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Study of the Inhibition Mechanism of Imidazolines by Electrochemical Impedance Spectroscopy

G. Gusmano,* P. Labella,** G. Montesperelli,,*** A. Privitera,** and S. Tassinari**

ABSTRACT
In this paper, the results of evaluating the activity of imidazoline-based corrosion inhibitors by means of electrochemical impedance spectroscopy (EIS) and other traditional electrochemical methods are reported. Tests were carried out on AISI 1040 (UNS G10400) mild steel specimens immersed in solution simulating the composition of an aqueous phase during oil production and transportation: high salinity, presence of carbon dioxide (CO2), anaerobic environment, 40C temperature. Two different inhibitor formulations were tested in the presence of different salting agents (acetic acid [CH3COOH] and thioglycolic acid [HSCH2COOH or TGA]). EIS data were analyzed using equivalent circuits. The electrochemical tests indicated evidence of different mechanisms and activity depending on inhibitor formulation. KEY WORDS: carbon dioxide corrosion, carbon steel, corrosion inhibitors, electrochemical impedance spectroscopy

INTRODUCTION
Corrosion is one of the most serious problems in the oil and gas production and transportation industry. The environmental conditions in oileld systems can
Submitted for publication May 2005; in revised form, October 2005. Corresponding author. E-mail: g.montesperelli@univpm.it. * Dipartimento di Scienze e Tecnologie Chimiche, Universit di Roma Tor Vergata, Via della Ricerca Scientica, 00133 Rome, Italy. ** Nalco Italiana S.r.l., Via Ninna II, 04012 Cisterna di Latina (Lt), Italy. *** Dipartimento di Fisica ed Ingegneria dei Materiali e del Territorio, Universit Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy.

be very different, but they can be generally summarized as follows: anaerobic conditions, a high concentration of carbon dioxide (CO2), high salinity, and a variable concentration of suldes.1-2 Depending on environmental composition, different forms of corrosion can take place in oil and gas wells and ow lines.3 Among them, CO2 corrosion, usually called sweet corrosion, is one of the most severe because the effect of CO2 and/or carbonic acid (H2CO3) can enhance the electrochemical cathodic reaction.4-6 The use of corrosion inhibitors is currently used to protect against corrosion in all petrochemical facilities in the world, because it is cost-effective and exible.7-8 The total consumption of corrosion inhibitors in the United States has doubled from approximately $600 million in 1982 to nearly $1.1 billion in 1998.9 It also has been reported that the U.S. market for corrosion inhibitors is estimated to be up to $1.6 billion per year by the year 2006.10 Some of the most effective corrosion inhibitors for oil and gas pipeline application are the fatty acid imidazolines. The general chemical structure of imidazoline inhibitors is shown in Figure 1. It consists of three parts: a ve-atom ring with two nitrogen elements (part A), a pendant side chain with a functional group (part B), and a long hydrocarbon chain (part C). The inhibition mechanism of imidazoline inhibitors is poorly understood and some discrepancies can be observed in the main literature.11-17 It can be depicted as follows:

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The head group (part A) promotes a strong bonding of the molecule to the surface of the metal and forms an ordered lm of one or more layers. The lone pair on the CH2CH2NH2 pendant chain group (part B) could also help to improve the molecular adsorption to the surface, thereby improving the corrosion inhibition performance. The hydrocarbon tail (part C) promotes a hydrophobic surface covering of the metal surface. The hydrocarbon tail and pendant group must have a favorable partition coefcient between hydrocarbon and water phase, to permit the lm to build a hydrophobic barrier that blocks water from the surface. Recent works, based on surface binding energies calculations, demonstrated a favorable adsorption of imidazolines on iron oxide (Fe3O4)18 and iron carbonate (FeCO3)19 that could form a rst layer on the metal surface, but no experimental evidences are conrmed. Moreover, imidazolines have very low solubility in a water phase, and to increase solubility, these compounds are usually converted to a salt with acids. The most common acid of these types of formulations is acetic acid (CH3COOH). It has been demonstrated that carboxylates can inuence the orientation of organic inhibitors on the steel surface.20 In practice, the application of inhibitors can be very problematic because of the variation of the environment composition. For these reasons, the use of some monitoring techniques able to evaluate inhibitor efciency and to determine critical concentration, depending on the environmental condition, is essential. There are many techniques that can be used for inhibitor testing. A few of them are able to give an improved fundamental knowledge of corrosion processes and the mechanisms of corrosion inhibitors, to acquire better control methods in relation to the environmental corrosiveness. Electrochemical impedance spectroscopy (EIS) has often been used in various corrosion elds such as coatings, passive layer buildup and breakdown, and inhibitor evaluation.21-23 EIS is well known as a powerful tool able to provide information on corrosion rate, both on corrosion and protection kinetics and mechanism. In this work, EIS, together with other traditional electrochemical techniques, were used to study the imidazoline-based inhibitor lm formation and evaluation. In particular, the effect of thioglycolic acid (HSCH2COOH [TGA]) in conjunction with acetic acid as the salting agent in the inhibitor formulation was studied.
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FIGURE 1. General chemical structure of imidazolines used in this work.

