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Inhibition Effect of Sodium Nitrite and Silicate on Carbon Steel Corrosion in Chloride-Contaminated Alkaline Solutions
O. Girciene,,* R. Ramanauskas,* L. Gudavi iute,* and A. Martuiene* c

ABSTRACT
The ability of some corrosion inhibitors to protect carbon steel against corrosion was investigated using the voltammetric and electrochemical impedance spectroscopy (EIS) techniques. The surface analysis of samples was carried out by x-ray photoelectron spectroscopy (XPS). EIS measurements have shown that prolongation of steel exposure to solution containing sodium nitrite (NaNO2) from 0.5 h up to 240 h leads to an approximately tenfold increase in charge-transfer resistance (Rt) values. After 240 h of exposure to the solution with the NaNO2 + sodium silicate (Na2SiO3) mixture, Rt values were about threefold higher as compared to those obtained in the solution containing only one inhibitor, NaNO2. The XPS data revealed that an up to 4 nm thick passive layer was formed after 240 h of carbon steel exposure to the solution with NaNO2. An additional introduction of Na2SiO3 into the same solution increased the thickness of the oxide layer >8 nm. In the outer part of the oxide layer, Fe was detected in the form of ferrous oxide (FeO), while magnetite (Fe3O4) was the main constituent of the inner part of the oxide layer. KEY WORDS: alkaline solution, carbon steel, chloride ions, corrosion, corrosion inhibitor

INTRODUCTION
Corrosion of iron or steel embedded in concrete is the subject of extensive research and discussion with regard to instrumental techniques and data interpreSubmitted for publication April 11, 2011; in revised form, July 15, 2011. Corresponding author. E-mail: olgag@chi.lt. * State Scientific Research Institute, Centre for Physical Sciences and Technology, Institute of Chemistry, Gotauto 9, LT-01108, Vilnius 2600, Lithuania.

tation.1-4 Concrete-reinforced structures are usually very resistant to corrosion because the alkaline concrete environment (pH ~13) passivates steel by formation of the iron passive layer. Passive oxide films have been described to have a bilayer structure consisting of an inner layer that grows directly on the metal surface and an outer layer precipitated via the hydrolysis of cations ejected from the inner layer.4-7 Corrosion of the embedded steel occurs if this protective film is disrupted as in, for instance, the presence of chlorides from deicing salts. The mechanism by which steel embedded in concrete corrodes in the presence of chlorides is not fully understood in spite of the fact that the local breakdown of the passive layer formed under highly alkaline conditions of the concrete is the most frequent reason for reinforcement corrosion. It is assumed that corrosion initiates when the chloride concentration reaches its critical value at the rebar surface. This critical chloride concentration is known as the chloride threshold level.8-12 The chloride thresholds determined are expressed as total and free chlorides as well as the chloride/hydroxide ratio. The chloride threshold is one of the key parameters needed for service life prediction of concrete structures. The main difficulty that the determination of this parameter encounters is that the chloride threshold-inducing active corrosion is not a unique value and depends on several variables.12 The corrosion of steel in concrete is difficult to investigate, mainly because of experimental problems such as high resistivities, highly porous materials, cell design, and macrocells. An alternative way of tackling the problem is to use solutions that simulate

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TABLE 1 Chemical Composition of the Steel (wt%)

