Available online at www.amse.org.

cn
Acta Metall. Sin.(Engl. Lett.)Vol.25 No.1 pp10-18 February 2012

Application of Argan plant extract as green corrosion inhibitor for steel in 1 mol/L HCl
L. Aa 1) , R. Salghi 1) , L. Bammou 1) , Lh. Bazzi 2) , B. Hammouti 3) and L. Bazzi 4)
1) Laboratory of Environmental Engineering and Biotechnology, ENSA, University Ibn Zohr, PO Box 1136, 80000 Agadir, Morocco 2) Laboratory of Establishment of Autonomous Control and Coordination of Export, 80000 Agadir, Morocco 3) LCAE-URAC 18, Faculty of Science, University of Mohammed Premier, PO Box 717, 60000 Oujda, Morocco 4) Laboratory of Materials & Environment, Faculty of Science, University Ibn Zohr, BP 8106, 80000 Agadir, Morocco Manuscript received 12 April 2011; in revised form 7 July 2011 The eect of Argan plant extract (APE) on the corrosion of the steel in hydrochloric acid medium was studied using gravimetric, electrochemical polarization and impedance spectroscopy (EIS) measurements. Inhibition eciency increases with APE concentration to attain 95% at 2.5 g/L. We note good agreement between gravimetric and electrochemical methods (potentiodynamic polarization and EIS). Eect of temperature is also made in the 298328 K range. Polarization measurements show also that APE act as a mixed inhibitor. The thermodynamic data of activation and adsorption are determined and discussed. KEY WORDS Corrosion; Steel; Inhibition; Argan plant extract; Adsorption; Kinetic parameter

1 Introduction Hydrochloric acid is a strong inorganic acid that is used in many industrial processes. The most important areas of the applications are acid pickling, acid descaling and oil well acidizing. During these processes, metal such as steel is subjected to serious acid corrosion and inhibitors are often needed to reduce corrosion rates in this media. The use of inhibitors is the most practical methods of protection against corrosion, especially in acidic solutions. Their addition is necessary to secure the attack of metal from corrosiveness media such chemical cleaning and pickling generally used to remove mill scales (oxide scales) from the metallic surface. The electrochemical corrosion is generally caused by dissymmetry potentials between metal and strong acid. The aggressively of hydrogen ion is inevitable in uninhibited acid. H+ and dissolved O2 are named natural motors of corrosion[1,2] . Survey of literature reveals that azole[315] , pyridine[1619] and amino acid[20,21] compounds are eective corrosion inhibitors. However, there is increasing concern about the

Corresponding author. Professor; Tel: +212 668 632273; Fax: +212 536 500603.

E-mail address: hammoutib@yahoo.fr (B. Hammouti)

 11 toxicity of most corrosion inhibitors. The toxic eect does not only aect living organisms but also poison the environment[22] . In our laboratories, many studies have been done on the corrosion inhibition by natural plant extract and their oils on steel in acidic solutions. Menthols[23,24] , rosemary oil[2527] , thymus oil[28,29] , artemisia[3032] , black pepper extract[33] , eugenol and acetyleugenol[34] , ginger[35] , lavender oil[36] , limonene[37] , pulegone and pulegone oxide[38] , jojoba oil[39] and bifurcaria bifurcata extract[40] have been investigated; however, the constituents that provide inhibitive action, the mechanisms and the best condition for inhibition are still unclear. The encouraging results obtained by naturally oils as corrosion inhibitor of the steel in acid solutions permit to test more substance oils. Up to now, a never study is about the effect of the addition of Argania plant extract on the corrosion of the steel in hydrochloride solution. In the present work, inhibitive action of Argania plant extract (APE) as a cheap, eco friendly and naturally occurring substance on corrosion behaviour of C38 steel in 1 mol/L HCl has been studied by gravimetric method and electrochemical techniques such as potentiodynamic polarisation, linear polarisation and electrochemical impedance spectroscopy (EIS). 2 Experimental 2.1 Electrochemical tests The electrochemical study was carried out using a potentiostat PGZ100 piloted by Voltamaster soft-ware. This potentiostat is connected to a cell with three electrode thermostats with double wall (Tacussel Standard CEC/TH). A saturated calomel electrode (SCE) and Pt electrode were used as reference and auxiliary electrodes, respectively. The material used for constructing the working electrode was C38 steel that had the following chemical composition (wt pct): 0.179 C, 0.165 Si, 0.439 Mn, 0.203 Cu, 0.034 S and Fe balance. For electrochemical tests, the commercial C38 steel samples are in the form of a surface parallelepiped of 0.056 cm2 used as a work electrode that is mechanically abraded with 180, 320, 800 grades of emery papers, rinsed with distilled water then with ethanol before plunging the electrode in the solution. Anodic and cathodic potentiodynamic polarization curves were plotted separately at a polarization scan rate of 0.5 mV/s. Before all experiments, the potential was stabilized at free potential during 30 min. The solution test is there after de-aerated by bubbling nitrogen. Gas pebbling is maintained prior and through the experiments. EIS measurements are carried out with the electrochemical system (Tacussel), which included a digital potentiostat model Voltalab PGZ100 computer at corrosion potential (Ecorr ) after immersion in solution without bubbling. After the determination of steadystate current at a corrosion potential, sine wave voltage (10 mV) peak to peak, at frequencies between 100 kHz and 10 mHz are superimposed on the rest potential. Computer programs automatically controlled the measurements performed at rest potentials after 0.5 h of exposure. The impedance diagrams are given in the Nyquist representation. Experiments are repeated three times to ensure the reproducibility. 2.2 Weight loss measurements Coupons were cut into 2 cm2 cm0.08 cm dimensions used for weight loss measure-

