Corrosion Science 49 (2007) 10271044 www.elsevier.

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Corrosion inhibition of aluminum alloy AA 2014 by rare earth chlorides

Ajit Kumar Mishra, R. Balasubramaniam
Received 16 August 2005; accepted 6 June 2006 Available online 20 September 2006

Department of Materials and Metallurgical Engineering, Indian Institute of Technology, Kanpur 208 016, India

Abstract The eect of LaCl3 and CeCl3 inhibitor additions in 3.5% NaCl solution on the corrosion behaviour of aluminum alloy AA2014 has been investigated. Four dierent concentrations (250, 500, 750 and 1000 ppm) of LaCl3 and CeCl3 were studied. The polarization resistance increased signicantly and the corrosion rate decreased by an order of magnitude with the addition of 1000 ppm of LaCl3 and CeCl3, with maximum decrease noticed for CeCl3. EIS studies showed that there was a significant increase in overall resistance after addition of 1000 ppm LaCl3 and CeCl3, when compared to the case without inhibitor. The double layer resistance and lm resistance increased after inhibitor addition. Scanning electron microscopy conrmed formation of precipitates of oxide/hydroxide of lanthanum and cerium on cathodic intermetallic sites, which reduced the overall corrosion rate. 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Aluminum alloy; A. Lanthanum chloride; A. Cerium chloride; B. Polarization; B. EIS; B. SEM; C. Inhibitors

1. Introduction Aluminum and its alloys are widely used in engineering applications because of their low density, favorable mechanical properties, good surface nish and relatively good corrosion resistance. Research eorts in the aeronautical industry have focused on the

Corresponding author. E-mail address: bala@iitk.ac.in (R. Balasubramaniam).

0010-938X/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2006.06.026

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study of AlCu and AlZn alloys. The electrochemical behaviour of Al and its alloys has attracted the attention of many investigators. The natural oxide lm on aluminum does not oer sucient protection against aggressive anions. In this context, inhibitors are used to improve protective features of the surface. Currently, chromates are widely used in anticorrosive pre-treatments of aluminum alloys [15]. However, because of their high toxicity, an intense research eort is underway for their replacement. Rare earth chlorides have been tested as corrosion inhibitors for Al alloys like AA5083 [6], AA7075 [7], AA8090 [8], AA6061 [9] and AA2024 [10]. These rare earth chlorides act as cathodic inhibitors [6,11,12]. Bethencourt et al. [6] observed, from weight loss and polarization results, that lanthanum, cerium and samarium chlorides are eective uniform corrosion inhibitors of AA5083 in aerated 3.5% NaCl solution. As no pits were observed in samples immersed in solutions containing inhibitors, they concluded that these rare earth salts also act as pitting corrosion inhibitors. Arnott et al. [7] investigated the corrosion inhibition behaviour of 1000 ppm concentration of dierent rare earth chlorides (YCl3, PrCl3, LaCl3 and CeCl3) and other salts such as FeCl2, CoCl2 and NiCl2, on AA7075 in 3.5% NaCl solution. and Damborenea The best degree of inhibition was achieved by CeCl3 addition. Davo [8] studied the eect of dierent concentrations of LaCl3 and CeCl3 on the corrosion of AA 8090 in 3.56% NaCl solution. Maximum inhibition was obtained after addition of 1000 ppm CeCl3 and 250 ppm LaCl3. Cerium chloride inhibited intergranular corrosion more eectively than lanthanum chloride. Neil and Garrard [9] studied the eect of cerium pre-treatments on AA6061 prior to immersion in 3.5% NaCl solution. They immersed the samples in 0.1 M NaCl/1000 ppm CeCl3 solution for one week and then transferred them to the test solution. They concluded that cerium pre-treatment decreased the corrosion susceptibility, but the eect of the treatment was short lived. Aldykewicz et al. [10] reported that the corrosion inhibition of cerium chloride addition in NaCl solution was related to the development of a cerium-rich lm over the cathodic copper surface in the case of AA2024. Aballe et al. [11] analyzed the eect of CeCl3, LaCl3 and mixture of both CeCl3 and LaCl3 on the corrosion of AA 5083 alloy in NaCl solution. They found that corrosion resistance oered by these rare earth metal chlorides was of same order as those found with classical Cr-based compounds. They further observed that there was a two-fold increase in polarization resistance after addition of 500 ppm LaCl3, four-fold after 500 ppm CeCl3 and nearly six-fold after addition of 250 ppm each of LaCl3 and CeCl3. They concluded that mixed solutions of LaCl3 and CeCl3 in optimum ratio showed a better performance than solely LaCl3/CeCl3 inhibitor. The aim of the present work was to study the eect of LaCl3 and CeCl3 inhibitors at dierent concentration levels on the corrosion behaviour of AA2014 in NaCl solution. AA2014 is one of the most corrosion prone Al alloys because of the presence of cathodic CuAl2 precipitates. 2. Experimental procedure The 2014 alloy was obtained from HINDALCO, Renukoot, India in the form of a cylindrical rod of diameter 4.2 cm. The composition of the alloy 2014 was (in wt.%) 3.95.0 Cu, 0.20.8 Mg, 0.41.2 Mn, 0.51.2 Si, <0.7 Fe, <0.1 Cr and remainder Al. Specimens for electrochemical tests (of thickness 6.5 mm) were sectioned from the as-received rod. The cross section of the rod was exposed to the electrolyte in all the

