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Journal of The Electrochemical Society, 148 11 B482-B488 2001

0013-4651/2001/148 11 /B482/7/$7.00 The Electrochemical Society, Inc.

A Study of Corrosion Behavior of Copper in Acidic Solutions Containing Cetyltrimethylammonium Bromide

Houyi Ma,a,b Shenhao Chen,b,c, z Shiyong Zhao,b Xiangqian Liu,b and Degang Lib
a

Key Laboratory for Colloid and Interface Chemistry of State Education Ministry, Shandong University, Jinan 250100, China b Department of Chemistry, Shandong University, Jinan 250100, China c State Key Laboratory for Corrosion and Protection of Metal, Shenyang 110015, China The inhibitive effect of cetyltrimethylammonium bromide CTAB on copper corrosion in aerated H2SO4 solutions was investigated by means of electrochemical impedance spectroscopy EIS and potentiodynamic polarization techniques. CTAB inhibited copper corrosion more strongly than tetramethylammonium bromide TMAB under the same conditions due to the chemisorption of the n-cetyl group on the copper surface. The surface of the copper electrode was positively charged in sulfuric acid solution at the corrosion potential. The copper corrosion inhibition of CTAB and TMAB was attributed to the synergistic effect between bromide anions and positive quaternary ammonium ions. The C16H33N CH3 3 and N CH3 4 ions may electrostatically adsorb on the copper surface, which is primarily covered with adsorbed bromide ions. The inhibition efciency of CTAB depended on the CTAB concentration and the immersion time for the copper electrode in corrosive solutions. Based upon the variation of impedance display of copper with the CTAB concentration and the immersion time, an adsorption model of CTAB on the copper surface was proposed. The C16H33N CH3 3 ions adsorbed on the copper surface by horizontal binding to hydrophobic hydrocarbon chains at the low CTAB concentrations, whereas a perpendicular adsorption dominated as a result of an interhydrophobic chain interaction when the CTAB concentration increased. 2001 The Electrochemical Society. DOI: 10.1149/1.1409543 All rights reserved. Manuscript submitted August 29, 2000; revised manuscript received July 10, 2001. Available electronically October 12, 2001.

It is well known that surfactant molecules are composed of polar hydrophilic moiety, the head, attached to a nonpolar hydrophobic moiety, the tail.1 The existence of amphiphilic groups in one molecule makes surfactants show some unique properties, such as enrichment at water/air or oil/water interface, which greatly decreases the surface tension of water, the complex self-assembling phenomena in the case of the concentration above critical micelle concentration CMC , and so on.2-4 Although surfactants have been widely used in the chemical and light industries and their properties have also been a subject which has attracted many chemists attention, only a few studies focus on the application of surfactants for corrosion prevention of metals and alloys as inhibitors. Adsorption of inhibitors at the metal/solution interface is usually accepted as the formation of electrostatic or covalent bonding between the metal surface atoms and the adsorbates.5,6 Compared with common inhibitors, adsorption of surfactants at the metal surface seems to be much more complicated. In aqueous solutions, the surfactant molecules may absorb on the solid surface through electrostatic attraction or chemisorption depending on the charge of the solid surface and the free energy change of transferring hydrocarbon chains from water to the solid surface.6,7 Luo and co-workers results have shown that sodium dodecyl benzene sulfonate SDBS adsorbs on the surface of mild steel via electrostatic forces, whereas sodium oleate chemisorbs on the surface of mild steel in acidic solution.6 Under appropriate conditions, enough surfactant molecules may adsorb to the solid surface, forming an organized structure, i.e., the hemimicelle,6,7 which can effectively prevent metals from corrosion in an aggressive environment. In this sense, it is important to investigate the inhibition of metal corrosion by the surfactants. In this paper, the inhibitive effect of cetyltrimethylammonium bromide CTAB on copper corrosion in acidic solutions was investigated. The reason for selecting CTAB as an inhibitor is that CTAB is not only a typical anionic surfactant which is commercially available and easily puried, but is also a kind of quaternary ammonium salt with a long hydrocarbon chain, whose homologues have been used extensively as inhibitors against the acid corrosion of iron and steels.8 In particular it is reported that the halides were the most