TABLE 1 Composition of Inhibitors

Components Imidazolines Acetic acid (CH3COOH) Thioglycolic acid (HSCH2COOH) Isopropanol ([CH3]2CHOH) Water A (wt%) 25 6 10 59 B (wt%) 25 3 3 10 59

EXPERIMENTAL PROCEDURES
Tests were performed on AISI 1040(1) (UNS G10400)(2) mild steel samples. Test electrodes were rods, 4 mm in diameter. The surface preparation consisted of abrading the specimen with silicon carbide (SiC) 500-grit paper, washing in water then in ethanol (C2H5OH), and drying in air. The surface electrode was delimitated by enamel and the exposed area was 10.2 cm2. Tests were carried out in an unstirred solution of 30 g/L sodium chloride (NaCl) in which a constant CO2 bubbling was performed throughout the tests. A sealed cell was used with a vent to prevent overpressure. The cell was thermostat-controlled at 40C and oxygen concentration was measured using an Orbisphere Laboratories model 2713 probe and kept under 10 ppb during all the tests. The pH value measured throughout the tests was in the range from 3.8 to 4.0. Inhibitors were a commercial mixture of imidazolines with an aliphatic chain varying between 12 and 18 carbon atoms, as shown in Figure 1. Two different commercial inhibitors (Nalco Italiana [Rome, Italy]), at concentrations of 25 ppm or 50 ppm were used and their compositions are reported in Table 1. Blank tests were also performed. EIS measurements were performed using a Solartron 1260 frequency response analyzer and a Solartron 1287 electrochemical interface. An alternating current (AC) signal, 5 mV in amplitude, was applied at the open-circuit potential (OCP) in the frequency range of 5 mHz to 500 kHz. Data were collected and

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American Iron and Steel Institute (AISI), 1140 Connecticut Ave., Ste. 705, Washington, DC 20036. UNS numbers are listed in Metals and Alloys in the Unied Numbering System, published by the Society of Automotive Engineers (SAE International) and cosponsored by ASTM International. Trade name.

