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Thin Solid Films 518 (2010) 27452749

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Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

pH and iodide ion effect on corrosion inhibition of histidine self-assembled monolayer on copper
Da-Quan Zhang a,b,, Xian-Ming He b, Qi-Rui Cai b, Li-Xin Gao a, Gui Soon Kim c
a b c

Department of Environment Engineering, Shanghai University of Electric Power, Shanghai 200090, PR China College of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444, PR China Department of Environmental Horticulture, The University of Seoul, Seoul 130-743, South Korea

a r t i c l e

i n f o

a b s t r a c t
Self-assembled monolayer (SAM) of histidine (His) was prepared on copper surface at various pH values. The effect of KI additives on corrosion protection efciency of His SAM was also studied. The protection abilities of these lms against copper corrosion in 0.5 M HCl aqueous solution were investigated using electrochemical impedance spectroscopy and polarization techniques. The results show that the lm formed on the electrode is more stable at pH = 10 than that at other pH values. When the iodide ions were added into the His selfassembly solution (pH = 10), protection efciency was further improved. The inhibition mechanism has been discussed by quantum chemical calculations. Crown Copyright 2009 Published by Elsevier B.V. All rights reserved.

Article history: Received 12 February 2009 Received in revised form 25 October 2009 Accepted 27 October 2009 Available online 31 October 2009 Keywords: Copper Electrochemical impedance spectroscopy Polarization Acid inhibition Self-assembled monolayers Histidine Corrosion

1. Introduction Self-assembled monolayer (SAM) formed spontaneously by chemical adsorption and self-organization on the surface of the metal offers great exibility for the control of surface structure and interfacial properties [1]. Substances with a long alkyl chain, which form dense and ordered monolayer on metal surface, can stop the corrosion of the base metal [2,3]. Copper is a kind of metal widely used in chemical industry, machinery manufacturing and construction industry and so on. Therefore, it is necessary to investigate its corrosion and protection properties. Up to date, the types of molecules studied for SAM formed on the copper surface are mainly alkanethiols [48], alkyl thiosulfates [9,10], mercaptoalkanols [11] and Schiff bases [1216]. Owing to increasing ecological awareness and strict environmental regulations, attention is now focused on the development of substitute nontoxic alternatives to inorganic inhibitors applied earlier. Thus, amino acids, which contain polar functions with nitrogen, oxygen or sulfur in their molecules, have been attractive as inhibitors in many corrosion systems. However, all of the reported studies so far are concentrated in amino

acid being added into corrosion medium directly [1720]. The amino acid SAM for controlling metal corrosion is seldom reported. In this paper, we have studied the protection efciency of histidine (His) self-assembled lm on copper surface in 0.5 M hydrochloric acid (HCl) solution at the room temperature. Histidine has an imidazoly moiety in its molecular structure, which is expected to have selfassembling ability on copper surface [21]. The inuence of iodide ions on the protection properties of His SAM has also been studied in order to ascertain the specic mode (ionic or molecular) in which the compound exerts its inhibiting action. Corrosion inhibition was studied by means of polarization curves and electrochemical impedance spectroscopy (EIS).We gained an insight into some theoretical information by quantum chemical calculations. The structure of His is shown in Fig. 1. 2. Experimental details 2.1. Electrode treatment and formation of SAMs Saturated calomel was used as reference electrode; the counter electrode was a platinum auxiliary electrode. The working electrode (WE) was prepared from a rectangular copper (99.9%) embedded in epoxy resin so that only the rectangular cross section (0.4 cm2) of the copper was exposed. The WE was gradually polished with different grades of emery paper (#1, #3 and #6). The freshly WE was

Corresponding author. Department of Environment Engineering, Shanghai University of Electric Power, Shanghai 200090, PR China. Tel./fax: +86 21 65700719. E-mail address: (D.-Q. Zhang).

0040-6090/$ see front matter. Crown Copyright 2009 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.tsf.2009.10.150


D.-Q. Zhang et al. / Thin Solid Films 518 (2010) 27452749

Fig. 1. Molecular structure of histidine.