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experiments. All the surfaces of the specimens were mechanically polished down to ne emery paper (starting from grit number 220 to 1000, ANSI), de-greased with acetone and then rinsed in distilled water before being used for each electrochemical experiment. All this procedure was followed prior to each electrochemical experiment. All experiments reported in this paper were repeated a minimum of two times. Corrosion tests were carried out in freely aerated 3.5% NaCl solution. Lanthanum and cerium chlorides were added at concentrations of 250, 500, 750 and 1000 ppm. Freshly prepared NaCl solution was used in all the experiments. All the experiments were conducted at room temperature (25 C). Separate samples were immersed for 4 and 168 h in solutions containing dierent concentration of inhibitors, and later their surfaces were observed in a scanning electron microscope (SEM) (FEI QUANTA 200). Local compositions were studied with energy dispersive analysis using X-ray (EDAX) unit attached to the SEM. Electrochemical measurements were performed in a at cell (Amtek, USA) using a 2263 PARSTAT (Amtek, USA) potentiostat controlled through a personal computer. In the at cell, the area of exposure of the sample was 1 cm2. An Ag/AgCl electrode was employed as the reference electrode. The potential of this electrode with respect to standard hydrogen electrode is +0.197 V. All the potential data presented in this paper are referred to this Ag/AgCl reference electrode potential. All electrochemical experiments were performed after stabilization of free corrosion potential (FCP). In conducting linear polarization experiments, the potential was scanned from the cathodic to anodic direction at a rate of 0.166 mV/s. The potential range for linear polarization experiments were 20 mV from FCP. Potentiodynamic polarization curves were obtained from 250 mV to +1600 mV from FCP using a scan rate of 1 mV/s. Electrochemical impedance spectroscopy (EIS) measurements were performed by applying a sinusoidal potential perturbation of 10 mV at FCP. The impedance spectra were measured with a frequency sweep from 100 kHz to 10 mHz in logarithmic increment. The impedance data was analyzed using the ZSimpWin 3.00 software (Amtek, USA). The impedance data were tted to appropriate equivalent electrical circuit using a complex nonlinear least-squares tting routine, using both the real and imaginary components of the data. Dierent parameters obtained from the best t equivalent circuit were tabulated and analyzed. 3. Results and discussion 3.1. Polarization All the experiments were conducted after stabilization of free corrosion potential (FCP). In all the cases, the FCP increased in the noble direction and stabilized. The linear polarization plots obtained after immersion in 3.5% NaCl solution, with and without LaCl3 additions are shown in Fig. 1, while those after CeCl3 additions in Fig. 2. Generally, the slope (i.e., the polarization resistance, Rp) increased after inhibitor additions. A higher Rp value indicates lower corrosion rate. The estimated Rp values are tabulated in Table 1. The polarization resistance increased with increase in CeCl3 concentration (Table 1). For the case of LaCl3 addition, a similar feature was observed but for the anomalous data at 750 ppm LaCl3 addition.