 12 ments. Prior to all measurements, the exposed area was mechanically abraded with 180, 320, 800 grades of emery papers. The specimens are washed thoroughly with bidistilled water degreased and dried with ethanol. Gravimetric measurements are carried out in a double walled glass cell equipped with a thermostated cooling condenser. The solution volume is 80 cm3 . The immersion time for the weight loss is 8 h. 2.3 Solution preparation Sample of ground leaves of Argan plant was collected from the area of Biougra located at Chtouka Ait Baha (Morocco) in December. Stock solution of the plant extract was prepared by stirring cold weighed amounts of the dried and ground leaves of Argania plant for 24 h in 1 mol/L HCl solution (The solution 1 mol/L HCl was prepared by dilution of analytical grade 37% HCl with double distilled water). The resulting solution was ltered and used for preparing other solutions. This extract was used to study the corrosion inhibition properties and to prepare the required concentrations of APE. The solution tests are freshly prepared before each experiment. 3 Results and Discussion 3.1 Eect of concentration 3.1.1 Polarization curves The cathodic and anodic polarisation curves of C38 steel in 1 M HCl in the absence and presence of APE at dierent concentrations at 298 K are presented in Fig. 1. Values of the associated electrochemical parameters are given in Table 1. In this case, the inhibition eciency (E%) is dened as follows: E% = 1 Icorr 100 Icorr (1)
-2

10

-1

10

-2

cm

10

-3

10

-4

corr

2.5 g/L 2 g/L

10

-5

1.5 g/L 1 g/L

10

-6

0.5 g/L 5x10

-2

g/L

Blank

10

-7

-0.8

-0.7

-0.6
E / V (vs SCE)

-0.5

-0.4

Fig. 1 Cathodic and anodic polarisation curves of C38 steel in 1 M HCl in the presence of dierent concentrations of Argan plant extract at 298 K

where Icorr and Icorr are the uninhibited and inhibited corrosion current densities, respectively, determined by extrapolation of cathodic Tafel lines to corrosion potential (Ecorr ). The values of the electrochemical parameters for dierent Argan plant extract concentrations are given in Table 1. Inspection of the Fig. 1 reveals that the polarization curves are shifted toward more negative potentials and less current density upon addition of Argan plant extract. This result conrms the inhibitive action of the Argan plant extract toward acid corrosion of steel[42] . As seen, addition of Argan plant extract aects both anodic dissolution of the steel and cathodic reduction reactions indicating that the extracts could be classied as mixed-type inhibitors[43] . We also remark that the cathodic current-potential curves give rise to parallel Tafel lines, which indicate that hydrogen evolution reaction is activation controlled and that the addition of the APE does not modify the mechanism of this process (Fig. 1)[31] .