effective derivatives since they increased the inhibiting tendency of the positive quaternary ammonium ions through a synergistic effect.8 Copper is a relatively stable metal and can hardly be attacked in the solutions without oxidizing agents or complex agents as it normally does not displace hydrogen from acid solutions.9,10 However, most solutions used in industry contain dissolved air. The dissolved oxygen may be cathodically reduced on copper, which leads to the occurrence of some corrosion on copper surface.9,11-14 The presence of halides in electrolytes will promote the aqueous corrosion of copper.15,16 The aim of this work is to study the inhibitive mechanism of CTAB on copper in 0.5 mol dm 3 H2SO4 using electrochemical impedance spectroscopy EIS and potentiodynamic polarization techniques, and to compare the effect of the CTAB concentration on the inhibitive action, thereby giving a good understanding concerning how CTAB inhibits the copper corrosion. Experimental The copper electrode was made from 99.9% pure copper rods of 5.8 mm diam. The rod specimen was embedded in an epoxy resin mould and only its cross section was allowed to contact the electrolyte solutions. The electrode was rst briey ground with no. 600 emery paper, subsequently polished with no. 2000 emery paper, and nally rinsed with alcohol and triply distilled water before each experiment. The cell for carrying out all electrochemical experiments was a three-electrode cell. The main compartment held the working electrode and the reference electrode, a saturated calomel electrode SCE , with a Luggin capillary leading to the surface of working electrode. The other compartment contained a platinum black counter electrode with a 4 cm2 surface area. All potentials were measured with respect to the SCE. The concentrated solutions of 2.0 mol dm 3 H2SO4, 1.0 10 3 mol dm 3 CTAB, and 1.0 10 3 mol dm 3 tetramethylammonium boride TMAB were prepared with analytical grade chemicals and triply distilled water. The 0.5 mol dm 3 H2SO4 dilute solution was prepared through diluting concentrated H2SO4. The CTAB-containing or TMAB-containing H2SO4 solutions were, respectively, prepared by mixing various proportions of the concentrated H2SO4 with CTAB or TMAB concentrated solutions.

E-mail: shchen@sdu.edu.cn

Journal of The Electrochemical Society, 148 11 B482-B488 2001

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Figure 1. Polarization curves for a copper electrode with various concentrations of CTAB in 0.5 mol dm 3 H2SO4. No CTAB; ---- 1.0 1.0 10 4 mol dm 3 CTAB; .... 10 5 mol dm 3 CTAB; 5.0 10 3 mol dm 3 CTAB; 1.0 10 3 mol dm 3 CTAB; 2 3 1.0 10 mol dm CTAB.

The cell was submerged in an automatic temperature-controlled water bath to carry out polarization and EIS experiments at the constant temperature (22 0.2C . The steady-state polarization curves were obtained by means of the linear potential sweep of 0.2 mV s 1 from the cathodic to the anodic side. EIS measurements were performed at the corrosion potentials in the frequency range from 65 kHz to 10 mHz at ve points per hertz decade under excitation of a sinusoidal wave of 5 mV amplitude. All measurements were conducted using a Zahner IM6 electrochemical workstation. Results and Discussion Polarization measurements.The dissolution kinetics of copper in sulfuric acid has been studied by Smyrl,10 Mattsson and Bockris,17 Cordeiro et al.,18 and Wong et al.19 According to these authors, the anodic dissolution of copper takes place in two continuous steps
K1

