Current Applied Physics 8 (2008) 9398 www.elsevier.com/locate/cap www.kps.or.

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Studies on corrosion protection of Al2024 T6 alloy by electropolymerized polyaniline coating

V. Karpagam, S. Sathiyanarayanan, G. Venkatachari
Central Electrochemical Research Institute, Karaikudi 630 006, India Received 22 May 2006; accepted 7 May 2007 Available online 12 June 2007

Abstract Aqueous electropolymerized polymer coatings on aluminum alloys can replace the carcinogenic chromate coating. In this work, the corrosion protection ability of electropolymerized polyaniline coating on Al2024 T6 alloy has been found out. The polyaniline coatings on aluminum were formed by galvanostatic and potentiostatic methods from a bath of 0.5 M oxalic acid containing 0.1 M aniline. The corrosion protection ability of the coating was found out by Tafel polarization and EIS in 1% NaCl solution. It has been found that polyaniline coated aluminum alloy has exhibited higher corrosion activity due to the presence of pores in the coating. However, the corrosion resistant property of polyaniline coated aluminum has been found to be improved to 90% by post-treatment in cerium containing solution at 60 C. 2007 Elsevier B.V. All rights reserved.
PACS: 81.15.pq; 81.65.kn; 82.35.cd Keywords: Electropolymerization; Aniline; Al2024 T6; Corrosion; EIS

1. Introduction Aluminum alloys because of its lightweight and high strength properties nd application in aerospace applications. Protecting reactive metals like aluminum by covering their surface with an organic coating is a good way of taking advantage of the mechanical property of the metal while protecting them from corrosion. Adhesion of these organic coatings on aluminum is very poor and needs some pretreatment like chromating. Due to the carcinogenic nature of chromate conversion coatings, there is a high demand for an environmentally friendly surface treatment. Aqueous electrochemical polymerization has been found to be an attractive process for the production of primer coating on metal, which will replace hazardous method of traditional coating techniques and chromate pretreatment. The advantages of aqueous electropolymerization
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Corresponding author. E-mail address: gvchari@gmail.com (G. Venkatachari).

are: (1) the aqueous solutions used are environmentally favorable, (2) the technique combines the formation of polymer and deposition of coating in one process and this process can be easily automated, (3) the production cost is relatively low and (4) the properties of the coatings can be controlled by varying the electrochemical parameters. In recent years, polypyrrole and polyaniline coatings have been tried on steel [110]. Electrodeposition of conducting polymer coatings on aluminum is dicult due to the existence of adherent naturally formed Al2O3. Hulser and Beck [11] reported both a polypyrole (Ppy) lm and a porous type Al2O3 formation on a pretreated aluminum from an aqueous solution containing oxalic acid and pyrrole. It is also reported that the pretreatments are essential for successful formation of both lms (porous Al2O3 and Ppy lm in their pores). Beck and Husler [12] also reported the formation of a similar type of Al2O3/PPy composite using some non-aqueous media such as acetonitrile and methanol. Cheung et al. [1] conrmed the formation of a PPy lm formation on a thin Al2O3 lm in a propylene carbonate