 13
Table 1 Electrochemical parameters of steel at various concentrations of Argan plant extract in 1 mol/L HCl and corresponding inhibition eciency Inhibitor/(g/L) Blank 5102 0.5 1.0 1.5 2.0 2.5 Ecorr /(mV/SCE) 615 609 620 632 643 652 652 Icorr /(A/cm2 ) 84 45 39 26 17 13 4 bc /(mV/dec) 100 90 103 95 84 80 90 ba /(mV/dec) 93 81 92 91 93 90 99 E% 46 54 69 80 85 95

Note: bc is cathodic Tafel slope, ba is anodic Tafel slope. The displayed data show that increasing APE concentration decreases the Icorr , reaching 95% at 2.5 g/L Argan plant extract, but slightly aect the values of Ecorr signifying that it could act as pickling inhibitor[44] . The higher inhibition eciency obtained at these concentrations suggests that, the extracts could serve as eective corrosion inhibitor. The values of ba and bc are slightly changed indicating that the inhibition mechanism occurred by simple blocking of the available cathodic and anodic sites of the metal surface[45] . 3.1.2 Electrochemical impedance spectroscopy measurements In order to get more information about the corrosion behaviour of the steel, in acidic solution with and without APE, EIS measurements have been carried out at 298 K after 30 min of immersion (Fig. 2). The inhibition eciency determined by transfer resistance (ERt %) can be calculated by the following formula:
0 (Rt Rt ) ERt % = 100 Rt

3000

2000

cm

2.5 g/L 2 g/L

im

1.5 g/L 1 g/L

1000

0.5 g/L 5x10 g/L Blank

-2

0 0 2000 4000
Z
re

6000
/ cm
2

8000

10000

(2)

Fig. 2 Nyquist diagrams for the steel electrode with and without Argan plant extract after 30 min of immersion at 298 K

0 where Rt and Rt are the charge transfer resistances in inhibited and uninhibited solutions respectively. The values of the polarization resistance were calculated by subtracting the high frequency intersection from the low frequency intersection[32] . Double layer capacitance values were obtained at maximum frequency (fmax ), at which the imaginary component of the Nyquist plot is maximum and calculated using the following equation:

Cdl =

1 2fmax Rt

(3)

where Cdl means double layer capacitance (Fcm2 ). The data collected are gathered in Table 2. As it can be seen from Fig. 2, impedance diagrams show a semi-circular appearance, indicating a charge transfer process mainly controls the corrosion of steel[33] . Deviations

 14
Table 2 Impedance parameters for the corrosion of steel in acid at various contents of Argan plant extract Blank C/(g/L) 5102 0.5 1.0 1.5 2.0 2.5 Rt /(kcm2 ) 21 41 48 70 107 134 200 fmax /Hz 50 28 26 20 18 13 11 Cdl /(F/cm2 ) 149 138 127 114 83 91 72 ERt % 48 56 69 80 84 90

Argan plant extract

of the perfect circular shape are often referred to the frequency dispersion of the interfacial impedance. This anomalous phenomenon may be attributed to the inhomogeneity of the electrode surface arising from the surface roughness or interfacial phenomena[46,47] . The general shape of the curves is very similar for all samples; the shape is maintained throughout the whole concentrations, indicating that almost no change in the corrosion mechanism occurred due to the inhibitor addition[34] . From the impedance data given in Table 2, we conclude that the value of Rt increases with increase in the concentration of the inhibitors (APE). This behavior reveals the adsorption of inhibitors on the steel[48] and this indicates an increase in the corrosion inhibition eciency in the acidic solution. Values of double layer capacitance are also brought down to the maximum extent in the presence of inhibitor and the decrease in the values of Cdl follows the order similar to that obtained for Icorr in this study. The results obtained from the polarization technique in the acidic solution were in good agreement with those obtained from the EIS with a small variation. 3.1.3 Weight loss, corrosion rates and inhibition eciency The eect of the addition of APE tested at dierent concentrations on the corrosion of the steel in 1 mol/L HCl solution was studied by using weight-loss at 298 K after 8 h of immersion. The inhibition eciency determined by weight loss (Ew %) is calculated as follows: Wcorr Wcorr 100 (4) Ew % = Wcorr where Wcorr and Wcorr are the corrosion rates of the steel in 1 mol/L HCl in absence and presence of inhibitor, respectively. Table 3 gives the values of the inhibition eciency obtained from the weight loss measurements for dierent concentrations of APE in 1 mol/L HCl at 298 K after 8 h of immersion. As it is clear in Table 3, that the gravimetric measurements show a decrease of the corrosion rate with the concentration of the APE and its corrosion eciency increases and reaches 94% at 2.5 g/L for APE. The results obtained from weight loss are in good agreement with the electrochemical studies. 3.2 Eect of the temperature 3.2.1 Weight loss tests The eect of the temperature on the corrosion rate of the steel in free acid and added