thoroughly rinsed with deionized water and anhydrous ethanol as soon as possible, and immersed in the aqueous solution containing 10 mM His at various pH values (pH = 2, 4, 7, 10, 13) or 10 mM His/KI (1 mM ~ 5 mM) at pH = 10, allowing the self-assembling for 2 h at room temperature. The electrode was rinsed with enough anhydrous ethanol and deionized water in order to get rid of the physically adsorbed His molecules. The pH was adjusted at room temperature to the appropriate level using reagent-grade sodium hydroxide (NaOH) or sulfuric acid (H2SO4) as appropriate. 2.2. Apparatus Electrochemical measurements were performed in a three-electrode cell using a PARC M283 potentiostat (EG&G) with a PC. A PARC Model 1025 frequency response analyzer was also used for the EIS measurements. M352 and M398 software packages were used to obtain the polarization curves and electrochemical impedance spectra, respectively. 2.3. EIS and potentiodynamic curve measurements Each experiment was carried out in 0.5 M HCl solution. After 1 h of immersion, the corrosion potential (Ecorr) had been stable. The EIS experiments were performed at open circuit potential over a frequency range of 0.02 Hz100 kHz. The cell was open to air and the measurements were conducted at room temperature. During the measurements, the solution was not stirred or deaerated. The sinusoidal potential perturbation was 5 mV in amplitude. Polarization studies were carried out in the potential range 250 mV versus corrosion potential (Ecorr) at a scan rate of 1 mV s 1. All potentials were presented in mV (SCE). 3. Results and discussion 3.1. Electrochemical impedance measurements 3.1.1. Protection efciency of His lms with different pH Fig. 2 shows the Nyquist and Bode impedance plots of bare copper and the copper modied by His SAM in 0.5 M HCl solution. As shown in Fig. 2, each of them has an obvious capacitive loop in high frequency and a straight line (Warburg impedance) in low frequency. The capacitive loop is attributed to the relaxation time constant of the charge-transfer resistance (Rct) whose value is approximately equal to the diameter of the capacitive loop and the double-layer capacitance (Cdl) at the copper electrolyte interface. The Warburg impedance reects the anodic diffusion process of soluble copper species (CuCl) 2

Fig. 2. Nyquist plots of a copper electrode covered with His lm at various pH in 0.5 M HCl.

from the surface of the electrode to the bulk solution and the cathodic diffusion process of dissolved oxygen from the bulk solution to the surface of the electrode. These plots can be simulated by the equivalent circuit with the ZSIMPWIN software in Fig. 3(b), where

Fig. 3. Equivalent circuit model for the corrosion of copper: (a) the bare copper; (b) the SAM-covered electrode.

D.-Q. Zhang et al. / Thin Solid Films 518 (2010) 27452749 Table 1 Electrochemical impedance parameters in 0.5 M HCl for a copper electrode covered with His lm at various pH. Value of pH Blank 2 4 7 10 13 Rs ( cm2) 2.66 2.86 2.93 3.01 2.84 2.81 Rsam ( cm2) 34.6 46.4 55.1 98.0 44.6 CPEsam (F cm 2) 63.4 61.0 60.7 26.9 68.3 n1 0.84 0.81 0.82 0.87 0.81 Rct (k cm2) 0.739 0.888 1.059 1.357 2.811 1.498 CPEdl (F cm 2) 72.7 751 564 670 372 523 n2 0.60 0.57 0.64 0.59 0.56 0.58 W cm 2 6.4 10 3 7.4 10 3 8.7 10 3 4.6 10 3 2.7 10 3 2.6 10 3


% 17 30 46 74 51

Rs stands for the solution resistance, Rct is the charge-transfer resistance, Rsam is the transfer resistance of electrons or ion through the monolayer, which reects the protective properties of the SAM. A constant phase element (CPE) replaces the Cdl for accurate simulation. CPEsam and CPEdl represent the capacitance of the SAM and the double-layer capacitance, respectively. The impedance parameters are shown in Table 1. Admittance of a CPE is described as: YQ = Y0 j

copper surface [24]. Feng et al. demonstrated that the copper surface was covered mainly with a cupric oxide (CuO) layer at pH = 13 [25]. The surface states of copper at pH = 13 have adverse effect for the adsorption of His. It is noteworthy that the value of n2 in Table 1 is in the region of 0.5, which reveals the presence of a diffusion process at the interfacial layer. The formation of His SAM on the copper surface provides a diffusion barrier to copper corrosion. 3.1.2. Effect of KI additives Fig. 4 shows the impedance behavior of copper electrode in 0.5 M HCl solution. The copper electrodes were self-assembled in the aqueous solution containing 10 mM His and different concentrations of KI at pH = 10. As KI concentration reached 5 mM, the impedance spectra displayed only one capacitive loop. The disappearance of the impedance diffusion tail is most likely due to the limited low frequency range [26]. The impedance spectra can be analyzed with the equivalent circuit in Fig. 3(c) and the obtained results are summarized in Table 2. The values of the coverage were estimated using Eq. (2). The results show that when the concentration of KI increased from 1 mM to 5 mM, the value of Rct enhanced from 5.45 k cm2 to 6.59 k cm2 and the surface coverage improved from 86% to 89% compared to the surface coverage of 74% for His SAM lms alone. This shows that His/KI SAM lms have better inhibition effect than His SAM lms. Amino acid compounds are ampholyte, which have two functional groups of carboxyl and amine in their molecular structure. The presence of anions, which are usually characterized by strong adsorb ability on the metal surface, may enhance the adsorption of the amino acids [20]. The I ion adsorbed on the metal surface forms interconnecting bridges between the copper surface and the positive center in His molecules and thus, facilitates the adsorption process [22]. The increased adsorption leads to an improved corrosion inhibition of the SAM on the copper surface. 3.2. Polarization curve measurements Fig. 5 shows the polarization curves in 0.5 M HCl for the bare copper and the copper electrodes covered with KI, His and His/KI SAM lms. The anodic curve for the bare copper electrode in 0.5 M HCl