Steel Carbon steel C 0.21 Mn 1.2 Si 0.6 Cr 0.3 Ni <0.3 Cu <0.3 P <0.04 S <0.045

the chemical environment present in the pores of concrete. Since the pore solutions in cement and concrete are thought to consist mainly of aqueous potassium hydroxide (KOH), sodium hydroxide (NaOH), and calcium hydroxide (Ca[OH]2), it is possible that the studies of the cyclic voltammetry of iron in these solutions could be useful as a basis for understanding the electrochemical corrosion behavior of steel reinforcement in porous concrete structures. The electrochemistry and corrosion of iron and carbon steel in hydroxide solutions have been studied by many authors.4-6,13-18 Corrosion and passivation of Fe in alkaline solutions are relatively complex processes that are not yet fully understood because the composition and structure of the passive layer are still not completely understood. This is partly because the passive films are so thin and because the structure should ideally be studied in the wet electrochemical environment in which these films are formed. The composition of the passive layer (oxides or hydroxides) and its structure (crystalline or amorphous) remains controversial, despite the use of in situ and ex situ techniques.15 The electrochemical and ellipsometric responses of Fe electrodes were studied in alkaline electrolytes (NaOH and saturated Ca[OH]2) under potentials at which the passive layer is formed.5-6 These results suggest that the passive layer has a composite structure involving a inner layer that is difficult to electroreduce, probably similar to magnetite (Fe3O4) in composition, and a gelatinous iron hydroxide outer layer, where a reversible Fe2+/Fe3+ reaction has been detected by cyclic voltammetry.6 Many approaches can be used to mitigate the corrosion of reinforcing steel, among which protective coatings, cathodic protection, concrete realkalinization, and corrosion inhibitors are commonly used. The use of corrosion inhibitors is probably more attractive from the point of view of economics and ease of application. The most commonly used inhibitors are formulated on the basis of nitrite ions.19-24 Studies also showed that the nitrite ion, an anodic inhibitor,21 modifies the oxide film on the steel bar in concrete. The nitrite ions compete with the chloride ions for ferrous ions produced in concrete and incorporate them into a passive layer on the iron surface.21 When the passive state can be compromised because of the presence of chlorides, the corrosion risk is determined by the chloride content, usually evaluated as the chloride/hydroxyl ratio.8-12 On the other hand, the efficiency of nitrite as inhibiting agent in the presence of chloride is evaluated in terms of the nitrite/chlo-

ride ratio. There is no clear agreement on the threshold value of this ratio. Different authors23-24 have given values ranging from 0.34 to more than 1 as those necessary to prevent corrosion in concrete. Along with calcium nitrite (Ca[NO2]2), which is a traditional commercial inhibitor used for application in reinforced concrete structures, many substances have been tested as inhibitors against the corrosion of carbon steel in the alkaline media.21,25-31 Sodium silicate (Na2SiO3) has been used as a corrosion inhibitor for years.25-30 It is greatly attractive in terms of nontoxicity, cost, and availability. A number of authors have discussed the mechanism of formation and the nature of protective layers formed on metals in solutions of sodium silicate.25-30 The film formed on iron in the presence of silicate is usually described as a twolayer deposit, the inner layer being composed of corrosion products and the outer one of a conglomerate of adsorption compounds of silica, meta-hydroxide, and silica gel.28 Surveys of the behavior of several inhibitors in a single and mixed manner also have been reported.29,31 In this paper, the effects of chloride ions on the breakdown of passive films formed on carbon steel in a 0.1 M NaOH solution have been studied, and sodium nitrite, sodium silicate, and their synergistic effect on the corrosion prevention of carbon steel have been discussed.

EXPERIMENTAL PROCEDURES
The corrosion behavior of carbon steel was investigated in an aerated stagnant 0.1 M NaOH solution containing 0 to 1 M sodium chloride (NaCl) at 25C. The substances tested as corrosion inhibitors were sodium nitrite (NaNO2, SN), Na2SiO3 (SS), and their mixture (SN+SS). All solutions were prepared from analytical grade chemicals and deionized water. The working electrode was a carbon steel sample, the composition of which is listed in Table 1, with an area of 4 cm2, whose nonworking surface was masked with epoxy resin. The steel samples were polished with no. 600 silicon carbide (SiC) paper and rinsed with distilled water. All electrochemical measurements were made using a standard three-electrode system with a Pt counter electrode and a saturated silver/silver chloride (Ag/AgCl) reference electrode. All potentials are reported vs. a saturated Ag/AgCl reference electrode. The polarization measurements were performed using a potentiostat with potential scan rates of

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0.002 V s1 and 0.05 V s1. The cyclic voltammetric (CV) scans started at an initial open-circuit potential. Before voltammetry experiments, the open-circuit potential of electrodes in the solution was monitored for 0.5 h. The potential generally was cycled between 1.25 VAg/AgCl and 0.35 VAg/AgCl. The electrodes were cycled at least 20 times, and the twentieth cycle was recorded. The corrosion current densities (icorr) were determined by Tafel line extrapolation. The breakdown potential was determined from anodic polarization curves since the intercept of the tangents drawn at the point of sudden current density increase in the passive region. The data on corrosion potential (Ecorr) and pitting potential (Epit) values were the average of five measurements. The inhibition efficiencies (IE%) for the steel electrode were calculated from icorr using the following equation:24,29 IE % = [( i 0 i corr ) / i 0 ] 100 [ ( corr corr (1)

where i0 and icorr are the corrosion current values of corr the specimens in solutions without and with the addition of an inhibitor. IE% was also calculated from the charge-transfer resistance (Rt) by:24-25,29 IE % = [( R t R ) / R t ] 100 [(
0 t

FIGURE 1. Cyclic voltammograms (cycles 1 through 5 and 20) for carbon steel in a 0.1 M NaOH solution; 0.05 V s1, 25C. Vertical lines refer to equilibrium potentials calculated from the equations given by Misawa32 for electrochemical couples.