where Cu I ads is an adsorbed species at the copper surface and does not diffuse into the bulk solution. It is inferred from the reaction model that the steady-state polarization curve of copper should give an apparent Tafel region of 40 mV/decade slope, which has been conrmed by some authors.19-21 Figure 1 shows a set of polarization curves for the copper electrode measured in 0.5 mol dm 3 H2SO4 solution alone and in the presence of various concentrations of CTAB. In each case, the polarization measurement was carried out after the corrosion potential reached an approximately stable value to ensure the reaction system was in the steady state. The polarization curve for copper solid line in the CTAB-free H2SO4 solution presented a monotonic increase of current with the potential, and displayed a narrow linear region of about 43 mV/decade slope from 80 to 50 mV, which is almost in agreement with those reported in Ref. 18 though 21. By comparing polarization curves in the absence and presence of CTAB, it is observed that the increase in CTAB concentration shifted the opencircuit potential in the negative direction and a slight lowering of both the anodic and cathodic current densities. It is interesting to note that in the case of the relatively low concentration (5.0 10 5 mol dm 3 , CTAB did not inhibit, but enhanced the corrosion of copper; in addition, the corrosion potential moved anodically to a value more positive than that of copper in the pure H2SO4 solution. The cathodic and anodic Tafel slopes in uninhibited and inhibited solutions were obtained by using IM6 tting software, as shown by Table I. The addition of CTAB led to a change of anodic and cathodic Tafel slopes besides decreasing both currents. The corrosion potential and corrosion current for copper in the six reaction systems were obtained by the Tafel extrapolation method and the results are listed in Table I. The inhibition efciency IE of CTAB in each case can be calculated in terms of the formula i corr i corr i corr

IE %

100

where i corr and i corr are, respectively, the corrosion current density in the absence or presence of CTAB. Table I shows that the IE increases with the CTAB concentration up to a maximum 63.0% in a concentration of 1.0 10 3 mol dm 3 and then it decreases. Electrochemical impedance spectroscopy (EIS).Impedance behavior of copper in 0.5 mol dm 3 H2SO4 solution is somewhat similar to that of copper in the HCl solution of the same concentration, as shown by Fig. 2. The corrosion of copper in H2SO4 and HCl solutions is inuenced to some extent by mass transport. The anodic dissolution of copper in the halide-containing solutions has been proved to be diffusion limited.22,23 The diffusion step was due to the transport of CuX2 to the bulk solution according to Lee and Nobe.23 However, the corrosion reaction of copper in halide solutions at the open-circuit potential is composed of the oxidation of copper and the reduction of oxygen dissolved in the solutions. The oxygen reduction is diffusion limited and usually controls the rate of the whole corrosion reaction. The diffusion of dissolved oxy-

Cu

e
K 1 K2

Cu I

ads

fast step

Cu I

ads

e
K 2

Cu II

the rate-determining step

Table I. Electrochemical parameters and inhibition efciencies for copper in 0.5 mol dm3 H2SO4 in the presence of CTAB. Conc. mol dm 0 1.0 1.0 1.0 5.0 1.0 10 10 10 10 10
3

E corr mV 89.1 63.3 136.8 164.8 206.6 212.6

i corr mA cm 1.80 7.89 1.03 6.61 7.52 9.14

2 3 3 3 4 4 4

ba mV 43.2 149.1 71.4 66.2 71.2 65.3

bc mV 109.9 192.3 81.1 92.7 101.4 99.6

IE % 42.5 63.0 58.1 49.0

5 4 3 3 2

10 10 10 10 10 10

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Journal of The Electrochemical Society, 148 11 B482-B488 2001 oxygen copper corrodes readily with the reduction of oxygen being diffusion controlled. Therefore, the appearance of the Warburg impedance in the impedance spectrum for copper measured at the corrosion potential can be attributed to the oxygen diffusion from the bulk solution to the electrode surface. Figure 3 shows six groups of impedance diagrams for the copper in 0.5 mol dm 3 H2SO4 solutions with various CTAB concentrations at the respective corrosion potential after the copper electrode was exposed to the solutions for different times. Compared with Fig. 2, the impedance display of the copper in the CTAB-containing solutions greatly changed in shape and size. Taking Fig. 3c as an example, even if the electrode was immersed in H2SO4 solution containing 1.0 10 4 mol dm 3 CTAB for only 5 min, the presence of CTAB led to changes of impedance behavior in the following two aspects: i the Warburg impedance almost disappeared and ii the diameter of the capacitive loop obviously increased, from 1130 cm2 in the absence of CTAB to more than 8120 cm2 in the presence of CTAB. The effect of immersion time on the shape and size of impedance spectra is characterized in Fig. 3. When the CTAB concentration was low 5.0 10 6 to 1.0 10 4 mol dm 3, see Fig. 3a-c , the capacitive loop increases in size with the increase of immersion

Figure 2. Nyquist impedance spectra for copper in 0.5 mol dm and 0.5 mol dm 3 HCl at the corrosion potentials.

