effect of corrosion protection
and protection may not occur at all. The ratio between active
performance of PANI/zinc oxide/GF
PANI area to active metal area is also important. Because
nanocomposite
when facing large defects in protective coating the critical
Effect of zinc oxide/GF content on nanocomposite corrosion current density for the iron passivation could not be provided
performance was investigated using DC polarization plots in by PANI coating. Hence, the pinholes and small cracks are
3.5% NaCl solution. The DC polarization curves for epoxy- better protected than large defects. This mechanism is
coated mild steel, PANI, and PANI/zinc oxide/GF-in-epoxy schematically presented in Figure 8. Due to the conducting
matrix-coated mild steel working electrodes are shown in nature of the coating, the oxygen reduction takes place on the
Figure 7. Table 4 presents the values of electrochemical PANI coating, while the oxidation of metal ions to passive
corrosion parameters including corrosion potential (Ecorr), iron oxides takes place on the exposed iron surface at pin
cathodic Tafel slope (bc), anodic Tafel slope (ba), and hole areas. It is also possible that the passivation of pinholes
corrosion current (Icorr). Compared to epoxy-coated sample, takes place by the cathodic complementary reaction of

TABLE 4 DC polarization curves parameters for coated carbon steel in 3.5% NaCl solution
Sample name ba (mV dec−1) bc (mV dec−1) ICorr (μA) ECorr (mV)
Neat epoxy 177.87 195.31 50.77 −882.99
PANI 64.22 155.41 39.14 −843.72
PANI/zinc oxide (0.5%)/GF (5%) 134.67 97.74 10.20 −753.25
PANI/zinc oxide (1%)/GF (5%) 143.99 81.95 6.19 −735.71
PANI/zinc oxide (2%)/GF (5%) 59.99 113.98 5.07 −723.76
ROUHOLLAHI AND BARZEGAR KHALEGHI
| 7

conducting to non-conducting type. Therefore, the OCP

values are not shifted toward noble region.[57,58] Another
mechanism that is widely discussed is the intelligent release
of corrosion inhibiting dopant anions. This reaction is
triggered by the corrosion activity at the defect most likely
due to correlated interfacial potential changes or increase
in pH (in case of PANI). In this work phosphate ions which
are good inhibitors were released during corrosion protection
process. This must be also noted that in order to enhance the
ability for inhibitor anion release, amount of PANI needs to be
in electric contact with the metal at the defect needs to be as
high as possible.[59,60]
FIGURE 8 Mechanism of crack protection by PANI

3.6 | SEM and weight loss studies

PANI(ES) → PANI(LS). If the re-oxidation rate is high SEM images of bare steel, neat epoxy-coated steel and PANI/
enough ES prevails during and after passivation of the ZnO (1%)/GF (5%) coated steel are presented in Figure 9. It is
defects. If the passivation current density is too high, in the obvious that epoxy matrix is relatively porous and addition of
presence of larger defects or too acidic pH, then this does not PANI/ZnO/GF can decrease porosity of coating. This will
work anymore (as ES is too quickly reduced due to the lead to better barrier effect and reduce corrosion rate of steel.
galvanic coupling with the defect sites) and the ES fully The weight loss of carbon steel samples were monitored
breaks down to LS. Hence, the coating may be changed from for 50 days immersion in 3.5% NaCl solution. In this study,

FIGURE 9 SEM images of bare steel (a), epoxy-coated steel (b), and PANI/ZnO (1%)/GF (5%) coated steel (c)

TABLE 5 The weight loss parameters of carbon steel samples during the immersion test in 3.5% NaCl for 50 days at 30 ± 2 °C
Initial weight Final weight (mg) after 50 days of Weight loss Weight loss
Sample name (mg) immersion in 3.5% NaCl solution (mg) (%)
Bare steel 3285.1 2181.7 1103.4 33.59
Neat epoxy-coated steel 3385.2 2604.4 780.8 23.06
PANI/ZnO (0.5%)/GF (5%) coated 3400.1 3303.2 96.9 2.85
steel
PANI/ZnO (1%)/GF (5%) coated steel 3401.3 3329.9 71.4 2.1
PANI/ZnO (2%)/GF (5%) coated steel 3404.8 3304.0 100.8 2.96
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| ROUHOLLAHI AND BARZEGAR KHALEGHI