(2)

where Rt and R0 are the charge-transfer resistance t values in the base solution with and without inhibitors, respectively. Electrochemical impedance spectroscopy (EIS) tests were performed at the open-circuit potential after 0.5 h and 10 days (240 h) of aging. The EIS measurements were carried out in a frequency range from 20 kHz to 0.001 Hz using an impedance spectrum analyzer. The perturbation signal amplitude was 10 mV at the open-circuit potential. The EIS data were fitted using commercial software. The XPS spectra were recorded by a spectrometer using x-radiation of MgKa (1,253.6 eV, pass energy of 20 eV). To obtain depth profiles, the samples were etched in the preparation chamber by ionized argon at a vacuum of 5 104 Pa. An accelerating voltage of ca. 1.0 kV and a beam current of 20 A cm2 were used, which corresponded to an etching rate of ca. 2 nm min1.

RESULTS AND DISCUSSION Potentiodynamic Polarization

Cyclic voltammetry has proven to be a useful technique for studying various aspects of the electrochemical behavior of iron and steel in alkaline solutions.1-3,6,13-18 Typical CV (cycles 1 through 5 and 20) for carbon steel in a 0.1 M NaOH solution, when the

potential generally was cycled between 1.25 VAg/AgCl and 0.35 VAg/AgCl, are shown in Figure 1. Equilibrium potentials (vs. Ag/AgCl) for some possible reactions on iron in 0.1 M NaOH (pH = 13) were calculated from the equations given by Misawa,32 and they are marked in Figure 1 by vertical lines. Line 1 represents the potential for the formation of iron(II) hydroxide (Fe[OH]2), lines 2 and 3 represent the potentials for the formation of Fe3O4, and lines 4 through 7 represent the potentials for the formation of a-FeOOH (goethite) and -FeOOH (lepidocrocite).14 The voltammograms that are shown in Figure 1 are similar in appearance to those previously reported, with some variations in the number and shape of the peaks.1,13-18 A sharp anodic peak (ap) at ~ 0.64 VAg/AgCl and one cathodic peak (cp) at ~ 0.99 VAg/AgCl can be identified. Additionally, two anodic shoulders, a1 (0.97 VAg/AgCl 1.07 VAg/AgCl) and a2 (0.7 VAg/AgCl 0.18 VAg/AgCl), and one cathodic shoulder, c2 (0.85 VAg/AgCl 0.69 VAg/AgCl) were observed on the anodic and cathodic sweeps. Shoulder a1 was observed at 1.04 VAg/AgCl 0.82 VAg/AgCl, i.e., where Hugot-Le Goff, et al.,14 identified two anodic peaks on iron in a deaerated 1 M NaOH solution. Peak ap grew with the number of cycles, as did peak cp, indicating a direct relationship between the two peaks (Figure 1). The observed relationship between anodic and cathodic peaks shows that the product formed at peak ap is reduced at peak cp. Shoulder c2 is considered to be a reverse (reduction) reaction corresponding to an anodic reaction at shoulder a2.13 It has been shown14 that Fe3O4 is formed in a wide range of anodic polarization values, starting

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FIGURE 2. Cyclic voltammograms for carbon steel in the solution (a): 1- 0.1 M NaOH, 2- 0.01 M NaOH + 0.01 M NaCl, 3- 0.1 M NaOH + 0.05 M NaCl, 4- 0.1 M NaOH + 0.1 M NaCl; (b): 5- 0.1 M NaOH + 0.2 M NaCl; cycle 20, 0.05 V s1, 25C.