H2SO4

gen from the bulk solution to the surface of the copper electrode causes the appearance of the Warburg impedance in the corresponding impedance diagram. If there is no oxygen dissolved in dilute H2SO4 solution, copper corrosion will not take place. However in the presence of dissolved

Figure 3. Complex plane plots of the impedance data obtained from the copper electrode exposed for different times to the 0.5 mol dm with different CTAB concentrations.

H2SO4 solutions

Journal of The Electrochemical Society, 148 11 B482-B488 2001 lowing formula IE % Rt R t /R t 100

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Figure 4. a, top The equivalent circuit to t the EIS for copper displaying a Warburg impedance. b, bottom The equivalent circuit to t the EIS for copper displaying one or a capacitive loops.

time, reaching a maximum in 2 h, and then it decreased with the immersion time. Either it reduced to be almost the same size as it was measured after 5 min immersion in the presence of 1.0 10 4 mol dm 3 CTAB or it became even smaller than that measured in the 5 min immersion in the CTAB-containing solutions of 5.0 10 5 and 5.0 10 6 mol dm 3. On the contrary, when the CTAB concentration was high 1.0 10 3 to 1.0 2 3 10 mol dm , see Fig. 3d-f , the size of the capacitive loop increased with the increase of immersion time. It is interesting to note that the Nyquist diagrams for copper in the H2SO4 solutions with 5.0 10 3 and 1.0 10 2 mol dm 3 CTAB displayed an obvious Warburg impedance after a 5 min immersion, indicating that the corrosion process was controlled by the diffusion of reactants or products. As stated earlier, the corrosion reaction of copper in dilute sulfuric acid comprises the reaction of dissolved oxygen and the oxidization of copper. When large amounts of bromide ions are introduced to the solutions, bromide ions will complex with the oxidized Cu I ions and form CuBr2 species on the copper surface which subsequently transfer from the copper surface to the bulk solution, thereby leading to the appearance of the Warburg impedance. The Nyquist impedance spectrum for copper in 0.5 mol dm 3 H2SO4 was analyzed by the equivalent circuit shown in Fig. 4a. R s represents the solution resistance, R t the charge-transfer resistance; W, the Warburg impedance; and CPEdl , the double-layer capacitance. One constant phase element CPE was substituted for the capacitive element to give a more accurate t.24 All impedance spectra obtained from the copper electrode exposed for 2 h to the CTAB-containing H2SO4 solutions were analyzed by the equivalent circuit in Fig. 4b. The physical meaning of R s , R t , and CPEdl is the same with what they represent in Fig. 4a. The tting results are listed in Table II. According to the fol-

where R t is the charge-transfer resistance for the inhibited solutions and R t is the one for the uninhibited solutions. IE values of CTAB after 2 h immersion are calculated see Table II . Comparison of IE data in Tables I and II indicates that the immersion time has a great inuence on the IE of CTAB. The IE has exceeded 96% after 2 h of immersion even if the CTAB concentration is only 5.0 10 6 mol dm 3. The polarization curves in Fig. 1 have shown that CTAB inhibited both the cathodic reaction and the anodic reaction provided that its concentration was higher than 1.0 10 5 mol dm 3. The impedance spectra for the copper in the CTAB-containing solutions at the corrosion potentials did not display new low frequency capacitive or inductive loops in addition to the well-known high frequency semicircle. Thus, we can draw a conclusion that CTAB is a kind of mixed-type inhibitor for copper corrosion in sulfuric acid. The inhibitive action is realized by the geometric coverage of CTAB on the copper surface. In this case, IE may be considered as the surface coverage by the surfactant molecules on the copper surface.25,26 If adsorption of CTAB on the copper surface obeys the Langmuir adsorption isotherm C/ C 1/K 5

