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A Study on Mechanism of Corrosion Protection of Polyaniline Coating and Its Failure

A Study on Mechanism of Corrosion Protection of Polyaniline Coating and Its Failure

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A study on mechanism of corrosion protection of polyaniline coating and its failure
Jianjun Fang, Ke Xu, Lihua Zhu
*
, Zhixiong Zhou, Heqing Tang
*
Department of Chemistry and Chemical Engineering, Huazhong University of Science and Technology,Wuhan 430074, PR China
Received 27 November 2006; accepted 1 May 2007Available online 19 July 2007
Abstract
Polyaniline (PANI) coatings were electrochemically deposited on substrates of stainless steel andplatinum in solutions of 0.2 M H
2
SO
4
and 0.1 M aniline by cyclic voltammetry. The corrosion pro-tection of the PANI coatings and their failure were investigated in 0.2 M H
2
SO
4
solution. It wasobserved that the corrosion protection ability of the coating to steel substrate was increased withthe increase of the coating thickness. The corrosion protection ability was mainly attributed tothe passivating effect of PANI due to its oxidizing ability in its emeraldine state. During its opera-tion, the PANI coating in emeraldine state tended to gradually lose its corrosion protection ability.This gradual failure of the PANI coating, but faster than expected, was confirmed to be related to agradual reduction of the emeraldine PANI and a gradually increased resistance between the PANIcoating and the stainless steel substrate. These findings lead to a new mechanism for the corrosionprotection of PANI coating and its failure.
Ó
2007 Elsevier Ltd. All rights reserved.
Keywords:
A. Polyaniline; A. Stainless steel; C. Corrosion; C. Electrodeposited films; C. Galvanic coupling
1. Introduction
Intrinsically conducting polymer, because of its specific properties, has a wide rangeof applications. One of the important and promising applications is corrosion protection.
0010-938X/$ - see front matter
Ó
2007 Elsevier Ltd. All rights reserved.doi:10.1016/j.corsci.2007.05.017
*
Corresponding authors. Tel.: +86 27 87543432; fax: +86 27 87543632.
E-mail addresses:
lhzhu63@yahoo.com.cn(L. Zhu),hqtang62@yahoo.com.cn(H. Tang). Corrosion Science 49 (2007) 4232–4242
www.elsevier.com/locate/corsci
 
Of the conducting polymers the polyaniline (PANI) families have been the most widelystudied, due to their environment stability and ease of synthesis. In the field of corrosionprotection, PANI can be used either as corrosion inhibitors or as protective coatings.PANI can function as inhibitors, because of the presence of the functional group C
@
Nwhich can be adsorbed on the metal surface. It was found that soluble PANI absorbedon the metal restrain the anodic or cathodic reaction[1,2]. In much more cases, PANIwas used as protective coatings. Since DeBerry[3]showed in 1984 that the electrochemi-cally deposited PANI protected stainless steel by anodic protection, PANI was investi-gated for protection of stainless steel[3,4], iron[5,6], mild steel[7], copper[4], aluminum[8]and zinc[9]. It was also shown that PANI protects mild steel in chloride medium[7,10]. PANI can also be used as a blend with epoxy resin, or as an under layerwith an epoxy top-layer[10–12]. Pereira da Silva et al.[13]studied PANI acrylic coatings for corrosion inhibition and found that counter-ions were a crucial factor for determiningthe protective performances of the coatings.Many researches have been done to clarify the mechanism for the corrosion protectionof PANI coatings. Wessling[4]found that coats of chemically synthesized PANI inducedan oxide formation on the metal surface, making corrosion potential of stainless steel shiftto the direction of noble metals and leading to a decreasing of corrosion current. Hugot-LeGoff and coworkers[14,15]reported the iron coated with electrochemical PANI was actu-ally in the passive state by means of in situ micro-Raman spectroscopy. Gasparac andMartin[16]showed that the presence of conducting polymers could even passivate thepre-introduced pinholes, and found by XPS analysis that the outer part of oxide filmwas Fe
2
O
3
, while the under-film was Fe
3
O
4
. It is generally accepted that the oxidationof the metallic surface during the exposure to an aggressive environment is linked to thereduction of PANI[17], which is re-generated by the reoxidation of PANI coating throughthe reduction of dissolved oxygen at the PANI/electrolyte interface.Until to the present time, various and even contradictive experimental results and opin-ions on the corrosion protection of PANI coating and its mechanism have been reported,because of the complicated corrosion systems (different metals to be protected, differentcorrosion media, different methods of PANI synthesis, and different synthesis conditions).In the aspect of experimental findings, most of reported research works claim that PANIprotects when doped[6]. The protection can be achieved with undoped PANI[5,18], which is in contradiction with Araujo’s work[19]that undoped PANI give little protection com-paring with common paint. The reports that PANI protects in chloride medium[7,10]areagainst the claim that PANI does not protect in chloride medium[6]. Kenneth’s finding[20]that electrochemically deposited PANI had little protection on pure aluminum is dif-ferent from the work of Racicot et al.[8]that it can protect aluminum. Santos et al.[21] reported excellent adhesion properties for undoped PANI tested in 3% NaCl solution,whereas Lu et al.[22]found poor adhesion in 3.5% NaCl solution. In the aspect of theprotection mechanism, both the presence of metallic oxides[23]and metallic complexes[17]at the metallic surface were proposed as components in the passive layer. In contrastto the general opinion that the reoxidation of PANI coating through the reduction of dis-solved oxygen at the PANI/electrolyte interface takes an important role in the passivatingeffect of PANI coating[17], Rammelt et al.[24]claimed that the reduction of both the dis- solved oxygen and the conductive polymer form a redox couple with the metal oxidationreaction, and that the less noble substrate would corrode even much faster throughthe pores, because a local element would be formed with the pores acting as anodes.
J. Fang et al. / Corrosion Science 49 (2007) 4232–4242
4233
 