 15
Table 3 Inhibition eciencies for various concentrations of Argan plant extract in 1 mol/L HCl from weight loss Argan plant extract/(g/L) Blank 5102 0.5 1.0 1.5 2.0 2.5 Wcorr /(mgcm2 h1 ) 0.2327 0.1256 0.1026 0.0726 0.0499 0.0356 0.0139 Ew % 46 56 69 79 85 94

with 2.5 g/L of APE at 8 h immersion period is made from 298 to 328 K as shown in Table 4. It is clear that the increase of the corrosion rate is more pronounced with the rise of the temperature for blank solution. In the presence of the inhibitor, Wcorr is highly reduced. Also, the inhibition eciency decreases slightly with increasing temperature. This can be explained by the decrease of the strength of the adsorption processes at elevated temperature and suggested a physical adsorption mode[49] . From this result, we can conclude that APE is an excellent inhibitor. 3.2.2 Kinetic parameters The variation of the logarithm of corrosion rate of the steel in 1 mol/L HCl at 2.5 g/L APE as function of temperature reciprocate was illustrated in Fig. 3. It shows that the corrosion reaction can be regarded as an Arrhenius-type process equation: Wcorr = kexp(Ea /RT ) Wcorr = k exp(Ea /RT ) (5)

where Wcorr and Wcorr are the corrosion rates of steel with and without inhibitor, respectively. Ea and Ea are the apparent activation energies in the presence and absence of inhibitor, respectively. k and k are constants, R is gas constant, T is temperature. The apparent activation energy was determined from the slopes of lnWcorr vs 1/T graph depicted in Fig. 3. It is seen that the presence of APE modies the values of dierent activation energies (Ea =72 kJ/mol; Ea =90 kJ/mol). We remark that the activation energy increases in the presence of inhibitor that indicates the poorer performance of APE at higher temperature. The increase of activation energy is generally interpreted by an electrostatic adsorption process of the inhibitor on the steel surface[50,51] . The activation parameters for the studied system (H , G and S ) were estimated
Table 4 Eect of the temperature on the steel in 1 mol/L HCl and added of 2.5 g/L of APE T /K 298 308 318 328 1 mol/L HCl Wcorr /(mgcm2 h1 ) 0.2327 0.4814 1.1340 3.3726 1 mol/L HCl+2.5 g/L Wcorr /(mgcm2 h1 ) Ew % 0.0139 94 0.0407 92 0.1135 90 0.4255 87

 16 from the transition state equation[52] : Wcorr = RT H S exp exp Nh R RT G = H T S (6) (7)

where N is the Avogadro s number, h is the Plank s constant, S , H and G is the entropy, enthalpy and free energy of activation, respectively. Figure 4 shows the plots of ln(Wcorr /T ) against 1/T of APE. Straight lines are obtained with a slope of (H /R) and an intercept of (lnR/N h + S /R) from which the values of H and S are calculated respectively (Table 5).

K ))

h ))

-1

-1

Blank

-5

Blank +2.5 g/L

-2

-1

+2.5 g/L

cm

-6

/ (mg

cm

-2

-7

corr

-2

T/(mg
corr

-8

ln (

-4

ln (

-9

-10 3.0 3.1 3.2

(1000/

3.0

3.1

3.2
(1000/

3.3

3.4

3.3
-1

3.4

T) / K

-1

T) / K

Fig. 3 Arrhenius plots of the steel in 1 mol/L HCl with and without 2.5 g/L APE

Fig. 4 Relation between ln(Wcorr /T ) and 1000/T in acid at dierent temperatures

Table 5 Values of the activation parameters H , S and G for the steel in 1 mol/L HCl in the absence and the presence of 2.5 g/L of APE Inhibitor/(g/L) Blank 2.5 H /(kJ/mol) 69 87 S /(Jmol1 K1 ) 8 30 G /(kJ/mol) at 298 K 72 78

From the data obtained in Table 5, it can be concluded that: (1) The positive signs of H reect the endothermic nature of the steel dissolution process. It is obviously that the activation energy strongly increases in the presence of the inhibitor. Some authors[3840] have attributed this result to the inhibitor species being physically adsorbed on the metal surface. (2) The positive values of entropies S in the presence of inhibitor imply that the activated complex in the rate determining step represents an association rather than a dissociation step, meaning that an increase in disordering takes place on going from reactants to the activated complex[41] . (3) The G values for inhibited systems were more positive than that for the uninhibited systems revealing that in presence of inhibitor addition the activated corrosion complex becomes less stable as compared to its absence.

