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Corrosion Science 53 (2011) 14841488

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Novel thiophene symmetrical Schiff base compounds as corrosion inhibitor for mild steel in acidic media
S. Issaadi a,, T. Douadi a, A. Zouaoui a, S. Chafaa a,b, M.A. Khan b, G. Bouet b
a b

Laboratoire dlectrochimie des Matriaux Molculaires et Complexes, Facult des Sciences de lIngnieur, Universit Ferhat Abbas, DZ-19000 Stif, Algeria Universit dAngers, Chimie de coordination, SONAS, EA 921, France

a r t i c l e

i n f o

a b s t r a c t
The inhibiting effect of two Schiff bases on the corrosion of the mild steel (MS) in 1 M HCl has been studied by electrochemical impedance spectroscopy (EIS) and Tafel polarisation measurements. The Schiff bases, 4,40 -bis(3-carboxaldehyde thiophene) diphenyl diimino ether (L1) and 4,40 -bis(3-carboxaldehyde thiophene) diphenyl diimino ethane (L2), were synthesized using 3-carboxaldehydethiophene and its corresponding amine. Polarisation curves reveal that both compounds are mixed type (cathodic/anodic) inhibitors and inhibition efciency (% IE) increases with increasing concentration of compounds. It is suggested that their effects depend on their concentrations and the molecular structures. Adsorption of compounds on mild steel surface is spontaneous and obeys Langmuirs isotherm. Published by Elsevier Ltd.

Article history: Received 2 May 2010 Accepted 13 January 2011 Available online 21 January 2011 Keywords: C. Corrosion C. Inhibitor C. Schiff base A. Mild steel A. Hydrochloric acid

1. Introduction The use of inhibitors is one of the most practical methods for protection against corrosion especially in acidic media [1,2]. Acid solutions are generally used in several industrial processes. HCl is widely used in picking solutions. Because of their aggressiveness, the use of corrosion inhibitors is considered as the most effective method for the protection of many metals and alloys against such acid attack [3,4], reduces the dissolution rate of metals. Compounds containing functional groups with heteroatoms, which can donate one pair of electrons, are found to be very efcient as inhibitors against metal corrosion in many environments. Many heterocyclic compounds with polar groups and/or p electrons are efcient corrosion inhibitors in acidic solutions. Organic molecules of this type can adsorb on the metal surface and form a bond between their N-electron pair and/or p electron cloud and the metal surface, thereby reducing the corrosion in acidic solutions [57]. Some Schiff bases inhibitors have been previously reported as effective corrosion inhibitors for various metals in acid media, such as Schiff bases containing thiophene substituents [8,9] and furoin thiosemicarbazone [10]. The aim of the present investigation is to examine the inhibitory action of two Schiff bases containing nitrogen and sulphur heteroaromatic compound as substituents in their structures for the corrosion of mild steel in 1 M HCl solution. Effects of concentra Corresponding author.
E-mail address: issaadi-s@univ-setif.dz (S. Issaadi). 0010-938X/$ - see front matter Published by Elsevier Ltd. doi:10.1016/j.corsci.2011.01.022

tions and molecular structures on the inhibition efciencies of the selected Schiff bases have been studied systematically. Differences in behaviour of inhibitors were explained based on structural properties of investigated inhibitors. 2. Experimental Compounds L1 and L2 were synthesized according to published methods [11,12]. Diamine (1 mM) (hot ethanol, 20 mL) was added dropwise 2 mM of thiophene 3-carbaldehyde (Fluka Chemical Company). These products are soluble in ethanol/H2O and DMF solutions. The structures of these products were conrmed by elemental analysis (service dAnalyse, ICSN- CNRS, Gif sur Yvette (France)) and FT-IR spectroscopy. The molecular structures of L1 and L2 are shown in Fig. 1. Elemental analyses: Anal. Cal. For L1: C, 68.04; H, 4.12; N, 7.21. Found: C, 67.6; H, 4.08; N, 7.31%; Yield = 91%; M.P = 211 C; IR bands (KBr): m(C@N) = 1618 cm1. Anal. Cal. For L2: C, 71.96; H, 5.03; N, 6.99. Found: C, 71.27; H, 4.82; N, 7.03%; Yield = 88%; M.P = 208 C; IR bands (KBr): m(C@N) = 1614 cm1. The 1H-RMN spectrum of L2 exhibits a singulet at 3.1 ppm, corresponding to the four aliphatic protons. In both ligands, the aromatic protons give a multiplet centered at 7.2 ppm (L1) and 7.1 ppm (L2), respectively. A singulet at 8.5 ppm (L1) and 8.4 ppm (L2) is due to the imino proton, the three thiophene protons lead to the following signals: singulet at 7.8 ppm, and a doublet at 7.4 and 7.7 ppm, respectively. The electrolyte solution was 1 M HCl, prepared from analytical grade 37% HCl (Merck) and double distilled water. The concentration range of inhibitor