where C is the CTAB concentration and K is the adsorption equilibrium constant, the plot of C/ against C will be straight with a slope of unity. Figure 5 presents the dependence of C/ on C. The data obtained gave a straight line with the regression coefcient equal to 0.9994, which suggests the experimental data are well described by the Langmuir adsorption isotherm. The slope and the equilibrium constant were determined to be 1.02 and 2.12 105 dm3 mol 1, respectively. The results further support the above-mentioned viewpoint that the inhibitory action of CTAB is realized by a simply geometric coverage. Determination of the potential of zero charge (pzc).An inhibitor usually realizes its inhibitive action by adsorption as a thin lm onto the surface of a corroding metal or by inducing formation of a thick corrosion product. Adsorption depends mainly on the charge of the metal surface, the charge or the dipole moment of inhibitors, and the adsorption of other ionic species.6 The potential of zero charge pzc plays a very important role in the electrostatic adsorption process. It is possible to determine whether the charge of electrode surface is positive or negative from the difference between the corrosion potential and pzc of a corroding metal. The data concerning pzc of a solid metallic electrode has been limited so far. The pzc for copper in 0.01 mol dm 3 Na2SO4 may be taken to be 30 mV vs. standard hydrogen electrode SHE or 214 mV vs. SCE according to Bockris and Reddys report,27 whereas the pzc for copper in H2SO4 solutions has not been found in references. In this research, we have measured a series of impedance spectra of copper in

Table II. Fitting the EIS for copper in sulfuric solutions without and with the different concentrations of CTAB after a 2 h immersion. Values of the elements of equivalent circuits in Fig. 4a and b and inhibition efciencies of CTAB on copper corrosion. Conc. mol dm 0 5.0 5.0 1.0 1.0 5.0 1.0 10 10 10 10 10 10
3

Rt cm2 1.14 1.20 1.14 1.36 1.52 1.62 1.33 103 104 104 104 104 104 104

Rs cm2 0.71 0.71 0.69 0.62 0.43 0.40 0.42

C dl F cm 3.93 6.90 9.76 12.4 12.6 14.7 17.4

W cm2 5.59 10
5

IE % 97.3 97.2 97.6 97.9 98.0 97.6

6 5 4 3 3 2

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Journal of The Electrochemical Society, 148 11 B482-B488 2001

Figure 7. Nyquist impedance spectra for copper in 0.5 mol dm 3 H2SO4 solutions at the corrosion potentials in the presence of 1.0 10 4 mol dm 3 TMAB after being immersed for 5 min and 2, 5, and 7 h in the solution.

Figure 5. Langmuir plot for the adsorption of CTAB on the copper surface from 0.5 mol dm 3 H2SO4 solutions.

0.5 mol dm 3 H2SO4 solution over a wide potential range between 512 and 20 mV vs. SCE , analyzed these impedance spectra by means of IM6 impedance analysis software, and plotted the doublelayer capacitance against potential see Fig. 6 in the light of Luo and co-workers method. The pzc of copper in 0.5 mol dm 3 H2SO4 is estimated as 140 mV from the dependence of the double-layer capacitance on potential shown in Fig. 6, which is more negative than the corrosion potential 96 mV . This means that the copper surface is positively charged at the corrosion potential. If only considering the electrostatic attraction, it is unlikely that positive quaternary ammonium ions will directly adsorb