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RESULTS AND DISCUSSION

OCP trends as a function of immersion time for tests at an inhibitor concentration of 50 ppm are reported in Figure 2, in which the curve for a blank test is also reported. Curves for inhibited solutions show a similar trend, with a very strong potential ennoblement with respect to the blank test, already detectable in the rst hours of immersion. After 4 h, OCP kept a stable value of 650 mV vs. silver/silver chloride (Ag/AgCl) to 640 mVAg/AgCl in spite of the 710 mVAg/AgCl measured in the blank test. Polarization curves were carried out in the same conditions. Figure 3 reports polarization curves acquired after 0, 2, and 6 h of immersion for a test with inhibitor A at 50 ppm. Curves conrmed an OCP shifted toward anodic values and evidenced a marked variation with time of both anodic (a) and cathodic (c) Tafel slopes. In the anodic segment of polarization curves collected after 2 h and 6 h of immersion, a slope variation could be detected, as shown with arrows in Figure 3. This potential, usually called desorption potential (Ed),24 reveals the potential at which the lm breakdown begins. The lm formation and stabilization was conrmed by the increasing of Ed from 584 mV to 557 mV, with immersion time increasing from 2 h to 6 h. Data from the polarization curves after 6 h of immersion are summarized in Table 2 in which a, c, and Ed for tests on both inhibitors and a blank test are reported. A comparison of data coming from inhibitors A and B revealed a strong decrease of the cathodic Tafel slope of inhibitor B with respect to inhibitor A and a clear lm stabilization. The anodic part remained unaffected. Polarization curves collected in the solution of inhibitor B presumably reveal the effect of TGA. It has been reported that TGA can have an inhibition or activation effect in aqueous environments containing CO2, depending on pH, temperature, and its concentration. It has also been reported that TGA can have inuence on the cathodic Tafel slope, without any appreciable inuence on the anodic part.25 A corrosion rate calculation by LPR, shown in Figure 4, conrmed this nding. After about 12 h of immersion, the corrosion rate for inhibitor A at 25 ppm settled at 0.15 mm/y, while the curve related to the same inhibitor at 50 ppm settled at 0.10 mm/y. The same tests for inhibitor B showed values lower than 0.02 mm/y after only 5 h for both concentrations. Blank tests evidenced an average corrosion rate of 1.40 mm/y. Figures 5(a) and (b) show an EIS plot in Bode format recorded on a test with 25 ppm of inhibitor A at different immersion times. The increasing of impedance magnitude during the test indicates that the presence of the inhibitor strongly reduced the rate of electrochemical reactions on the electrode surface. Total resistance increased with immersion time,

FIGURE 2. OCP trend as a function of time for inhibited solutions (50 ppm) and for a blank test.

FIGURE 3. Polarization curves for a test with inhibitor A (50 ppm) at different immersion times.

TABLE 2 a, c, and Ed After 6 h of Immersion

Blank a (mV) c (mV) Ed (mV) 93 318 Inhibitor A 130 217 557 Inhibitor B 129 89 439

analyzed using Zplot-Zview software. Polarization curves were carried out using a Solartron model 1285 potentiostat-galvanostat, with a scan rate of 4 mV/s. Corrosion rate measurements were performed using linear polarization resistance (LPR) with a corrosimeter using a three-electrode corrosion probe. Although tests were run in triplicate, data are presented as individual experiments. The calculated error was within 10 % for each test.

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(a)
FIGURE 4. Corrosion rate by LPR as a function of immersion time.

reaching a maximum value after 22 h, thus reaching a steady state. The vs. log plot recorded of electrodes after immersion, and shown in Figure 5(b), shows a single phase angle shift at 100 Hz that can be ascribed to charge-transfer and double-layer characteristics.15 After 2 h from the immersion, the phase plot showed a new phase angle shift at a higher frequency range (>1 kHz), which was more pronounced with increasing time. This new peak means that the structure of the electrode interface has changed as a consequence of lm buildup. At the same time, the charge-transfer peak shifted at lower frequencies (10 Hz and lower). The presence of the two-phase angle shifts in the vs. log plot suggests that there are two main kinetic processes on the electrode surface. Consistent with other authors,15,26-27 the highfrequency loop can be ascribed to the inhibitor lm because of its small time constant that causes a phase shift in the high-frequency limit. Figures 5(a) and (b) also show an EIS plot for a blank test after 4 h of immersion. As expected, a very low total resistance and only one time constant were detected. Usually, impedance data are analyzed by using an equivalent circuit, taking into account the contribution of each phenomenon such as polarization resistance, double layer, lm formation, etc. The nonlinear least-square (NLLS) method is usually used to simultaneously and iteratively adjust the circuit element values to obtain the best match between the experimental and simulated data. The statistical relevance of the simulation is usually given by the chi-squared (2) test that easily gives the goodness of a t by calculating the square of the standard deviation between the experimental data and the calculated spectrum. Another signicant parameter is the weighted sum of squares (WSOS), which is proportional to the average percentage error between the experimental data and the calculated values. The best

(b)
FIGURE 5. Bode plot of EIS data during lming process with 25 ppm of inhibitor A.