1567-1739/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.cap.2007.05.005

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solution. Saidman [13] studied the eect of pH on the electrochemical polymerization of pyrrole on aluminum and conrmed electropolymerization only at pH 12 by potentiostatic conditions. He also suggested the nucleation of polymer initiation at defects in the passive lm and the competition between the metal passivation and Ppy electropolymerization resulted in highly localized deposits of polymer. Naoi et al. [14] reported simultaneous formation of Al2O3/Ppy lms on aluminum electrode using sodium ndodecylbenzenesulfonate and suggested a bilayer consisting of barrier type Al2O3 and an electronically conducting PPy lm. The eect of electrolyte anions in the electrochemical formation of Al2O3/PPy is also studied [15]. Polyaniline, polypyrrole, poly(N-ethyl aniline), poly(O-anisidine) and their composite coatings were electrodeposited on Al2024 alloy [16]. Infrared spectroscopy was used to explain the chemical structure of the coating and the eect of substitution. It has been found that the adhesion of the coatings to the substrate depends on the electro deposition parameters and the structure of the polymer. However, the corrosion performance of these coatings is not well established. Hence in this study, electropolymerization of aniline on aluminum alloy Al2024 T6 has been attempted. The corrosion resistant property of thus formed polyaniline coating over Al2024 T6 has been evaluated by electrochemical methods such as Tafel polarization and electrochemical impedance spectroscopy in sodium chloride solution. 2. Experimental Aluminum Al2024 T6 alloy sheet of 12 mm thick was procured from M/s. Virat Aluminum, Mumbai. Samples of 1 10 cm were cut from the sheet. All the chemicals used for electropolymerization and evaluations were of AR grade chemicals. Electrochemical measurements were made using Solatron electrochemical system (Model 1280 B). Pretreated Al2024 T6 alloy was used as working electrode, platinum foil as counter electrode and saturated calomel electrode (SCE) as reference electrode. 2.1. Pretreatment of Al2024 T6 The aluminum alloy was mechanically polished with 1/0, 2/0, 3/0 emery papers successively and then dipped in 5% NaOH solution for 2 min to activate the surface. After this stage, the samples were cleaned with cleaning powder to remove the black colored smudge formed over the surface and were washed thoroughly with running water and dipped in concentrated HNO3 solution for half a minute. The samples were then washed with distilled water and used for electropolymerization. 2.2. Electropolymerization of Al2024 T6 The pre-treated Al2024 T6 samples were masked with adhesive tape to get an eective working area of 1 cm2 at one of its ends. Electropolymerization was carried out by

two methods viz. potentiostatic polarization and galvanostatic polarization from the oxalic acid based bath of the following composition: Oxalic acid: 0.5 M Aniline: 0.12 M 2.3. Potentiostatic polarization From the cyclic voltammetric studies (Fig. 1), it has been found that the electropolymerization of aniline over Al2024 T6 occurs beyond the potential range of 1.6 V vs. SCE. Hence potentiostatic electropolymerization was carried out at three dierent potentials viz. 1.7, 1.8 and 1.9 V vs. SCE for a duration of 60 min and the current transients were recorded. 2.4. Galvanostatic polarization Electropolymerization of aniline over Al2024 T6 surface was also carried out by keeping a xed current for a xed duration of time. In this regard, three current densities viz. 15 mA, 20 mA and 25 mA were attempted and the corresponding potential transients were recorded for a period of 60 min. 2.5. Characterization of electropolymerized layers The electropolymerized polyaniline over Al2024 T6 was scraped and the IR spectrum of the polymer powder thus obtained was taken using a KBr pellet in Nicolet 380 FTIR instrument. 2.6. Corrosion resistant property evaluation The Al2024 T6 samples having electropolymerized polyaniline coating over it were evaluated for their corrosion resistance property in aerated 1% NaCl by Tafel polarization and electrochemical impedance spectroscopy.
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Fig. 1. Cyclic voltammogram of aniline electropolymerization on Al2024 T6.

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In the case of Tafel polarization, the scanning of potential was done from OCP to +0.2 V with respect to OCP at a scan rate of 1 mV/s. From this anodic polarization curve, the anodic Tafel region was identied and extrapolated to Ecorr to get corrosion potential icorr using the Corr View software. In the case of electrochemical impedance spectroscopy, a.c. signals of 20 mV amplitude and various frequencies from 100 kHz to 0.1 Hz were impressed. The results were analyzed in the Nyquist format using the Z view software. The semicircular t was made and the charge transfer resistance Rct and the double layer capacitance values was obtained by analyzing the data using the following equivalent circuit:

where ba is the anodic Tafel slope obtained from the anodic polarization studies. The protection eciency of the coating has been obtained from the following relationship: Protection efficiency icorr icorr c 100; icorr