Also Tan and Blackwood[25]believed that PANI accelerated the corrosion of carbon steelin a manner akin to bimetallic corrosion.The above-mentioned divergent research results and contradictions in the mechanismfor corrosion protection of PANI coating inspired us to further study on mechanism of corrosion protection of PANI coating and its failure. In the present work, the corrosionprotection of PANI to stainless steel and its gradual loss were investigated in 0.2 MH
2
SO
4
. The use of H
2
SO
4
instead of HCl favors avoiding the influences of aggressiveCl
À
ions. Moreover, the ions exchange between the electrolytic solution and the dopedPANI coating can be neglected, and hence we can focus on the impact of interface prop-erty on the corrosion protection and failure of PANI coatings.
2. Experimental
Aniline (Aldrich) was distilled and stored in the dark before use. PANI coatings weredeposited from solutions of 0.2 M H
2
SO
4
+ 0.1 M aniline. Electrochemical polymerizationof aniline was adopted to prepare PANI coatings on stainless steel (SS) and Pt-foil sub-strates, because it provides good adhesion between the PANI with the electrode and easeof control the thickness of the PANI film. The areas of both SS and Pt working electrodeswere 1 cm
2
. In the preparation, the counter-electrode was Pt-foil and the reference elec-trode was saturated calomel electrode (SCE), which all the potentials throughout thiswork are referred to. Prior to each experiment, the working electrode were polished withemery paper down to 2400 grit, washed with distilled water and finally with ethanol.PANI coatings were electrochemically deposited by potential cycling at 10 mV s
À
1
from
À
0.2 V to 1.0 V in the first cycle, and then from
À
0.2 V to 0.9 V in the successive cycles.The decreased high potential limit (0.9 V) in the successive cycles favors to avoid degrada-tion of PANI[26], and the low scan rate (10 mV s
À
1
) can make sure the films more com-pact and adhesion to the substrate. The thickness of PANI coatings was controlled byadjusting the total number of potential cycling. In the present work, three types of PANIcoatings were obtained on the SS by controlling the total cycle number as 5,10 and 15.When these coatings were switched from leucoemeraldine (LE, the reduced form of PANI)to the emeraldine (EM, the partially oxidized form of PANI) state, they yielded an oxida-tion charge of 0.381,2.00 and 4.66 mC cm
À
2
. According to the correlation between the filmthickness and the oxidation charge, these films were estimated with a film thickness of 0.014,0.074 and 0.172
l
m, respectively. When the electrodeposition was performed onPt substrates, the resultant PANI coatings were found to yield an oxidation charge of 0.35,2.3 and 3.9 mC cm
À
2
, which were slightly different from that of the PANI coatingcorrespondingly obtained on SS substrates. Because the small differences between the filmthickness on SS and Pt substrates did not cause a marked effect on the corrosion protec-tion ability of the coatings, we could neglect the differences between the thickness of thePANI coatings on SS and Pt substrates. For simplicity, these coatings are referred to asPANI-1, PANI-2 and PANI-3 in the order of film thickness increasing.After being cleaned with 0.2 M H
2
SO
4
to wash off the un-reacted monomer, both thecoatings on SS and on Pt were polarized at the potential of 0.4 V to achieve an EM state.Then, the corrosion protection of PANI coating was studied with measurements of open-circuit potential (OCP), polarization curves and electrochemical impedance spectroscopyin 0.2 M H
2
SO
4
. Electrochemical experiments were performed in a single compartment cell
4234
J. Fang et al. / Corrosion Science 49 (2007) 4232–4242

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