equivalent circuit is that which can minimize 2 and WSOS. Moreover, all the impedance spectra acquired had a form of a depressed semicircle in the Nyquist representation, as shown in Figure 6, for a test with 25 ppm of inhibitor A. This may have different explanations because of the roughness of a solid metal electrode,28 the inhomogeneous reaction rate on the electrode surface,29 or the varying thickness or composition of a coating.30 In these cases, constant phase elements (CPE) are generally used instead of a real capacitance. The CPE parameters were converted into capacitance values following the reported procedure.31 Figure 7 reports the equivalent circuits used in this paper. The rst EIS spectra acquired a few minutes after the immersion were analyzed through a simple equivalent circuit for the corrosion system under charge-transfer control reported in Figure 7(a), with Rs being the solution resistance, Rct the chargetransfer resistance, and Cdl the double-layer capacitance. No mass-transport phenomena were detected, but, in spite of a very low oxygen concentration, it

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FIGURE 6. Nyquist plot of EIS data during lming process with 25 ppm of inhibitor A.

FIGURE 8. Fitting of a typical Bode plot for a test with inhibitor A, using the equivalent circuit of Figure 7(b).

FIGURE 7. Equivalent circuits used in this paper.

may not be excluded that mass phenomena may appear at frequencies lower than 5 mHz. EIS data of electrodes immersed in inhibitor A solution were analyzed by different equivalent circuits. Among them, the circuit in Figure 7(b) gave the best results in terms of 2 and WSOS. The circuit in Figure 7(b) is often reported in the literature32-33 to simulate the behavior of coated metals, where Rf is the pore resistance that is due to the formation of an ionically conducting path across the lm and Cf is the capacitance of the lm. The use of this circuit gave satisfactory results as shown in Figure 8 for an EIS acquisition in a test with 25 ppm of inhibitor A. The 2 test and WSOS values were 4.2 104 and 3.6 102 for circuit 6b, thus conrming a good t. The use of circuit 6b permitted the analysis of all the spectra acquired after 2 h from immersion into the solution containing inhibitor A. The use of the equivalent circuit with the NLLS t permitted the calculation of the charge-transfer and lm parameters during the test. Figure 9 reports the trend of Rct and Rf for a typical test in inhibitor A

at 50 ppm. In the rst hours of immersion, Rct and Rf have very similar trends characterized by a quick increase, conrming that the lm formation is fast. After 10 h, Rct settled at a constant value of about 1,350 cm2, whereas Rf increased slightly. Figure 10 reports the trend of Cdl and Cf for the same test illustrated in Figure 9. Cdl and Cf show an inverse trend, with a strong decrease in Cdl in the very rst part of the test and a slight increase in Cf during the rst 20 h of the test. After that, both capacitances come to a constant and very close value of about 870 F/cm2. Considering that the electrode surface (A) is constant throughout the test, capacitance values are directly proportional to the dielectric constant of the lm (f) and inversely proportional to the thickness of the layer (d) following the relationship: Cf = f 0 A d (1)

where 0 is the permittivity of free space. Concerning the evolution of Cf with time, the growing of an inhibitor lm may, in principle, cause an increase in the thickness and density of the lm.

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FIGURE 9. Rct and Rf trend as a function of time for a typical test in inhibitor A at 50 ppm.

FIGURE 10. Cdl and Cf trend as a function of time for a typical test in inhibitor A at 50 ppm.

Theoretical calculation demonstrated that imidazoline lm presumably forms a bilayer on an inner lm of FeCO3 and/or Fe3O4 and takes place very quickly.18,34 Moreover, optical polarization studies have conrmed that the imidazoline molecules are at on the surface.35 In this hypothesis, the lm thickness could be assumed constant after a few hours from immersion. The growing lm becomes a more compact structure, closing the porosity and thus increasing density. The increase in the compactness generates an increase in the dielectric constant and therefore in capacitance. On the other hand, the decrease in Cdl can be explained by the decrease in charge density within the double layer as the imidazoline lm grows. EIS tests on inhibitor B were performed and analyzed with the same test procedure on inhibitor A. Figures 11(a) and (b) show some EIS spectra in Bode format, for a test with 25 ppm of inhibitor B at different immersion times. The magnitude vs. frequency plot shows a fast increase in total resistance. It arrived at a constant value after about 9 h, which is much faster than inhibitor A. The phase angle plot shows a very large angle shift that increases in width with time, which actually is formed from at least two or more different peaks. This large phase shift suggests a more complicated lm-metal interface structure with respect to inhibitor A. The role of TGA is not well understood at the moment. It has been reported that, under anaerobic conditions, a complex anion [Fe(II)(S-CH2-COO)2]2 is formed36-37 and can be oxidized to form iron disulde (FeS2) that precipitates on the metal surface.38 An XPS investigation on electrodes immersed in the same condition of corrosion tests has been undertaken. Preliminary results seem to conrm the presence of an iron sulde and/or disulde layer on the metal surface. For this reason, EIS data on inhibitor B were tted with the equivalent circuit of Figure 7(c), in which

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(b)
FIGURE 11. Bode plot of EIS data during the lming process with 25 ppm of inhibitor B.