where icorr and icorr(c) are the corrosion current densities in the absence and presence of polyaniline coating. 3. Results and discussion 3.1. Spectroscopic characterization Fig. 2 shows the IR spectrum for polyaniline deposited on Al2024 T6. The peak at 812 cm1 is characteristic of para-disubstituted aromatic rings indicating polymer formation. The bands at about 1160 and 550 cm1 are assigned to the in-plane and out-of-plane CH bending motions of the aromatic rings, respectively. A band appearing near 1260 cm1 represents the CN stretching vibration. The band at approximately 1640 cm1 is due to the quinoid ring units. The band at about 1450 cm1, demonstrates the presence of benzenoid rings. The band located at 3450 cm1 corresponds to the NH stretching vibration. The peak at 1730 cm1 is the C@O peak which is due to dopant oxalate ions. 3.2. Galvanostatic synthesis Fig. 3 shows the Et transient curves obtained during the formation of polyaniline coatings on aluminum for three dierent applied constant current densities viz. 15 mA, 20 mA and 25 mA. The induction period during

where Rs is the solution resistance, Rct is the charge transfer resistance and Cdl is the interfacial double layer capacitance. The impedance data were analyzed by using simple Randels circuit, since one semi-circle is obtained in the Nyquist plot. Since polyaniline coating is conducting in nature, the resistance of the coating is negligible and the impedance behavior represents the charge transfer process of the aluminum alloy dissolution. From the measured Rct values, the corrosion current values were estimated using the following relation: icorr ba ; 2:30 Rct

Fig. 2. FTIR spectrum of electropolymerized polyaniline.

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Fig. 3. ET transients of galvanostatic polymerization of aniline on Al2024 T6 alloy: , 15 mA; , 20 mA; , 25 mA.

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which metal dissolves decreases with increasing applied current densities. Passivation and polymerization potential values, on the other hand increase with increasing applied current density. Coatings of homogeneous appearance were obtained at various applied current densities. However, it has been found that the corrosion resistant properties of these electropolymerized coatings increased very marginally when compared to the uncoated blank Al2024 T6 alloy. In some cases, acceleration of corrosion is also noticed. This may be due to the presence of micropores in the electropolymerized coating which accelerated corrosion due to redox property of polyaniline. Hence a posttreatment for the electropolymerized coating is necessary to ll the pores. Treating the electropolymerized coatings in an aqueous solution containing cerium ions (1000 ppm) at 60 C for 30 min was attempted and it was found that the electropolymerized coating with cerium bath dipping would yield benecial results as for as corrosion resistance was concerned. It has been reported that cerium is found to be preferentially deposited over copper rich regions and reduce the oxygen reduction reaction and hence decrease the corrosion rate [17,18]. The corrosion current densities for the electropolymerized coatings with cerium post-treatment on Al2024 T6 in 1% NaCl obtained from the anodic polarization curves as shown in Fig. 4 are presented in Table 1. It can be seen that the corrosion current densities are decreased drastically from the blank value of 29.533.28 lA/cm2, 3.41 lA/cm2 and 2.71 lA/cm2 for 15 mA, 20 mA and 25 mA current densities, respectively. The protection eciencies of the coating are more than 80%. The charge transfer resistance Rct values of electropolymerized coatings with cerium post-treatment on Al2024 T6 in 1% NaCl obtained from the Nyquist plots shown in Fig. 5 are given in Table 2. It can be seen that the Rct values

I (Amps/cm )
Fig. 4. Anodic polarization curves of electropolymerized polyaniline on Al2024 T6 alloy in 1% NaCl: , blank; , 15 mA; , , 25 mA. 20 mA;

Table 1 Corrosion kinetic parameters of galvanostatically polymerized aniline over Al2024 T6 alloy in 1% NaCl Sl. no. 1 2 3 4 Current (mA) Blank 15 20 25 Ecorr (V) vs. SCE 0.691 0.701 0.700 0.686 ba (mV/s) 93 86 77 80 icorr (lA/cm2) 29.5 3.28 3.41 2.71 Protection eciency (%) 88.8 88.4 90.8

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Z''ohm
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Z'ohm
Fig. 5. Impedance behavior of uncoated and galvanostatic electropolymerized polyaniline coated Al2024 T6 alloy in 1% NaCl: , blank; h, 15 mA; j, 20 mA; s, 25 mA.