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-0.41 -0.42 -0.43 -0.44

E (V vs SSC)

-0.45 -0.46 -0.47 -0.48 -0.49 -0.50 -0.51 -0.52 -5 -4 -3 -2 -1

-6

3 5

1
2

I (*10 ) (A/cm )
Fig. 1. Linear polarization curves in 3.5% NaCl solution, with and without LaCl3 additions. (10 ppm, 2250 ppm, 3500 ppm, 4750 ppm, 51000 ppm).

-0.41 -0.42 -0.43 -0.44

4 1

E (V vs SSC)

-0.45 -0.46 -0.47 -0.48 -0.49 -0.50 -0.51 -0.52 -5 -4 -3 -2 -1

-6

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2

I (*10 ) (A/cm )
Fig. 2. Linear polarization curves in 3.5% NaCl solution, with and without CeCl3 additions. (10 ppm, 2250 ppm, 3500 ppm, 4750 ppm, 51000 ppm).

A.K. Mishra, R. Balasubramaniam / Corrosion Science 49 (2007) 10271044 Table 1 Variation in polarization resistance after LaCl3 and CeCl3 additions Solution Polarization resistance Rp (kX cm2) LaCl3 3.5% 3.5% 3.5% 3.5% 3.5% NaCl + 0 ppm NaCl + 250 ppm NaCl + 500 ppm NaCl + 750 ppm NaCl + 1000 ppm 2.19 7.12 20.52 6.98 104.75 CeCl3 2.19 18.83 53.82 103.62 205.21

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The Rp values were higher for CeCl3 addition at all the concentrations compared to LaCl3 additions (Table 1), indicating that CeCl3 is a better corrosion inhibitor. This was in agreement with the results obtained by other authors for dierent Al alloys, like AA5083 [6], AA7075 [7] and AA8090 [8]. The potentiodynamic polarization curves obtained after LaCl3 and CeCl3 additions are presented in Figs. 3 and 4, respectively. In both cases of inhibitor addition, the anodic portion remained similar whereas the cathodic portion shifted towards the left (i.e. to lower current densities), indicating decrease in overall corrosion rate. The polarization curves conrmed the cathodic nature of rare earth chloride inhibitors. The results of the present study are in conformity with earlier studies of LaCl3 and CeCl3 inhibitors where similar shifts in polarization curves were observed for AA5083 [6] and AA8090 [8].

0.0

-0.2

E ( V vs SSC)

-0.4

1 2
-0.6

4 5 3

-0.8 -9 -8 -7 -6 -5 -4
2

-3

-2

-1

log (I) log (A/cm )

Fig. 3. Potentiodynamic polarization curves in 3.5% NaCl solution, with and without LaCl3 additions. (10 ppm, 2250 ppm, 3500 ppm, 4750 ppm, 51000 ppm).

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0.0

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E ( V vs SSC)

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1 4
-0.6

5 3 2

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-2

-1

log (I) log (A/cm )

Fig. 4. Potentiodynamic polarization curves in 3.5% NaCl solution, with and without CeCl3 additions. (10 ppm, 2250 ppm, 3500 ppm, 4750 ppm, 51000 ppm).

3.2. Electrochemical impedance spectroscopy The EIS data (Bode phase plots and Bode magnitude plots) for 2014 alloy in 3.5% NaCl solution, with and without LaCl3, obtained at FCP, are presented in Fig. 5. The Bode phase plot indicates that two time constants could be identied in the EIS data for case without the addition of LaCl3, but only one time constant was exhibited for the data obtained with addition of inhibitor, as seen in Fig. 5a. It is also apparent that the phase angle maxima are quite broad after LaCl3 addition. The Bode magnitude plot (Fig. 5b) also indicates two slopes without inhibitor solution, whereas only one was obtained after addition of LaCl3. This kind of behaviour has been attributed to a dual protection mechanism of the passive lm, which behaves both as a barrier to corrosion and oers increased resistance to charge transfer processes [13]. The surface of aluminium and its alloys is covered by a ne layer of oxide (Al2O3) generated during its handling. In aqueous solution, the surface oxide lm is composed of Al2O3, Al(OH)3 and AlO(OH) phases [14]. Lee and Pyun [15] observed that the AlO(OH) phase enhances the passivity of the Al surface, and subsequently the corrosion resistance in chloride solution. One of the characteristics of this lm is the discontinuities present in the zone occupied by the particles of intermetallic compounds in the alloy [16]. In view of this, two physical aspects of the corroding surface are the lm and the metalsolution interface. It is anticipated that the locations where the intermetallics are present, the surface would be exposed to the environment and therefore, it is the double layer connected with intermetallicsolution interface that is really addressed while referring to metalsolution interface.