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FIGURE 12. Fitting of a typical Bode plot for a test with inhibitor B, using the equivalent circuit in Figure 7(c).

FIGURE 13. Rct, Rf, and Rz trend as a function of time for a typical test in inhibitor B at 50 ppm.

FIGURE 14. Cdl, Cf, and Cz trend as a function of time for a typical test in inhibitor B at 50 ppm.

Rz and Cz have been added to the previous circuit, in accordance with early experimental ndings of an iron sulde/disulde layer. At the moment, additional XPS investigations are in progress and nal results will be published soon. A comparison between experimental and calculated EIS spectra is shown in Figure 12. The use of circuit 6c provided a tenfold decrease of the 2 value from 2.3 103 to 3.2 104, thus justifying the introduction of the new element. Resistance values coming from EIS data tting are shown in Figure 13. Rct and Rf have the same trend since both of them are related to the lm formation. Rf is about one order of magnitude higher with respect to that of inhibitor A. As a consequence of this, Rct reached a steady value of 3,500 cm2. Rz gave a poor contribution to the total resistance (about 15 cm2) and is essentially unaffected by time. As a rst assumption, TGA seems to be inaccessible by

solution and acts as an inner layer. The very low Rz value indicates that it is not protective. Capacitance values are summarized in Figure 14. The Cdl showed a trend very comparable to that of test results with inhibitor A, with a decrease in the rst part of the test followed by reaching a constant value of about 500 F/cm2. This value is lower than that calculated for the tests in inhibitor A, as predicted from the higher level of protection of inhibitor B. The trend of Cf is strictly connected to the evolution of lm structure. The inhibitor adsorption on the metal surface is faster with respect to inhibitor A, probably because of the presence of TGA. It can be assumed that the adsorption stage takes approximately 2 h, in which Cf decreases as a consequence of the lm thickness increasing. After that, a trend comparable to that of inhibitor A has been detected with a slight increase of Cf due to the buildup of a more compact structure. The Cz contribution is approximately constant throughout the test and its value settled at about 50 F/cm2. This lead to the deduction that the effect of TGA occurred before imidazoline lm growth. In any case, its contribution took place in the very rst part of the test.

CONCLUSIONS
An electrochemical analysis by means of different techniques, using two imidazoline-based inhibitors with two different formulations, was performed. Tests were carried out in 30 g/L NaCl at 40C, with constant CO2 bubbling. Some blank tests, without the presence of an inhibitor, were also performed. All the electrochemical tests were consistent and demonstrated than inhibitor B has an activity higher than that of inhibitor A. OCP measurements evidenced a strong ennoblement of both the inhibitors with respect to the blank tests.

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Polarization curves revealed an increasing of anodic Tafel slopes for both inhibitors. The cathodic segment revealed a very strong depolarization effect for inhibitor B and a milder one for inhibitor A. The presence of a desorption potential revealed the growth of a lm on the electrode surface, more stable on inhibitor B with respect to inhibitor A. LPR evidenced very slow corrosion rates (0.10 mm/y and 0.02 mm/y for inhibitors A and B, respectively), with respect to blank tests (1.40 mm/y). EIS revealed two different protection mechanisms of the inhibitors evidenced by the use of two equivalent circuits to simulated EIS data. The presence of TGA within inhibitor B introduced an additional RC element in the equivalent circuit used to t the EIS data. Presumably, the TGA contribution is faster than imidazolines adsorption, and assists the growth of a thicker and more compact lm structure, as conrmed from the evolution of lm resistance and capacitance as a function of immersion time. Some surface investigations are ongoing to determine the role of TGA on the protection mechanism of inhibitor B. Preliminary results seem to indicate the presence of iron suldes on the metal surface.
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