V. Karpagam et al. / Current Applied Physics 8 (2008) 9398 Table 2 Impedance parameters of galvanostatically polymerized aniline over Al2024 T6 alloy in 1% NaCl Sl. no. Current (mA) Charge transfer resistance, Rct (X cm2) 1206.30 7885.60 5351.79 9308.06 Double layer capacitance, Cdl (F/cm2) 9.12E05 1.11E04 1.00E04 2.77E05 Corrosion current, icorr (lA/cm2) 32.4 4.4 6.3 4.2 Protection eciency (%) 86.4 80.6 87.0

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Blank 15 20 25

are increased to 7885 X cm2, 5351 X cm2 and 9308 X cm2 from the blank value of 1206.3 X cm2 for the case of 15 mA, 20 and 25 mA, respectively. The icorr values obtained from EIS studies are found to agree with the values obtained from anodic polarization studies. 3.3. Potentiostatic synthesis Potentiostatic It transients for polyaniline deposition on aluminum alloy electrode at dierent applied potentials of 1.7 V, 1.8 V and 1.9 V are shown in Fig. 6. On looking at these curves, it is observed that the current drops sharply at the beginning due to the electro deposition of the electrolyte and monomer. In the second stage, the current increases, which reects the formation of aluminum(II) oxalate. In the nal stage, the current starts to decrease, which is due to the formation of polymer on the aluminum substrate. The three distinct stages can be clearly seen for each applied potential in the gure. Similar observations have been reported for steel during electropolymerization of aniline from oxalic bath [19,20]. At high-applied potentials, because of the rapid formation of polyaniline lm and aluminum (II) oxalate, the current rise is much sharper. The coatings prepared by potentiostatic synthesis are very thin and found to have poor anti-corrosive properties.
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The anodic polarization curves of the electropolymerized coatings with cerium post-treatment on Al2024 T6 in 1% NaCl are shown in Fig. 7. The corrosion kinetic parameters derived from these curves are presented in Table 3. It can be seen that the corrosion current densities are decreased from the blank value of 29.5313.4 lA/cm2 for 1.7 V potential pulse. However, the corrosion current values are increased to 19.5 lA/cm2 and 25.1 lA/cm2 with subsequent increase in the potential pulse heights to 1.8 V and 1.9 V, respectively. The protection eciencies of the coating are less than 55%. The Nyquist behavior of the complex impedance of potentiostatically grown polyaniline layer on Al2024 T6 with cerium post-treatment in 1% NaCl is shown in Fig. 8. The charge transfer resistance Rct and the double layer capacitance Cdl values obtained from these curves are given in Table 4. It can be seen from the table that the Rct is increased from the blank value of 1206.30 2231.00 X cm2 for electropolymerized polyaniline coating at 1.7 V and 2010.84 X cm2 for 1.8 V. However, for 1.9 V the Rct value is very much decreased to 534 X cm2. The icorr values obtained from EIS data are shown in Table 4, which
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Fig. 7. Anodic polarization curves for uncoated and coated Al2024 T6 , blank; , 1.9 V; , 1.8 V; , alloy in 1% NaCl: 1.7 V.
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Table 3 Corrosion kinetic parameters of potentiostatically polymerized aniline over Al2024 T6 alloy in 1% NaCl Sl. no.
0.0 0 10 20 30 40

Potential (V) vs. SCE Blank 1.7 1.8 1.9

Ecorr (V) vs. SCE 0.690 0.698 0.678 0.683

ba (mV/s) 93 70 79 72

icorr (lA/cm2) 29.5 13.4 19.5 25.1

Protection eciency (%) 54.5 33.6 14.9

Time (Sec)

Fig. 6. It curves for potentiostatic polymerization of aniline on Al2024 , 1.8 V; , 1.9 V. T6 alloy: , 1.7 V;