on the surface. The reason why CTAB can inhibit copper corrosion in sulfuric solution is related to the synergistic effect resulting from the specic adsorption of bromide ions at the copper/solution. The addition of CTAB introduced bromide ions to the sulfuric acid solutions. Bromide ions rst adsorbed at the copper/solution interface at the corrosion potential through electrostatic attraction force due to the excess of positive charge at the copper/solution interface, leading to the change on the solution side of the interface changes from positive to negative. Thus, quaternary ammonium cations are able to electrostatically adsorb on the copper surface covered with primarily adsorbed bromide ions. The adsorption model of CTAB.Considering that CTAB is a kind of quaternary ammonium salt, in order to examine how the length of hydrocarbon chains affects the impedance behaviors of copper, impedance measurements of copper in the solution of 0.5 mol dm 3 H2SO4 1.0 10 4 mol dm 3 TMAB under identical conditions were carried out as contrasting tests. Figure 7 shows that, in the TMAB-containing H2SO4 solution, the dependence of the diameter of the capacitive loop on the immersion time was quite different from that observed in the CTAB-containing acidic solution see Fig. 3 . The capacitive loop increased in size with the immersion time, reaching an approximate constant value in about 2 h. The adsorption behavior of organic compounds at the electrode/ solution interface is somewhat similar to that in the gas/solution interface. For an organic compound with a polar group, such as quaternary ammonium salts, if the dissolvability permits, the increase in length of the hydrocarbon chain is favorable for enhancement of the surface activity. Generally, the longer the hydrocarbon chain is, the more easily the organic molecules adsorb at the electrode/solution interface. The structural difference between TMAB and CTAB is that the latter has a long hydrocarbon chain, n-cetyl, in the molecule. Therefore, CTAB adsorbs at the copper/ solution interface more strongly than TMAB. Theoretically, the adsorption model of CTAB on a copper surface may be either A or B in Fig. 8. Provided that CTAB molecules adsorb in the A way, the length of the carbon chain will have an insignicant inuence on the inhibitive action, as n-cetyl is approximately normal to the copper surface. If so, its inhibitive effect on copper corrosion should be almost the same with that of TMAB. However, the experimental results have shown that CTAB inhibited the copper corrosion more effectively than TMAB. The signicant difference in the inhibitive effect between both quaternary ammonium salts implies that CTAB molecules adsorb in the B way not in the A way, thus the long chain n-cetyl can cover more sites on the copper surface, resulting in the higher inhibitive effect. The dependence of the inhibitive effect of CTAB on the immersion time indicates that from one side the adsorption of the

Figure 6. Double-layer capacitance of copper as a function of potential in 0.5 mol dm 3 H2SO4 solution.

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Figure 8. Two possible adsorption models of CTAB.

surfactant-CTAB on copper surface has a special inuence on electrochemical behavior of copper. The adsorption style, arrangement, and orientation of CTAB on the surface of the copper electrode will change with the CTAB concentration and the immersion time. The N CH3 4 ion behaves as a simple inorganic positive ion complex with a symmetric tetrahedral structure. The number of the N CH3 4 ions adsorbed on the copper surface depends only on the number of adsorbed bromide ions on the surface, increasing with the increase of the adsorbed bromide ions. Obviously, the longer the immersion time of copper in the TMAB-containing solution, the more the bromide ions adsorb on the copper surface. Thus, more N CH3 ) 4 ion will be adsorbed electrostatically at copper/solution interface. This is the reason that the inhibition efciency of TMAB increases with the immersion time in the early stage. When the number of N CH3 4 ions adsorbed on the copper surface reaches a limiting value, the inhibition efciency of TMAB will approach a constant and no longer increase with immersion time. The adsorption of CTAB at the copper/solution interface, unlike TMAB, cannot be simply considered as an electrostatic adsorption attributed to the synergistic effect of bromide ions, because there is a sixteen-carbon long chain in the CTAB molecule. The adsorption of surfactants at the electrode/solution interface is quite a complicated problem, and few studies have focused on the topic so far as we know.6,8 It is well known that the molecules of ionic surfactants will aggregate in aqueous solution, forming micelles with different structures depending on the concentration of the surfactant, when the concentration of the surfactant is above the critical micelle concentration CMC . But the theory of aggregation and self-assembly of surfactants in solutions is not completely suitable for interpreting the adsorption or self-assembly of surfactants at electrode/solution interface. For example, the CMC of CTAB in 0.5 mol dm 3 H2SO4 solution was about 3.35 10 5 mol dm 3 see Fig. 9 . However, the impedance behavior of copper in the sulfuric solutions with 5.0 10 6 to 1.0 10 4 mol dm 3 CTAB was very similar see Fig. 3a-d . The impedance behavior will change signicantly only when CTAB concentration is relatively high ( 1.0 10 3 mol dm 3) see Fig. 3e and f . On the basis of the variation of the impedance measurements with the CTAB concentration and the immersion time, the adsorption model of CTAB on copper surface is proposed. In the case of the lower CTAB concentration ( 1.0 10 3 mol dm 3), it is inferred that the chemisorption of n-cetyl on the copper surface and the electrostatic attraction of the C16H33N CH3 3 ions with the bromide ions previously adsorbed on the copper surface takes place simultaneously. This adsorption mode is described schematically in Fig. 10a, in terms of which of the adsorbed C16H33N CH3 3 ions can cover much area, thereby more effectively preventing copper from corrosion. The inhibition efciency of CTAB increased with the increase of the immersion time and reached a maximum in 2 h. With a further increase of the immersion time, more bromide ions adsorbed on the copper surface and occupied more sites on the electrode surface, resulting in the fact that more C16H33N CH3 3 ions electrostatically adsorbed on the