 17 4 Conclusions We have studied the application of Argan plant extract as green corrosion inhibitor for the steel in 1 mol/L HCl by using various methods. The results obtained are as follows: (1) APE acts as an excellent mixed inhibitor. (2) The inhibition eciency increases with increased APE concentration to attain a maximum value of 95% at 2.5 g/L. (3) The data obtained from the three dierent methods: potentiodynamic polarisation, EIS and weight loss, are in good agreements. (4) The inhibition eciency of APE decreases with the rise of the temperature. (5) APE studied was adsorbed physically on the steel surface according to the Langmuir isotherm model. Thermodynamic parameters are determined.
REFERENCES [1] N. Putilova, S.A. Balezin and V.P. Barannik, Metallic Corrosion Inhibitors (Pergamon Press, New York, 1960) p.31 [2] M.A. Amin, S.S. Abd El-Rehim, E.E.F. El-Sherbini and R.S. Bayoumi, Electrochim Acta 52 (2007) 3588 [3] A. Eloua, B. Hammouti, H. Oudda, S. Kertit, R. Touzani and A. Ramdani, Anti Corros Meth Mater 49 (2002) 199 [4] A. Dafali, B. Hammouti, R. Touzani, S. Kertit, A. Ramdani and K. Elkacemi, Anti Corros Meth Mater 49 (2002) 96 [5] R. Salghi, L. Bazzi, B. Hammouti, E. Zine, S. Kertit, S. El Issami and E. Ait Eddi, Bull Electrochem 17 (2001) 429 [6] F. Touhami, A. Aouniti, Y. Abed, B. Hammouti, S. Kertit, A. Ramdani and K. Elkacemi, Corros Sci 42 (2000) 929 [7] F. Touhami, A. Aouniti, Y. Abed, B. Hammouti, S. Kertit and A. Ramdani, Bull Electrochem 16 (2000) 245 [8] R. Salghi, L. Bazzi, B. Hammouti and S. Kertit, Bull Electrochem 16 (2000) 272 [9] F. Touhami, S. Kertit, B. Hammouti and A. Aouniti, Ann Chim Sci Mater 24 (1999) 581 [10] B. Hammouti, R. Salghi and S. Kertit, J Electrochem Soc India 47 (1998) 31 [11] A. Aouniti, B. Hammouti, M. Brighli, S. Kertit, F. Berhili, S. El Kadiri and A. Ramdani, J Chim Phys Phys 93 (1996) 1262 [12] M. Mihit, R. Salghi, S. El Issami, L. Bazzi, B. Hammouti, E. Ait Addi and S. Kertit, Pigment Resin Technol 35(3) (2006) 151 [13] M. Mihit, S. El Issami, M. Bouklah, L. Bazzi , B. Hammouti, E. Ait Addi, R. Salghi and S. Kertit, Appl Surf Sci 252(6) (2006) 2389 [14] S. El Issami, L. Bazzi, M. Hilali, R. Salghi and S. Kertit, Ann Chim Sci Mater 27 (2002) 63 [15] M. Mihit, R. Salghi, S. El Issami, L. Bazzi, B. Hammouti, E. Ait Addi and S. Kertit, Pigment Resin Technol 35 (3) (2006) 151 [16] Y. Abed, B. Hammouti, S. Kertit, K. El Kacemi and A. Mansri, Bull Electrochem 17 (2001) 105 [17] Y. Abed, Z. Arrar, A. Aouniti, B. Hammouti, S. Kertit and A. Mansri, J Chim Phys Phys 96 (1999) 1347 [18] A. Aouniti, B. Hammouti, S. Kertit and M. Brighli, Bull Electrochem 14 (1998) 193 [19] A. Chetouani, K. Medjahed, K.E. Benabadji, B. Hammouti, S. Kertit and A. Mansri, Prog Org Coat 46 (2003) 312. [20] K. Barouni, M. Mihit, L. Bazzi, R. Salghi, S.S. Al-Deyab, B. Hammouti and A. Albourine, Open Corr J 3 (2010) 63 [21] K. Barouni, L. Bazzi, R. Salghi M. Mihit, B. Hammouti, A. Albourine and S. El Issami, Mater Lett 62 (2008) 3325 [22] N.O. Eddy and E.E. Ebenso, J Pure Appl Chem 2 (2008) 46 [23] Z. Faska, L. Majidi, R. Fihi, A. Bouyanzer and B. Hammouti, Pigm Resin Technol 36 (2007) 293