epoxy-coated sample did not provide much protection due to [10] L. T. Pedersen, presented at Marine Coating Conference,
its relative porosity in comparison with PANI/ZnO/GF- Hamburg, Germany, 24−25 September, 2008, pp. 25–48.
coated samples. Both SEM and weight loss study are in [11] U. Yilmazer, Compos. Sci. Technol. 1992, 44, 119.
[12] C. Jeyaprabha, S. Sathiyanarayanan, G. Venkatachiari, J.
correlation with this fact that addition of PANI/ZnO/GF
Electroanal. Chem. 2005, 583, 232.
nanocomposite to epoxy matrices can reduce coating porosity
[13] T. P. McAndrew, Trends Polym. Sci. 1997, 5, 7.
and provide barrier effect for steel substrate (Table 5). [14] P. J. Kinlen, V. Menon, Y. Ding, J. Electrochem. Soc. 1999, 146,
3690.
4 | CONCLUSIONS [15] S. Sathiyanarayanan, S. Muthkrishnan, G. Venkatachari, Electro-
chim. Acta 2006, 51, 6313.
[16] I. Šeděnková, M. Trchová, N. V. Blinova, J. Stejskal, Thin Solid
The present study was an investigation into the corrosion Films 2006, 515, 1640.
protection of carbon steel using the PANI/zinc oxide/GF [17] N. V. Blinova, J. Stejskal, M. Trchova, J. Prokes, Polymer 2006,
nanocomposite incorporated into an epoxy matrix. It was found 47, 42.
that adding GF to the coating, one can enhance mechanical [18] J. Prokes, J. Stejskal, Polym. Degrad. Stab. 2004, 86, 95.
properties and improve coating elasticity, which leads to more [19] N. Bahrami Panah, M. Payehghadr, I. Danaee, H. Nourkojouri, M.
durable coatings. An inspection of the GF content of coatings Sharbatdaran, Iran Polym. J. 2012, 21, 747.
revealed that the coating containing 5 w/w% of GF produced [20] Y. Hana, T. Kusunose, T. Sekino, Synth. Met. 2009, 159, 123.
[21] J. E. P. da Silva, S. I. C. de Torresi, R. M. Torresi, Corros. Sci.
the best strain-stress results. Regarding corrosion protection
2005, 47, 811.
performance, the coating containing 1 w/w% of zinc oxide [22] A. L. Briseno, T. W. Holcombe, A. I. Boukai, E. C. Garnett, S. W.
nanoparticles performed better, as indicated by the shifting of Shelton, J. J. M. Fréchet, P. Yang, Nano Lett. 2010, 10, 334.
the corrosion potential toward noble potentials on DC [23] A. Dey, S. De, A. De, S. K. De, Nanotechnology 2004, 15, 1277.
polarization plots. Briefly, it can be concluded that, PANI/ [24] D. Jiao, J. C. Bystryn, K. Murakoshi, R. Kogure, Y. Wada, S.
zinc oxide/GF nanocomposite in epoxy matrix can enhance the Yanagida, Sol. Energy Mater. Sol. Cells 1998, 55, 113.
mechanical characteristics and corrosion protection perfor- [25] A. Olad, R. Nosrati, Prog. Org. Coat. 2012, 68, 319.
mance of conductive PANI better than the addition of plain [26] M. Mizanur, R. Khana, Y. K. Weeb, W. A. Kamil Mahmood,
Synth. Met. 2012, 162, 1065.
PANI. Such a composite can prevent corrosion in cracks and
[27] S. Kondawar, R. Mahore, A. Dahegaonkar, S. Agrawal, Adv. Appl.
defects via forming a passive iron oxide layer and releasing Sci. Res. 2011, 2, 401.
phosphate ion. Furthermore, with porosity being reduced, [28] W. E. Mahmoud, A. A. Al-Ghamdia, Polym. Adv. Technol. 2011,
PANI/zinc oxide/GF nanocomposites can hinder corrosive 22, 877.
environment from diffusing into coating. [29] G. L. Teoh, K. Y. Liew, W. A. K. Mahmood, Mater. Lett. 2007, 61,
4947.
[30] T. Tuken, Prog. Org. Coat. 2006, 55, 60.
ORCID [31] E. Armelin, M. Marti, F. Liesa, J. I. Iribarren, C. Aleman, Prog.
Ahmad Rouhollahi http://orcid.org/0000-0002-6050-4011 Org. Coat. 2010, 69, 26.
[32] A. Kalendova, Prog. Org. Coat. 2003, 46, 324.
Mohammad Hamed Barzegar Khaleghi http://orcid.org/
[33] A. Moezzi, A. M. McDonagh, M. B. Cortie, Chem. Eng. J. 2012,
0000-0002-8894-3673 185, 1.
[34] E. Armelin, C. Aleman, J. I. Iribarren, Prog. Org. Coat. 2009, 65,
88.
[35] A. Tale, O. Forsen, S. Ylasaari, Synth. Met. 1999, 102, 1394.
REFERENCES
[36] Y. Shao, H. Huang, T. Zhang, G. Meng, F. Wang, Corros. Sci.
[1] D. Ratna, Compos.: Part A 2008, 39, 462. 2009, 51, 2906.
[2] S. Jongsung, P. Cheolwoo, M. Do Young, Compos.: Part B Eng. [37] S. Radhakrishnan, N. Sonawane, C. R. Siju, Prog. Org. Coat. 2009,
2005, 36, 504. 64, 383.
[3] P. Joung-Man, S. Wae-Gyeong, Y. Dong-Jin, Compos. Sci. [38] M. Rohwerder, Int. J. Mater. Res. 2009, 10, 100.
Technol. 1999, 59, 355. [39] G. Williams, H. N. McMurray, Electrochem. Solid-State Lett.
[4] S. Dong, R. Gauvin, Polym. Compos. 1993, 14, 414. 2005, 8, B42.
[5] S. Keusch, R. Haessler, Compos.: Part A 1999, 30, 997. [40] J. M. Gustavsson, P. C. Innis, J. He, G. G. Wallace, D. E. Tallman,
[6] W. Brostow, W. Chonkaew, K. P. Menard, T. Scharfd, Mater. Sci. Electrochim. Acta 2009, 54, 1483.
Eng. A 2009, 507, 241. [41] M. Rohwerder, S. Isik-Uppenkamp, C. A. Amarnath, Electrochim.
[7] T. Kanie, K. Fujii, H. Arikawa, K. Inoue, Dent. Mater. 2000, 16, Acta 2011, 56, 1889.
150. [42] C. Wu, X. Qiao, J. Chen, H. Wang, F. Tan, S. Li, Mater. Lett. 2006,
[8] F. Chen, D. Tripathi, F. R. Jones, Compos. Sci. Technol. 1996, 56, 60, 1828.
609. [43] J. Stejska, Pure Appl. Chem. 2002, 74, 857.
[9] P. K. Vallittu, J. Prosthet. Dent. 1999, 81, 318. [44] E. M. Genies, C. J. Tsintavis, Electroanal. Chem. 1985, 195, 109.
ROUHOLLAHI AND BARZEGAR KHALEGHI
| 9