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90 80 70 60

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0 ppm 250 ppm 500 ppm 750 ppm 1000 ppm

Phase of Z (degrees)

50 40 30 20 10 0 -10 -20 -30 0.01 0.1 1 10 100 1000 10000 100000

frequency (Hz)
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0 ppm 250 ppm 500 ppm 750 ppm 1000 ppm

|Z| (ohms cm2)

1000

100

10

1 0.01

0.1

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frequency (Hz)

Fig. 5. EIS plots in 3.5% NaCl solution, with and without LaCl3 additions, at free corrosion potential: (a) Bode phase plots; and (b) Bode magnitude plots.

Surface lms formed on 2014 without and after LaCl3 and CeCl3 addition was studied using scanning electron microscopy. Intermetallic particles in 2014 alloy are mainly spherical CuAl2 (h-phase) and irregularly shaped AlCuFeMnSi phase [17]. In the NaCl electrolyte, these intermetallics tend to be cathodic to the matrix [18]. Pits are likely to initiate in the copper-depleted zone around these particles and grow around the periphery of the particles [18]. The surface of 2014 after exposure to 3.5% NaCl solution for 4 h has been presented in Fig. 6a. Two particles A and B of dierent nature were indicated by their dierent contrast in the back-scattered electron image. Local compositional analysis using EDAX of region A in Fig. 6a conrmed the presence of CuAl2 intermetallic (Fig. 6b). The AlCuFeMnSi intermetallic was identied with particle B (Fig. 6c). It can be seen from Fig. 6a that these intermetallic particles are responsible for discontinuities in the surface

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Fig. 6. (a) SEM micrograph of surface after immersion for 4 h in 3.5% NaCl solution without inhibitor addition; (b) EDAX of point A in (a); and (c) EDAX of point B in (a), indicating dierent type of intermetallics.

lm formed in aqueous solution. Moreover, these particles, being cathodic in nature, are converted into permanent cathodes with mainly the reduction of oxygen to OH ions taking place [19]. This causes a local increase of the pH, further resulting in the dissolution of the oxide layer surrounding the particles. Once this layer has dissolved, the local increase in alkalinity can cause an intense attack on the matrix. The SEM image of 2014 surface after immersion for 4 h in 3.5% NaCl solution with 500 ppm LaCl3 is shown in Fig. 7a. It was observed that oxides/hydroxides of lanthanum were precipitated on or adjacent to the cathodic CuAl2 intermetallic. This was conrmed by EDAX analysis (Fig. 7c and d). These precipitates on cathodic intermetallic sites were responsible for a decrease in the overall corrosion rate. An SEM image after immersion for 168 h in 3.5% NaCl solution with 500 ppm LaCl3 addition is shown in Fig. 7b. EDAX

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Fig. 7. SEM micrograph after immersion in 3.5% NaCl solution with 500 ppm LaCl3 addition: (a) 4 h immersion; (b) 168 h immersion; (c) EDAX of point A in (a); and (d) EDAX of point B in (a).

analysis of the white product in this gure conrmed that these were lanthanum oxide/ hydroxide. Two dierent morphologies, large hexagonal shape plates and small leaf shapes were noticed on the surface. It was noted that with increased times of immersion, most of the imperfections on the surface were covered. Based on the surface observation in the current study and review of literature to date [10,11,20,21], the surface lm nature was proposed as shown in Fig. 8a. The protection mechanism after addition of rare earth chloride is schematically shown in Fig. 8b. In the absence of inhibitor, the solution is in contact with the metal surface (mainly cathode intermetallic location) and the porous surface lm. In the presence of inhibitor (either LaCl3 or CeCl3), the open locations in the porous layer (i.e. the exposed cathodic sites on surface) are blocked due to precipitation of La(OH)3 or Ce(OH)3. Utilizing the above

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Al alloy Porous Al2O3 film

c
Rs R1

Q1

Q2

R2

Al alloy

La(OH)3 product

Fig. 8. Surface lm model in NaCl solution: (a) without addition of rare earth chloride; (b) after addition of rare earth chloride addition; and (c) equivalent circuit model based on surface lm model.