S. Issaadi et al. / Corrosion Science 53 (2011) 14841488


10

1485

N L1 S
CH2-CH 2

N
1

1 2 3 4 5

i (mA/cm )
0.1

L2
S S

Fig. 1. Structures of synthesized Schiff bases L1 and L2.


0.01 -600 -550 -500 -450 -400 -350

1 : Blank -4 2 : 1.10 M -4 3 : 5.10 M -3 4 : 1.10 M -3 5 : 5.10 M


-300 -250

employed was 1 10 to 5 10 M in 1 M HCl. All tests have been performed in deaerated solutions and at 25 1 C. The working electrode was prepared from a cylindrical mild steel bar. The corrosion tests were performed on mild steel with a composition (in wt.%) C: 0.076, P: 0.012, Si: 0.026, Mn: 0.192, Cr: 0.050, Cu: 0.135, Al: 0.023, Ni: 0.050 and Fe balance. The electrode was inserted in Teon tube and isolated with polyester so that only its section (0.5 cm2) was allowed to contact the aggressive solutions. The electrodes were mechanically abraded with a series of emery papers (800 and 1200 grad). Then it was rinsed in acetone and double distilled water before their immersion in experimental solution. Electrochemical measurements were conducted in a conventional three-electrode thermostated cell. A platinum disk as counter electrode and standard calomel electrode (SCE) as the reference electrode have been used in the electrochemical studies. The potentiodynamic curves were recorded using a PGZ 301 voltalab 40 system connected to a personal computer. The working electrode was rst immersed into the test solution for 60 min to establish a steady state open circuit potential. After measuring the open circuit, potential dynamic polarisation curves were obtained with a scan rate of 0.5 mV/s. Corrosion rates (corrosion current densities) were obtained from the polarisation curves by linear extrapolation of the anodic and cathodic branches of the Tafel plots at points 75 mV more positive and more negative than the corrosion potential (Ecorr). Electrochemical impedance (EIS) measurements were performed at potential open circuit in the frequency range from 100 kHz to 10 MHz, with a signal amplitude perturbation of 10 mV. Measurements were carried out using a PC controlled Volta Lab PGZ 301 system with and Voltamaster 4 software. 3. Results and discussion 3.1. Tafel polarisation measurements Figs. 2 and 3 show anodic and cathodic polarisation plots recorded on mild steel electrode in 1 M HCl in absence and presence of different concentrations of L1 and L2 inhibitors. Table 1 shows the electrochemical corrosion kinetic parameters, i.e., corrosion potential (Ecorr), cathodic and anodic Tafel slopes (bc, ba) and corrosion current density icorr obtained by extrapolation of the Tafel lines. As it was expected both anodic and cathodic reactions of mild steel electrode corrosion were inhibited by the increase of the synthesized Schiff bases. This result suggests that the addition of the synthesized inhibitors reduces anodic dissolution and also retards the hydrogen evolution reaction [13]. The calculated inhibition efciency, IE (%) is also calculated from the following equation:

E (mVvs.SCE)
Fig. 2. Tafel polarisation curves for mild steel obtained at 25 C in 1 M HCl containing different concentrations of Schiff base L1.

10

2 3 4
1

i (mA/cm )
0.1

1 : Blank -4 2 : 1.10 M -4 3 : 5.10 M -3 4 : 1.10 M -3 5 : 5.10 M


-600 -550 -500 -450 -400 -350 -300 -250

0.01 -650

E (mVvs.SCE)
Fig. 3. Tafel polarisation curves for mild steel obtained at 25 C in 1 M HCl containing different concentrations of Schiff base L2.