 18
[24] A. Bouyanzer, B. Hammouti and L. Majidi, Mater Lett 60 (2006) 2840 [25] A. Chetouani, B. Hammouti and M. Benkaddour, Pigm Resin Technol 33 (2004) 26 [26] E. El Ouariachi, J. Paolini, M. Bouklah, A. Elidrissi, A. Bouyanzer, B. Hammouti, J.M. Desjobert and J. Costa, Acta Metall Sin (Engl Lett) 23 (2010) 13 [27] M. Bendahou, M. benabdallah and B. Hammouti, Pigm Resin Technol 35 (2006) 95 [28] A. Bouyanzer and B. Hammouti, Bull Electrochem 20 (2004) 63 [29] L. Bammou, B. Chebli, R. Salghi, L. Bazzi, B. Hammouti, M. Mihit and M. Elidrissi, Green Chem Lett Rev 3(3) (2010) 173 [30] M. Benabdellah, B. Hammouti, M. Benkaddour, M. Bendahhou and A. Aouniti, Appl Surf Sci 252 (2006) 6212 [31] L. Bammou, M. Mihit, R. Salghi, A. Bouyanzer, S.S. Al-Deyab, L. Bazzi and B. Hammouti, Int J Electrochem Sci 6 (2011)1454 [32] O. Ouachikh, A. Bouyanzer, M. Bouklah, J.M. Desjobert, J. Costa, B. Hammouti and L. Majidi, Surf Rev Lett 16 (2009) 49 [33] M. Dahmani, A. Et-Touhami, S.S. Al-Deyab, B. Hammouti and A. Bouyanzer, Int J Electrochem Sci 5 (2010) 1060 [34] E.L. Chaieb, A. Bouyanzer, B. Hammouti and M. Benkaddour, Appl Surf Sci 249 (2005) 183 [35] A. Chetouani and B. Hammouti, Bull Electrochem 19 (2003) 23 [36] B. Zerga, M. Sfaira, Z. Rais, M. Ebn Touhami, M. Taleb, B. Hammouti, B. Imelouane and A. Elbachiri, Mater Technol 97 (2009) 297 [37] E. Chaieb, A. Bouyanzer, B. Hammouti and M. Berrabah, Acta Phys Chim Sin 25 (2009) 1254 [38] Z. Faska, A. Bellioua, M. Bouklah, L. Majidi, R. Fihi, A. Bouyanzer and B. Hammouti, Monatshefte fr Chemie 139 (2008) 1417 u [39] A. Bouyanzer and B. Hammouti, Pigm Resin Technol 33 (2004) 287 [40] Y. Abboud, A. Abourriche, T. Ainane, M. Charrouf, A. Bennamara and O. Tanane, Chem Eng Commun 196 (2009) 788 [41] M. Elachouri, M.S. Hajji, M. Salem, S. Kertit, J. Aride, R. Coudert and E. Essassi, Corrosion 52 (1996) 103 [42] A.Y. El-Etre, Mater Chem Phys 108 (2008) 278 [43] A.M. Abdel-Gaber, B.A. Abd-El-Nabey, I.M. Sidahmed, A.M. El-Zayady and M. Saadawy, Corros Sci 48 (2006) 2765 [44] G. Lyberatos and L. Kobotiatis, Corrosion 47 (1991) 820 [45] A.M. Abdel-Gaber, B.A. Abd-El-Nabey and M. Saadawy, Corros Sci 51 (2009) 1038 [46] H. Shih and H. Mansfeld, Corros Sci 29 (1989) 1235 [47] S. Martinez and M. Metikos-Hukovic, J Appl Electrochem 33 (2003) 1137 [48] A. Yurt, A. Balaban, S. Ustn Kandemir, G. Bereket and B. Erk, Mater Chem Phys 85 (2004) 420. u [49] M. Bouklah, A. Attayibat, S. Kertit, A. Ramdani and B. Hammouti, Appl Surf Sci 242 (2005) 399 [50] A. Popova, E. Sokolova, S. Raicheva and M. Christov, Corros Sci 45 (2003) 33 [51] T. Szauer and A. Branbt, Electrochim Acta 22 (1981) 1209 [52] S.S. Abd-El-Rehim, S.A.M. Refaey, F. Taha, M.B. Saleh and R.A. Ahmed, J Appl Electrochem 31 (2001) 429