surface model, the equivalent circuit shown in Fig. 8c was used to model the experimental impedance data. This equivalent model can be represented as Rs(Q1(R1(Q2R2))), where Rs is the solution resistance, Q1 is the constant phase element (CPE) of the lm, R1 the resistance of the lm, Q2 the CPE of the double layer and R2 the resistance of the double layer. The impedance of a constant phase element is dened as [22] Z CPE Qjx ;
n 1

where Q and n are frequency independent parameters, and 1 6 n 6 1 [22]. CPE describes an ideal capacitor for n = 1, an ideal inductor for n = 1 and an ideal resistor for n = 0 [22]. The overall response of the system is obtained as a result of the superposition of the responses due to the lm (R1Q1) and to the metalsolution interface (R2Q2). It is important to note that the elements (R1Q1) encompass all the information related to the surface layer and the possible defects that may be present within it. On the other hand, all the processes related to charge transfer at the electrical double layer and also diusional transport from the metalsolution interface would be included in the (R2Q2) loop. Based on the t of R(Q(R(QR))) model to the experimental EIS data, the values of Rs, Q1, n1, R1, Q2, n2 and R2 were obtained and are tabulated in Table 2. The solution resistance did not vary notably, with and without LaCl3 addition (Table 2). It can be seen that the value of n1 were very close to 1 (n > 0.9). This indicated a near capacitive behaviour of the surface lm formed on AA2014 sample. It was observed that constant phase element (Q1) decreased with increase in LaCl3 concentration and was minimum for 1000 ppm

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Table 2 Results of modelling of experimental impedance spectra obtained for AA 2014 with and without LaCl3 and CeCl3 inhibitor to the Rs(R1(Q1(R2Q2))) model Circuit elements Parameters 0 ppm Rs (X cm2) Q1 (X1 sn cm2) n1 R1 (X cm2) Q2 (X1 sn cm2) n2 R2 (X cm2) 250 ppm LaCl3 9.7 1.58 E4 0.90 826 1.70 E3 1.00 1703 9.7 1.58 E4 0.90 826 1.70 E3 1.00 1703 10.8 2.84 E5 0.88 949 7.85 E5 0.74 4187 CeCl3 10.8 8.45 E6 0.90 8164 7.58 E5 0.81 7977 500 ppm LaCl3 13.1 6.80 E6 0.96 1442 8.13 E6 0.60 18210 CeCl3 12.5 7.35 E6 0.95 18800 1.41 E6 1.00 23390 750 ppm LaCl3 11.1 2.48 E5 0.90 3586 1.28 E4 0.96 3570 CeCl3 11.3 7.57 E6 0.93 16020 2.81 E5 0.60 137600 1000 ppm LaCl3 12.8 7.62 E6 0.94 17690 9.00 E7 1.00 33380 CeCl3 14.3 7.53 E6 0.94 158400 1.76 E5 0.76 56590