from the potentials of shoulder a1. The passivating film was suggested to be composed of an inner Fe3O4 layer and an outer layer containing other products of anodic iron oxidation. On this inner Fe3O4 layer can grow deposits of products such as Fe(OH)2, magnetite (Fe3O4) (from the transformation of other compounds), iron(III) hydroxide (Fe[OH]3), d-FeOOH, a-FeOOH, and iron(II) hydroxide (Fe2O3).14 The detrimental effect of chloride ions on the passive layer formed on iron exposed to alkaline environments has been reported extensively in literature.8-12,24 Therefore, a sequence of voltammograms was carried out in a solution contaminated with varying amounts of chloride ions (Figure 2). As can be seen from Figure 2(a), after addition of 0.01 M NaCl to a 0.1 M NaOH solution ([Cl]/[OH] = 0.1), the height of an ap increases fourfold from 0.001 A/cm2 to ~0.004 A/cm2. A further increase in chloride concentration in the solution from 0.01 up to 0.1 M ([Cl]/[OH] = 1) changes the height of ap only slightly (Figure 2[a]). Extensive depassivation upon exposure to 0.2 M NaCl in the 0.1 M NaOH solution ([Cl]/[OH] = 2) is evident, the voltammogram being extremely distorted with a very large current, especially in the normally passive region at the potentials of ap (Figure 2[b]). The instability of the currents at a high ap might be the result of localized corrosion. The influence of Cl ions on the passivity breakdown of carbon steel can be interpreted as a balance between two processes competing on the metal surface: stabilization of the passive film by OH adsorption and disruption of the film by Cl ions adsorption. When the activity of chlorides overcomes that of hydroxyls, pitting occurs.

To reduce the corrosion of carbon steel, an inhibitor can be used. The nitrites are the most commonly used inhibitors.19-25 The nitrite ion, which acts as an anodic inhibitor, modifies the oxide film on steel to be more protective than the film that naturally is formed in concrete.20-21 From the polarization curves presented in Figure 3(a), it is seen that the anodic and cathodic current densities decrease in the presence of inhibitor 0.1 M NaNO2 in the 0.1 M NaOH solu tion. A set of polarization curves with [NO2] = 0.1 M was recorded in a solution contaminated with various amounts of chloride ions and the [NO2]/[Cl] ratios ranging between 0.1 and 1, as presented in Figure 3. Low Cl concentrations such as 0.1 M and 0.2 M ([NO2]/[Cl] = 1 and 0.5) produced no significant difference in the polarization curves when they were compared with those in a chloride-free solution (Figure 3[b], curves 1 and 2). When the concentration of chloride ions in the solution is increased up to 0.75 M ([NO2]/[Cl] = 0.13), the polarization curves recorded (Figure 3[b], curves 3 and 4) practically coincide with the curves recorded in 0.1 M NaOH without the inhibitor (Figure 3[a], curve 1). However, in the presence of 1 M NaCl, [NO2]/[Cl] = 0.1 (Figure 3[b], curve 5), the rates of anodic and cathodic processes increase almost two-fold and steel undergoes general corrosion. The attack of chlorides on the passive film is marked by a sharp increase in current. An aggressive solution, 0.1 M NaOH + 1 M NaCl (base), was selected for further studies. The inhibition effect of NaNO2 (SN), Na2SiO3 (SS), and their mixture (SN+SS) on steel corrosion was investigated. The protective properties of the passive film formed

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FIGURE 3. Cyclic voltammograms for carbon steel in the solution (a): 1- 0.1 M NaOH, 2- 0.1 M NaOH + 0.1 M NaNO2; (b): 1- 0.1 M NaOH + 0.1 M NaNO2 + 0.1 M NaCl, 2- 0.1 M NaOH + 0.1 M NaNO2 + 0.2 M NaCl, 3- 0.1 M NaOH + 0.1 M NaNO2 + 0.5 M NaCl, 4- 0.1 M NaOH + 0.1 M NaNO2 + 0.75 M NaCl, 5- 0.1 M NaOH + 0.1 M NaNO2 + 1 M NaCl; cycle 20, 0.05 V s1, 25C.