Figure 9. The relation between the surface tension tration (C CTAB).

and CTAB concen-

copper surface. The adsorption density of the surfactant at some sites of the surface became so high so that interaction between long hydrocarbon chains was considered to occur through the Van der Waals force. Theoretically, the adsorption mode of some C16H33N CH3 3 ions will change. Hydrocarbon chains of some adsorbed C16H33N CH3 3 ions are believed to leave the surface and aggregate to form hemimicelles see Fig. 10b . In fact, compared with Fig. 10a, the effective area covered by C16H33N CH3 3 ions

Figure 10. Illustration of adsorption of C16H33 CH3 ) 3 ions at copper/ solution interface. a adsorption as single ions in the case of short immersion time and b hemimicelle formation at some sites of the surface in the case of long immersion time at low concentrations of CTAB; c formation of the hemimicelle barrier on the whole surface at high concentrations of CTAB. the copper/solution interface. CTAB and Br .

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Journal of The Electrochemical Society, 148 11 B482-B488 2001 Acknowledgments This project is supported by the Visiting Scholar Foundation of Key Laboratory in Shandong University, the Chinese National Natural Science Fund. References
1. S. Puvvada and D. Blankschtain, in Surfactants in Solution, Vol. 11, K. L. Mittal and D. O. Shah, Editors, p. 95, Plenum Press, New York 1990 . 2. C. A. Bunton, in Surfactants in Solution, Vol. 11, K. L. Mittal and D. O. Shah, Editors, p. 329, Plenum Press, New York 1990 . 3. S. I. Ahmad and S. Friberg, J. Am. Chem. Soc., 94, 5169 1972 . 4. P. Ekwall, L. Mandell, and K. Fontell, J. Colloid Interface Sci., 29, 639 1969 . 5. G. Trabanelli, in Corrosion Mechanism, F. Mansfeld, Editors, p. 119, Marcel Dekker, Inc., New York 1987 . 6. H. Luo, Y. C. Guan, and K. N. Han, Corrosion, 54, 619 1998 . 7. C. A. Miller and S. Qutubuddin, in Interfacial Phenomena in Apolar Media, H.-F, Eicke and C. D. Partt, Editors, Surfactant Science Series, Vol. 21, p. 166, Marcel Dekker, Inc., New York 1987 . 8. D. P. Schweisberg and V. Ashworth, Corros. Sci., 28, 539 1988 . 9. G. Quartarone, G. Moretti, T. Bellomi, G. Capobianco, and A. Zingales, Corrosion, 54, 606 1998 . 10. W. H. Smyrl, in Comprehensive Treatise of Electrochemistry, Vol. 4, J. OM. Bockris, B. E. Conway, E. Yeager, and R. E. White, Editors, p. 116, Plenum Press, New York 1981 . 11. W. D. Bjorndahl and K. Nobe, Corrosion, 40, 82 1984 . 12. H. P. Dhar, R. E. White, G. Burnell, L. R. Cornwell, R. B. Grifn, and R. Darby, Corrosion, 41, 317 1985 . 13. R. Schumacher, A. Muller, and W. Stockel, J. Electroanal. Chem., 219, 311 1987 . 14. A. H. Moreira, A. V. Benedetti, P. L. Calot, and P. T. A. Sumodja, Electrochim. Acta, 38, 981 1993 . 15. D. Tromans and R.-h. Sun, J. Electrochem. Soc., 138, 3235 1991 . 16. T. Aben and D. Tromans, J. Electrochem. Soc., 142, 398 1995 . 17. E. Mattsson and J. OM. Bockris, Trans. Faraday Soc., 55, 1586 1959 . 18. G. G. O. Cordeiro, O. E. Barcia, and O. R. Mattos, Electrochim. Acta, 38, 319 1993 . 19. D. K. Y. Wang, B. A. W. Coller, and D. R. Macfarlane, Electrochim. Acta, 38, 2121 1993 . 20. R. Caban and T. W. Chapman, J. Electrochem. Soc., 124, 1371 1977 . 21. T. Hurlen, G. Ottesen, and A. Staurset, Electrochim. Acta, 23, 23 1978 . 22. O. E. Barcia, O. R. Mattos, N. Pebere, and B. Tribollet, J. Electrochem. Soc., 140, 2825 1993 . 23. H. P. Lee and K. Nobe, J. Electrochem. Soc., 133, 2035 1986 . 24. X. Wu, H. Ma, S. Chen, Z. Xu, and A. Sui, J. Electrochem. Soc., 146, 1847 1999 . 25. M. M-Hukovic, R. Baric, and Z. Grubac, J. Appl. Electrochem., 28, 433 1986 . 26. M. M. Hukovic, R. Baric, Z. Grubac, and S. Brinic, J. Appl. Electrochem., 24, 772 1986 . 27. J. OM. Bockris and A. K. N. Reddy, in Modern Electrochemistry, Vol. 2, J. OM Bockris, B. E. Conway, E. Yeager, and R. E. White, Editors, p. 708, Plenum Press, New York 1970 .