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LaCl3. The 750 ppm data was anomalous, as noted from other techniques too. As Q1 is inversely proportional to thickness of the lm, a decrease in Q1 implies probably an increase in thickness of the lm. This increase in thickness may be related to the formation of a reaction product due to the presence of lanthanum ions in the solution (i.e. for example, lanthanide oxide/hydroxide both on and in the surface lm). The formation of reaction products can increase the thickness of the lm, thereby resulting in a decrease in Q1. It was observed that R1 increased with increase in concentration of LaCl3, as shown in Table 2. The constant phase element Q2 decreased drastically after LaCl3 addition, taking note of the anomalous data for 750 ppm additions. At cathodic intermetallic positions, rare earth ions precipitate their oxide/hydroxide [8]. This appears to have aected the nature of double layer at solution metal interface. This change in Q2 must be considered in association with n2. The parameter, n2, before inhibitor addition was 1, showing purely capacitive behaviour of the EDL. After LaCl3 addition, n2 value decreases until the 500 ppm inhibitor level where n2 was 0.6, as shown in Table 2. This may be indicative of diusion-related processes becoming important with inhibitor addition, due to lling up of hydroxides at the exposed solutionmetal interface. At the highest concentration of LaCl3, n2 value increased to 1, showing again pure capacitive behaviour. The reason for this increase in n2 value can be attributed to the fact that, at high concentration, lanthanum ions form a thicker lm of their oxides/hydroxides, which was clearly evident from the decrease in Q2 value too (Table 2), taking note of the anomalous data for the 750 ppm addition. The value of R2 is related to the charge transfer resistance of the electrical double layer on local cathodic sites, as per the proposed model. R2 increased with increase in LaCl3 concentration with the anomalous data for the 750 ppm LaCl3 addition. The increase is related to the formation of oxides/hydroxides of lanthanum on the cathodic intermetallic positions which, in the without inhibitor case, were exposed to solution. The EIS data (Bode phase plots and Bode magnitude plots) for 2014 alloy in 3.5% NaCl solution, with and without CeCl3, obtained at FCP, are presented in Fig. 9. As both Ce and La belong to the lanthanide group, their chlorides behave similarly with respect to their chemical nature. Therefore, the basic inhibition mechanism must be similar. The same model and the circuit (Fig. 8) proposed for LaCl3 addition was also used for CeCl3. The EIS results have been modelled and the results of the analyses are presented in Table 2. It was observed that, the solution resistance (Rs) was almost similar for both with and without CeCl3. Q1 values decreased after CeCl3 addition. Further, R1 values increased with increase in concentration of CeCl3 and were maximum for 1000 ppm CeCl3 addition. This increase in resistance can be attributed to the fact that growth of a protective cerium oxide/hydroxide lm blocks both anodic and cathodic active surface areas [23]. Q2 values decreased after CeCl3 addition, indicating the electrical double layer was aected by formation of oxides/hydroxides of cerium on cathodic intermetallic regions. Further it was observed from Table 2 that n2 values showed near capacitive behaviour until the 500 ppm CeCl3 inhibitor level, after that the value changed from 1 to 0.6 for 750 ppm and 0.76 for 1000 ppm CeCl3. The reason for this can be attributed to the fact that, at higher CeCl3 concentration, large clusters of oxides/hydroxides of cerium were formed, as shown in Fig. 10a. It was observed that after immersion for 168 h in solution containing 500 ppm CeCl3, precipitates of oxide/hydroxide of cerium possessed a plate-like morphology (Fig. 10b). The cluster-nature was also noted after immersion for 168 h in solution containing 1000 ppm CeCl3 (Fig. 10c). It was noticed that 1000 ppm CeCl3 addition

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90 80 70

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0 ppm 250 ppm 500 ppm 750 ppm 1000 ppm

Phase of Z (degrees)

60 50 40 30 20 10 0 -10 -20
0.01 0.1 1 10 100 1000 10000 100000

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|Z| (ohms cm2)

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Fig. 9. EIS plots in 3.5% NaCl solution, with and without CeCl3 additions, at free corrosion potential: (a) Bode phase plots; and (b) Bode magnitude plots.

resulted in better surface coverage. Moreover, two dierent morphologies, large hexagonal shaped plates and small leaf shapes were observed, like those noted with LaCl3 addition. EDAX analysis conrmed that the oxide/hydroxide precipitates were formed on, or adjacent to, cathodic intermetallic sites and thus reduced the overall corrosion rate by suppressing the cathodic reaction. Formation of these big clusters resulted in an increase in roughness and this could explain the lower value of n2 at high CeCl3 concentrations. Earlier, authors reported that n is a measure of surface roughness and that when it approaches 0.5, it represents a rough surface and when it moves towards 1, a smooth one [24]. R2 values increased after CeCl3 addition. This is because of the formation of a protective lm of oxides/hydroxides of cerium on cathodic intermetallic positions. It was noticed

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Fig. 10. SEM micrographs of surface after immersion in 3.5% NaCl solution with (a) 1000 ppm CeCl3 for 4 h immersion, (b) 500 ppm CeCl3 for 168 h immersion, and (c) 1000 ppm CeCl3 for 168 h immersion.