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T6 substrates has been demonstrated. Electro active and strongly adherent coatings can be obtained under potentiostatic and galvanostatic conditions. The polyaniline coatings were characterized spectroscopically and the corrosion resistant properties of these electropolymerized lms were evaluated using Tafel polarization and electrochemical impedance spectroscopy in 1% NaCl. Polyaniline coatings on Al2024 T6 alloys formed by galvanostatic method with cerium post-treatment exhibited very high corrosion protection performance in corrosive media containing chloride anions. Acknowledgements The authors thank The Director, Central Electrochemical Research Institute, Karaikudi for the support. They also thank DRDO, New Delhi for the nancial support. References
[1] K.M. Cheung, D. Bloor, G.C. Stevens, Polymer 29 (1988) 1709 . [2] C.A. Ferreira, S. Aeiyach, M. Delammer, P.C. Lacaze, J. Electroanal. Chem. 284 (1990) 351. [3] G. Troch Nagels, R. Winand, A. Weymeersch, L. Renard, J. Appl. Electrochem. 22 (1992) 756. [4] M. Schirmeisen, F. Beck, J. Appl. Electrochem. 19 (1989) 401. [5] F. Beck, R. Michaelis, J. Coat. Technol. 64 (1992) 59. [6] F. Beck, R. Michaelis, F. Schloten, B. Zinger, Electrochim. Acta 39 (1994) 229. [7] J.E. Stewart, J. Chem. Phys. 30 (1959) 1259. [8] M. Kalaji, L. Nyholm, L.M. Peter, J. Electroanal. Chem. 325 (1992) 269. [9] Wenchang Su, Jude O. Iroh, Electrochim. Acta 44 (1999) 2173. [10] Wenchang Su, Jude O. Iroh, Electrochim. Acta 46 (2000) 1. [11] P. Husler, F. Beck, J. Appl. Electrochem. 20 (1990) 596. [12] F. Beck, P. Husler, J. Electroanal. Chem. 280 (1990) 159. [13] S.B. Saidman, J. Electroanal. Chem. 534 (2002) 39. [14] K. Naoi, A. Oura, M. Yoshizawa, M. Takeda, M. Ue, Electrochem. Solid State Lett. 1 (1998) 34. [15] K. Naoi, M. Takeda, H. Kanno, M. Sakakura, A. Shimada, Electrochim. Acta 45 (2000) 3413. [16] K. Shah, J.O. Iroh, Surf. Eng. 20 (2004) 53. [17] A.J. Aldykiewiczs, H. Isaacs, A.J. Deuvanport, J. Electrochem. Soc. 142 (1995) 3342. [18] R.L. Twite, G.P. Bierwagen, Prog. Org. Coat. 33 (1998) 91. [19] A. Yagan, N.O. Pekmez, A. Yildiz, J. Electroanal. Chem. 578 (2005) 231. [20] J.O. Iroh, W. Su, Surf. Eng. 15 (1999) 249. [21] D.H. Vilca, S.R. Moraes, A.J. Mothew, J. Braz. Chem. Soc. 14 (2003) 52. [22] K.G. Conroy, C.B. Breslin, Electrochim. Acta 48 (2003) 721.

Z''ohm
-1000 0 0 1000 2000 3000

Z'ohm
Fig. 8. Impedance behavior of potentiostatically electropolymerized polyaniline on Al2024 T6 alloy in 1% NaCl: , blank; d, 1.7 V; j, 1.8 V; h, 1.9 V.

Table 4 Impedance parameters of potentiostatically polymerized aniline over Al2024 T6 alloy in 1% NaCl Sl. no. Potential (V) vs. SCE Blank 1.7 1.8 1.9 Charge transfer resistance, Rct (X cm2) 1206.30 2231.00 2010.84 533.97 Double layer capacitance, Cdl (F/cm2) 9.12E05 6.76E05 1.56E05 3.73E05 Corrosion current, icorr (lA/cm2) 32.4 11.7 17.3 57.0 Protection eciency (%) 63.9 46.6

1 2 3 4

are comparable to the values obtained from polarization studies. Earlier studies [21,22] on the corrosion protection ability of polyaniline on aluminum have shown that the polyaniline coated aluminum has shown higher corrosion rate values due to the redox ability of the coated polyaniline. In this study also it is found that cerium post-treatment of polyaniline coated aluminum alloy is necessary for the improved corrosion performance. 4. Conclusion The electrochemical synthesis of polyaniline coating in aqueous oxalic acid solutions on aluminum alloy Al2024