where Q is a CPE, Y0 is the modulus, j is the imaginary root, is the angular frequency ( = 2f where f is the frequency in Hz) and n is the exponential term of the admittance formula of CPE [22]. When n has a value of 0, 0.5 and 1, the impedance of the CPE would be that of a pure resistance, Warburg impedance and a pure capacitor, respectively. The coverage of the SAM on copper corrosion can be calculated according to the following formula [22,23]: 1 = Rct Rct

where R0 is the charge-transfer resistance of the bare electrode and ct Rct is the transfer resistance of the SAM-covered electrode. From Table 1, it can be seen that Rct of the bare electrode is the lowest. With the pH value increasing from 2 to 10, the coverage of the SAM-covered electrode increases quickly from 17% to 74%. While the pH value reaches 13, the coverage declines to 51%. The results imply that the lm formed on the electrode is denser and more stable at pH = 10 than that at acidic pH. However, the coverage of the SAM drops with the pH exceeding some value. As reported by Marti et al., the adsorption of His varies with the changes of oxygen coverage in

Table 2 Electrochemical impedance parameters for copper self-assembled in the aqueous solution containing 10 mM His and different concentrations of KI at pH = 10. KI conc. Rs Rct CPEdl n1 (mM) ( cm2) (k cm2) (F cm 2) Blank 1 2 5 2.66 3.75 2.84 2.83 0.739 5.45 6.01 6.59 72.7 524 479 370 0.60 0.56 0.57 0.58 Rsam CPEsam n2 ( cm2) (F cm 2) 68.4 68.8 95.0 44.4 41.7 23.3 0.80 0.81 0.85 % 86 87 89

Fig. 4. Nyquist plots of copper self-assembled in the aqueous solution containing 10 mM His and different concentrations of KI at pH = 10.


D.-Q. Zhang et al. / Thin Solid Films 518 (2010) 27452749

lm, icorr was 3.40 A cm 2, 3.63 A cm 2 and 2.19 A cm 2, respectively. This result indicates that SAM has the ability of inhibiting corrosion to some extent. Protection efciency (PE) was calculated from the polarization data as [23]: icorr i corr 100 icorr 3

PE =

where icorr and icorr are the corrosion current densities in the absence and presence of SAM lm, respectively. It is observed that the PE values obtained are in close agreement with the values that determined from EIS measurements. The synergistic effect of His/KI is also veried by the electrochemical polarization measurement. 3.3. Quantum chemical calculations
Fig. 5. Polarization curves measured in 0.5 M HCl. (1) the bare copper; (2) covered with KI lm (immersed in 15 mM KI at pH = 10); (3) covered with His lm (immersed in 10 mM His at pH = 10); (4) covered with His lm (immersed in 15 mM His at pH = 10); (5) covered with His/KI lm (immersed in 10 mM His and 5 mM KI at pH = 10).

solution exhibits a linear region and apparent Tafel slope. The anodic dissolution process of copper in the active dissolution region has two steps as follows [27,28]: Cu Cl CuClads e

CuClads Cl CuCl2 e : The cathodic portion of the polarization curve is the oxygen reduction reaction, and comes almost under diffusion control. The cathodic corrosion reaction is as follows: 4H O2 4e 2H2 O: The total corrosion reaction of copper in acidic chloride solution is as follows: 2Cu 4H 4Cl O2 2Cu

4Cl 2H2 O:

His or His/KI SAM lm depresses the cathodic part of the polarization curve in HCl solution, while the corrosion potential (Ecorr) is negatively shifted. This implies that His or His/KI SAM lm mainly functions by retarding the oxygen diffusion, without inuencing the anodic diffusion process (such as CuCl). The corresponding corrosion 2 potential (Ecorr), corrosion current (icorr) and anodic Tafel slope (a) were calculated by ParCalc method of Model 352 corrosion analysis software and listed in Table 3. An iterative non-linear least squares method was adopted in the ParCalc method. The corrosion current density (icorr) was determined by extrapolation of the anodic Tafel lines. For the bare copper, icorr was 13.8 A cm 2. For the copper electrode covered with 10 mM or 15 mM His lms and His/KI SAM