[45] S. H. Lee, D. H. Lee, K. Lee, C. W. Lee, Adv. Funct. Mater. 2005, [57] S. Sathiyanarayanan, S. Muthkrishnan, G. Venkatachari, Electro-
15, 1495. chim. Acta 2006, 6313, 6319.
[46] Y. Hana, T. Kusunose, T. Sekino, Synth. Met. 2009, 159, 123. [58] S. Sathiyanarayanan, S. Muthukrishnan, G. Venkatachari, Prog.
[47] Y. K. Han, S. G. Oh, S. I. Shin, W. D. Joung, S. C. Yi, C. G. Cho, Org. Coat. 2006, 5, 10.
Colloids Surf. B 2002, 24, 33. [59] S. Sathiyanarayanan, S. S. Azim, G. Venkatachari, Synth. Met.
[48] M. Oh, S. Kim, Electrochim. Acta 2012, 5, 196. 2007, 157, 751.
[49] Y. Hao, F. Liu, E. Han, Prog. Org. Coat. 2013, 76, 571. [60] M. Kendig, M. Hon, L. Warren, Prog. Org. Coat. 2003, 47,
[50] H. S. Abdulla, A. I. Abbo, Int. J. Electrochem. Sci. 2012, 7, 183.
10666.
[51] M. Khanmohammadi, F. Mizani, M. Barzegar Khaleghi, A.
Bagheri Garmarudia, Prot. Met. Phys. Chem. 2013, 49, 661.
[52] A. Mostafaeia, A. Zolriasatein, Prog. Nat. Sci. 2012, 22, 273.
[53] F. M. Zhao, N. Takeda, Compos. Part A Appl. 2000, 31, 1203. How to cite this article: Rouhollahi A, Barzegar
[54] R. A. RanadeA, J. Ding, S. L. Wunder, G. R. Baran, Compos. Part Khaleghi MH. Epoxy-based PANI/zinc oxide/glass
A Appl. 2006, 37, 2017.
fiber nanocomposite coating for corrosion protection
[55] V. Cech, R. Prikry, R. Balkova, J. Vanek, A. Grycova, J. Adhes.
of carbon steel. Materials and Corrosion. 2017;1–9.
Sci. Technol. 2003, 17, 1299.
[56] X. Shi, T. Anh Nguyen, Z. Suo, Y. Liu, R. Avci, Surf. Coat. https://doi.org/10.1002/maco.201609363
Technol. 2009, 204, 237.