reduced to some extent, although more C16H33N CH3 4 ions is adsorbed on the surface. In this way, it is not difcult to understand why the inhibition efciency decreased with a further increase of the immersion time when the immersion time is over 2 h. When the CTAB concentration was relatively higher ( 1.0 10 3 mol dm 3), especially at 5.0 10 3 and 2 3 1.0 10 mol dm CTAB concentrations, a large amount of bromide ions rapidly adsorbed on the copper surface and promoted the dissolution of copper.15,16 When the immersion time increased, C16H33N CH3 3 ions adsorbed strongly on the surface of copper through the electrostatic attraction force because of the large excess of negative charge. In this case, chemisorption of n-cetyl on the surface may be ignored. A hemimicelle barrier composed of C16H33N CH3 3 ions will form on the whole surface due to the interaction between hydrocarbon chains via the van der Waals forces as the concentration of CTAB in solutions is quite high. The barrier becomes more and more compact with adsorption of more C16H33N CH3 3 ions on the surface. In this way, the inhibition efciency of CTAB increases with the increase of immersion time. Conclusions CTAB is a quaternary ammonium salt with long alkyl chains, and acts as a mixed-type inhibitor against copper corrosion in 0.5 mol dm 3 sulfuric acid. Comparison of the inhibition efciency of CTAB and TMAB shows that the inhibitor effectiveness increases with the increasing length of the alkyl chains. Chemisorption of n-cetyl on copper surface enables CTAB molecules to cover much of the area on the copper surface, giving rise to a higher inhibition efciency than TMAB. The CTAB concentration and the immersion time of the copper electrode in the solutions have a great inuence on the inhibition efciency of CTAB. C16H33N CH3 3 ions may adsorb on the copper surface through both chemisorption and electrostatic attraction when the CTAB concentration is low ( 1.0 10 3 mol dm 3). On the contrary, chemisorption of n-cetyl may be ignored and C16H33N CH3 3 ions mainly adsorb on the surface by the electrostatic attraction force when CTAB concentration is high ( 1.0 10 3 mol dm 3). The copper surface was positively charged in sulfuric solutions at the corrosion potential. The electrostatic adsorption of C16H33N CH3 3 or N CH3 4 ions is attributed to the synergistic effect between bromide anions and positive quaternary ammonium ions.