IE%

icorr icorr icorr


0

100

where icorr and icorr are uninhibited and inhibited current densities, respectively. At a concentration of 5.103 M L1 exhibits maximum inhibition efciency (92%) and at the same concentration L2 showed 88.6%. It can be seen that the corrosion rate is decreased and inhibition efciency IE (%) is increased by increasing inhibitor concentration [13]. These inhibitors cause change in the anodic and cathodic Tafel slopes and no denite trend was observed in the shift of Ecorr values in the presence of different concentrations of the synthesized inhibitors, suggesting that these compounds behave as mixed-type (anodic/cathodic) inhibitors [1416]. Increase in inhibition efciencies with the increase of concentrations of studied Schiff bases shows that the inhibition actions are due to its adsorption on mild steel surface [17,18]. The difference in inhibition efciency between L1 and L2 is due to the effect of the oxygen bridge atom, which modies the electronic density along the symmetrical parts of the molecule. Fig. 4 shows the change of IE (%) with the inhibitor concentration. Compound L1 is observed to have the highest inhibition

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S. Issaadi et al. / Corrosion Science 53 (2011) 14841488

Table 1 Polarisation parameters and corresponding inhibition efciency for the mild steel in 1 M HCl with and without addition of various concentrations of Schiff bases. Compound Blank L1 C (M) 1 1 104 5 104 1 103 5 103 1 104 5 104 1 103 5 103 Ecorr (mV/SCE) 440 446 438 435 451 474 470 474 450 icorr (lA cm2) 891 442 218 169 71 524 385 199 101 bc (mV/dec) 123 111 115 120 119 152 156 133 139 ba (mV/dec) 118 106 76 81 67 126 106 93 52 IE (%) 50.3 75.5 81.0 92.0 41.1 56.7 77.6 88.6 h 0.50 0.75 0.81 0.92 0.41 0.56 0.77 0.88

L2

1.0
140

0.9

120 100

0.8

-Zi (ohm.cm )

IE (%)

0.7

80 60 40

blank -4 1.10 M -4 5.10 M -3 1.10 M -3 5.10 M

0.6

0.5

-2

0.4 0.000 0.001 0.002 0.003

compound L1 compound L2
0.004 0.005

20 0 0 30 60 90 120 150 180 210 240 270 300 330

c (M)
Fig. 4. Effect of inhibitor concentration on the efciencies of mild steel obtained at 25 C in 1 M HCl containing different concentrations of the synthesized Schiff bases L1 and L2.

Zr (ohm.cm2)
Fig. 5. Nyquist impedance diagrams for mild steel obtained at 25 C in 1 M HCl solution containing different concentrations of Schiff base L1.

efciency. The increase in the inhibition efciencies of mild steel, in 1 M HCl solution, with increasing additive concentration can be explained on the basis of additive adsorption. 3.2. Electrochemical impedance spectroscopy measurements

140

120

100

Nyquist plots of mild steel in uninhibited and inhibited acidic solutions containing various concentrations of Schiff base are shown in Figs. 5 and 6. From these plots, the impedance response of mild steel has signicantly changed on addition of the Schiff base. For analysis of the impedance spectra containing a single capacitive semi circle, the standard Randles circuit is used [19], where the circuit is composed of a solution resistance component (Rs), a polarisation resistance component (Rp) and a capacitance component (Cdl). Similar gures have been described in literature for the acidic corrosion of iron and steel in the presence and absence of inhibitor molecules [2022]. Polarisation resistance and the inhibitor efciency values are given in Table 2. 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 Eq. (2).

blank -4 1.10 M -4 5.10 M -3 1.10 M -3 5.10 M

-Zi (ohm.cm )

-2

80

60

40

20

0 0 30 60 90 120 150 180 210 240 270 300 330

Zr (ohm.cm2)
Fig. 6. Nyquist impedance diagrams for mild steel obtained at 25 C in 1 M HCl solution containing different concentrations of Schiff base L2.

C dI

1 1 2pfmax Rp

2 IE%

The results showed the Rp values, which were increased with increasing the additive concentration. Since Rp is inversely proportional to the corrosion current it could be used to calculate the inhibition efciency (IE), from the relation (3):

Rp R0 p 100 Rp

where Rp and R0 are the polarisation resistances in the presence and p absence of inhibitors, respectively. The decrease in the values of Cdl follows the order similar to that obtained for the icorr studies. This

S. Issaadi et al. / Corrosion Science 53 (2011) 14841488 Table 2 Electrochimical impedance parameters for mild steel in 1 M HCl without and with addition of various concentrations of studied Schiff bases. Compound Blank L1 C (M) 1 1 104 5 104 1 103 5 103 1 104 5 104 1 103 5 103 Rp (X cm2) 17.2 40.7 50.7 96.0 205 25.3 41.3 91.2 200 Cdl (lF cm2) 270.3 92.0 88.5 73.0 32.1 136.0 95.0 75.5 37.0 IE (%) 57.7 66.0 82.0 91.6 32.0 58.3 81.1 91.4