Theoretical calculations were carried out at the restricted Hartree Fock Level using semi-empirical PM3 methods in the MOPAC 7.0 packet program implemented on Pentium IV. As reported by Marti et al., His can have different charges at various pH values [24]. The structures of His were showed (Fig. 6) at various pH values. His is the structure of His at pH > isoelectric point (pI), it is anionic at basic pH (carboxylic group appears deprotonated). His0 is the structure of His at pH equal to pI, it is zwitterionic at neutral pH (amino group is protonated and carboxylic group is deprotonated). His+ is the structure of His at pH < pI, it is cationic at acidic pH (amino group appears protonated). His2+ is the structure of His at pH pI, it is cationic at acidic pH (amino group and imidazole side chain appears protonated). The values of pI, pKa1 and pKa2 at 25 C for His are 7.59, 1.82 and 9.17, respectively, where Ka1 stands for dissociation constant of the -COOH group on His, and Ka2 dissociation constant of the -N+H3 group on His. Values of energy of the lowest unoccupied molecular orbital (ELUMO), energy of the highest occupied molecular orbital (EHOMO), the dipole moments of molecules (D), the charge on oxygen in carboxyl group (O), and the charge on nitrogen in amino and imidazole groups (N), were calculated and the obtained results were collected in Table 4. It has been proved that the higher the EHOMO level of the inhibitor is, the greater is the ease of offering electrons to the unoccupied d orbital of metallic copper and the greater is the inhibition efciency of the inhibitor for copper [17]. The EHOMO of the specic ionic mode of His increased in the following order: His > His0 > His+ > His2+. The observed coverage of SAM at various pH values was in the same

Table 3 Polarization data of the SAM-covered electrode to t the polarization curves. KI conc. (mM) Blank 15 mM 10 mM 15 mM 10 mM KI His His His + 5 mM KI Ecorr (mV) 206.3 238.2 237.3 251.5 264.2 icorr (A cm 2) 13.8 7.29 3.40 3.63 2.19 a (mV dec 1) 51.38 67.47 56.24 63.12 59.79 Rp k 3.05 5.83 12.5 12.4 21.2 PE % 47 75 74 84

Fig. 6. The structures of His were showed at the various pH values. His is the structure of His at pH > pI (basic pH); His0 is the structure of His at pH = pI (neutral pH); His+ is the structure of His at pH < pI (acidic pH); His2+ is the structure of His at pH pI (acidic pH).

D.-Q. Zhang et al. / Thin Solid Films 518 (2010) 27452749 Table 4 Quantum chemical calculations data for His at the various pH values. Inhibitor EHOMO/eV ELUMO/eV Net atomic charges N N1 His His0 His+ His2+ 4.6217 9.5466 13.4367 18.8304 3.5619 0.1435 4.9505 9.3623 0.3375 0.1053 0.0794 0.0670 N2 0.1418 0.3303 0.3637 0.7198 N3 0.0931 0.6853 0.8308 0.8526 O O1 0.6299 0.5800 0.3062 0.2949 O2 0.6054 0.4535 0.1843 0.1695 10.377 8.292 4.404 8.719


Dipole moment/D

order: His > His0 > His+ > His2+. The present results show that His has the best protection effect on corrosion of copper in an acidic chloride solution and has the highest level of EHOMO. Therefore, His has the strongest interaction with copper in the assembling process. It is also conrmed that the more negative the atomic partial charges of the adsorbed center are, the more easily the atom donates its electrons to the unoccupied orbital of the surface atoms of the metal [23,29]. In Table 4, the oxygen atomic charges are more negative than the nitrogen atomic charges, so the oxygen atoms more easily adsorbed on the copper surface. The oxygen atomic charges of His at basic pH are more negative than those at neutral pH and acidic pH. Therefore, His at basic pH is more easily adsorbed on the copper surface. On the other hand, it is also found that there are positive charge centers in the different His molecule. The added I ion can interact with the positive charge center in His at basic pH. This enhances the adsorption of His and improves the protection effect of the SAM on the copper surface. 4. Conclusions Self-assembled monolayer (SAM) of histidine (His) was prepared on copper surface at various pH values. Self-assembled monolayer of His on copper can be used to inhibit copper corrosion. With the pH value increasing from 2 to 10 in the His solution, the His lm formed on the electrode is denser and more stable, and the and PE increase. While, when the pH value reaches 13, the and inhibition PE drop. Synergistic effects between His and KI have been observed. The addition of KI can promote the adsorption of His molecules and enhances the PE of SAM signicantly. Quantum chemical calculations were presented to analyze the mechanism. The result shows that His at basic pH is more easily adsorbed on the copper surface and has better protection effect. Acknowledgements The authors express their appreciation for support from the National Science Foundation of China (20776083, 20911140272) and Program

for New Century Excellent Talents in University (NCET-08-0895). This work was carried out in the Key laboratory of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry.

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