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that at 750 ppm CeCl3 addition, R2 increased signicantly and then decreased for 1000 ppm, as shown in Table 2, although the R1 value was relatively high for 1000 ppm CeCl3 addition. The EIS data is useful because it indicates that the increasing resistance for the 1000 ppm CeCl3 addition may be primarily due to the eect of Ce2O3 or Ce(OH)3 modifying the surface lm properties more than just blocking the cathodic sites and aecting double layer. This aect on the double layer appears to peak at the 750 ppm addition. Further experiments will be needed to clarify the role of both LaCl3 and CeCl3 at the 750 ppm concentration level. As observed from Table 2, the resistance (R2) oered by oxides/hydroxides of cerium at cathodic intermetallic region was much higher than that of lanthanum. Also, the overall surface resistance (R1 + R2) after cerium addition was larger compared to lanthanum additions. This showed cerium chloride as a superior inhibitor to lanthanum for 2014 alloy in NaCl solution. 3.3. Comparison of corrosion resistance The corrosion data obtained by several dierent techniques was compared. The total surface resistance, i.e, R1 + R2 (calculated from EIS) was plotted against polarization resistance Rp (calculated from linear polarization). This is shown in Fig. 11 for LaCl3 and CeCl3 additions. In the ideal case, there should be a directly linear relationship between R1 + R2 and Rp. Such a relationship was generally noticed in the present study. Exceptions were noted for 1000 ppm LaCl3 and 750 ppm CeCl3 additions, where there was deviation from the line drawn with a slope of 45 (see Fig. 11).

250000

LaCl 3 CeCl 3
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R 1 + R 2 (ohms-cm2)
Fig. 11. Relationship between Rp and R1 + R2 in 3.5% NaCl solution, with and without LaCl3 and CeCl3 additions, understood by plotting each on same gure. Data close to the line with 45 slope indicate good match.

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100

80

% Inhibitor Efficiency

60

40

R2
20

R1 + R2 Rp

0 0 250 500 750 1000 1250

LaCl3 (ppm)
Fig. 12. Variation of % inhibitor eciency as function of LaCl3 concentrations in 3.5% NaCl solution using dierent parameters.

100

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% Inhibitor Efficiency

60

40

R2 R1 + R2
20

Rp

0 0 250 500 750 1000 1250

CeCl3 (ppm)
Fig. 13. Variation of % inhibitor eciency as function of CeCl3 concentrations in 3.5% NaCl solution using dierent parameters.

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3.4. Inhibitor eciency The variation of inhibitor eciency with rare earth chloride addition was also understood. Dierent parameters were used to measure inhibitor eciency: R1, R1 + R2 (both calculated from EIS) and Rp (from linear polarization). The percentage inhibitor eciency (IE%) was calculated using the equations:   RWO IE% 1 100; 2 RWI where RWO is the resistance without inhibitor addition and RWI the resistance after inhibitor addition. The variation in inhibitor eciency as a function of LaCl3 and CeCl3 additions are shown in Figs. 12 and 13, respectively. All these parameters showed a similar trend in case of LaCl3 addition (Fig. 12). It was observed that the inhibitor eciency increased with increase in LaCl3 concentration and was maximum for 1000 ppm, with the anomalous behaviour at 750 ppm. After CeCl3 addition (Fig. 13), there was a signicant increase in inhibitor eciency. Even for 250 ppm CeCl3, there was signicant increase in inhibitor eciency, when compared to the case without inhibitor. Further, the inhibitor eciency for 500 ppm and 1000 ppm CeCl3 addition was nearly similar and on the higher side, which conrmed the superiority of CeCl3 as a protective inhibitor compared to LaCl3. 4. Conclusions Electrochemical techniques have been applied to evaluate the inhibitive eects of lanthanum and cerium chloride additions in NaCl solution on the corrosion of AA 2014 alloy. Polarization resistance measurements indicated a decrease in corrosion rate after addition of lanthanum and cerium chlorides to 3.5% NaCl solution, with a maximum decrease in corrosion rate observed for 1000 ppm addition for the case of both inhibitors. EIS studies showed that there was a signicant increase in overall resistances after addition of 1000 ppm LaCl3 and CeCl3. The corrosion resistance generally increased with increasing inhibitor addition. At all concentrations, CeCl3 was a better corrosion inhibitor compare to LaCl3. The formation of precipitates of oxides/hydroxides of lanthanum and cerium on cathodic intermetallic sites resulted in improved corrosion resistance. Acknowledgement The authors thank HINDALCO, Renukoot, India for providing the alloy used in the study. References
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