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Table 3 Adsorption equilibrium constant (Kads) and the free energy of adsorption (DG0 ) of L1 ads and L2 on mild steel surface immersed in 1 M HCl. Compound L1 L2 Kads 7.74 10 4.46 103
3

R2 0.9999 0.9997

DG0 (kJ mol1) ads


32.16 30.79

L2

equilibrium (Kads) calculated from the Langmuir adsorption isotherm for L1 and L2 were 7.74 103 and 4.46 103, respectively. The relatively high values of the adsorption equilibrium constant reect the high adsorption ability of these molecules on mild steel surface. The value of Kads is related to the standard free energy of adsorption, DG0 , by the following Eq. (6). ads

can be explained on the basis of compound adsorption on the metal surface leading to the formation of a surface lm in the acidic solution [2325]. The impedance study also gave the same efciency trend as found in Tafel polarisation methods. 3.3. Adsorption isotherm and thermodynamics calculations The interactions between the inhibitor and the mild steel surface can be examined by the adsorption isotherm. The degree of surface coverage values (h) for various concentrations of the inhibitors in the solution have been evaluated from the polarisation measurements (Table 1). Suitable adsorption isotherm was obtained, using these calculated values. The linear relationships of C/h versus C, depicted in Fig. 7, suggest that the adsorption of L1 and L2 on the mild steel obeyed the Langmuir adsorption isotherm [2628]. This isotherm can be represented as:

K ads

1 DG0 ads exp 55:5 RT

! 6

C 1 C h K ads

where R is the universal gas constant and T is the absolute temperature. The values of 55.5 is the molar concentration of water in solution expressed in mol l1. The calculated DG0 and Kads were listed ads in Table 3. The negative values of DG0 indicating the spontaneads ously adsorption of these molecules on the metal surface were found to be 32.16 and 30.79 kJ mol1 for L1 and L2, respectively. Values of DG0 around 20 kJ mol1 or lower are consistent with ads the electrostatic interaction between charged organic molecules and the charged metal surface (physisorption); those around 40 kJ mol1 or higher involve charge sharing or transfer from the organic molecules to the metal surface to form a co-ordinate type of bond (chemisorption). The values of DG0 for both comads pounds being less than 40 kJ mol1 indicate a physical adsorption. In addition to electrostatic interaction, there may be some other interactions [29]. 3.4. Molecular structure and inhibitor properties The mechanism of the inhibition processes of the corrosion inhibitors under consideration is mainly the adsorption one. The process of adsorption is governed by different parameters almost depend on the chemical structure of these inhibitors. The presence of sulfur in the organic structures makes the formation of dpdp bond resulting from overlap of 3d electrons from Fe atoms to the 3d vacant orbital of the sulphur atom possible, which enhances the adsorption of the compounds on the metal surface. These molecules are able to adsorb on the metal surface through N and S atoms, azomethine groups, heterocyclic and aromatic rings which are electron donating groups [30]. Among the compounds investigated in this study, L1 has been found to give the best performance. This can be explained on the basis of the presence of oxygen molecule in the middle of L1 molecular structure which rises the possibility of transferring the unshared electron of this molecule to iron in comparison to L2 and therefore results in a better adsorption [31]. 4. Conclusion The corrosion behaviour of mild steel was investigated in 1 M HCl with and without addition of various concentrations of Schiff bases at different concentrations, using potentiodynamic and electrochemical impedance techniques. Polarisation curves reveal that both compounds are mixed type (cathodic/anodic) inhibitors and inhibition efciency (% IE) increases with increasing concentration of compounds. The adsorption of Schiff bases on mild steel in 1 M HCl solution obeys Langmuir adsorption isotherm. The negative values of DG0 show the spontaneity of the adsorption. ads

The degree of surface coverage of each inhibitor at a given concentration can be calculated using the equation:

icorr icorr icorr


0

The strong correlation (R2 = 0.9999 and 0.9997) of the Langmuir adsorption isotherm for L1 and L2 was observed. Langmuir adsorption isotherm assums that the adsorption of organic molecule on the adsorbent is monolayer. Values of constant adsorption

0.006 0.005 0.004

C/

0.003 0.002 0.001 0.000 0.000 0.001

Compound L1: R = 0.9999 Compound L2: R = 0.9997


0.002 0.003 0.004 0.005
2

C (M)
Fig. 7. Langmuirs adsorption plots for mild steel in 1 M HCl containing different concentrations of the synthesized Schiff bases L1 and L2 at 25 C.

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