on the steel surface were investigated measuring the film breakdown potential (Epit) induced by chloride ions. Oxide layers were formed by immersion of the steel electrode in the working solution for 0.5 h or for 10 days (240 h), where anodic polarization was later measured. Anodic polarization curves of preliminary passivated samples in the working solution without/ with inhibitors are presented in Figure 4. The values of Ecorr and Epit were determined and the differences between them in various solutions are listed in Table 2. The scatter of the Ecorr data was no more than 0.025 V and of the Epit data was no more than 0.015 V. The studies performed have shown that after 0.5 h of immersion in the base solution, the difference of Epit Ecorr was ~0.14 V (Figure 4, curve 1), while the highest detected value of difference was ~0.4 V in the presence of 1 M NaNO2 (Figure 4, curve 5). Whereas, in the presence of 0.1 M Na2SiO3 in the base solution, the Epit Ecorr value was ~0.2 V, i.e., only ~0.05 V higher than that in the solution free from the inhibitor (Figure 4, curve 2). Polarization measurements performed using a steel electrode after 240 h of exposure to the studied solution have shown that in the presence of 1 M NaNO2, the difference Epit Ecorr increases about 10% up to ~0.44 V (Figure 4, curve 6). Long-term studies in the base solution without inhibitor and in the presence of SS were not performed because steel corrosion actively proceeds under such conditions. The most positive Epit potentials were detected for carbon

steel electrodes after 240 h of immersion in the base solution with the inhibitors mixture (Figure 4, curves 7, 8). In solutions of such composition, the measured difference Epit Ecorr markedly increases and reaches 0.8 V (Table 2). Corrosion currents (icorr) of the carbon steel samples investigated after immersion in the base solution for 0.5 h and 240 h with various inhibitors and their mixtures were determined from Tafel line extrapolation (Figure 4). The values of icorr and the IE% obtained from electrochemical measurements are listed in Table 2. As seen from the data presented in Table 2, the lowest icorr values after immersion for 0.5 h in the studied solution were determined when 1 M NaNO2 was added to the solution, IE = 94%, while the IE% of Na2SiO3 was about 55%. When the exposure time was extended to 240 h in solution with a SN value of icorr = 1.8 107 A/cm2, with SN+SS mixture the values of icorr declined to 6.4 108 A/cm2 (Table 2) and IE% reached ~98%. The data obtained imply that the highest detected values of the difference of Epit Ecorr and the smallest icorr were detected for carbon steel electrodes after 240 h of immersion in the base solution in the presence of the SN and SN+SS inhibitor mixture.

Electrochemical Impedance Spectroscopy Measurement

The EIS diagrams for carbon steel samples exposed for 0.5 h and 240 h to the base 0.1 M NaOH + 1 M NaCl solution without and with corrosion inhib-

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FIGURE 4. Tafel polarization curves measured after immersion of the carbon steel electrode for 0.5 h in the solution: 1- 0.1 M NaOH + 1 M NaCl, 2- 0.1 M NaOH + 1 M NaCl + 0.1 M Na2SiO3, 3- 0.1 M NaOH + 1 M NaCl + 0.1 M NaNO2, 4- 0.1 M NaOH + 1 M NaCl + 0.5 M NaNO2, 5- 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 and for 240 h in the solution: 6- 0.1 M NaOH + 1 M NaCl + 1 M NaNO2, 7- 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 0.01 M Na2SiO3, 8- 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 0.1 M Na2SiO3; 0.002 V s1.

itors are given in Figure 5. The impedance data were fitted using two equivalent circuit models that are used generally to describe corrosion processes, which are shown in Figure 6.18,25 The impedance spectra recorded on the carbon steel samples exposed for 0.5 h to the base solution without/with the inhibitor indicated the presence of only one capacitive time constant (Figure 5, curves 1

through 3). Curves 1 through 3 were modeled by an equivalent circuit consisting of one Rt-CPE (chargetransfer resistance-constant phase element) and uncompensated ohmic resistance (R) in series (Figure 6[a]). CPE consists of the capacitance (C, F cm2) and frequency dispersion (n), a dimensionless parameter (n 1), which usually is correlated with the surface roughness.33 If n is close to 1, this means CPE is most capacitive. The exponent n of the CPE was between 0.77 and 0.95 for all experiments (Table 3). For fitting the data, all capacitances in the equivalent circuit had to be replaced by a CPE34 to adapt for nonideal behavior. The appearance of the CPE is often related to the electrode roughness or to the inhomogeneity in conductance or dielectric constant.35-36 The corrected values of the capacitances were obtained from the fitting program of Zahner electric, which uses the equation ZCPE = 1/[oV(j/o)n] for calculation.36-38 According to Schiller and Strunz,38 CPE is similar to the capacitive element, but with an absolute phase angle of less than 90. The CPE was extended through a normalization factor /0, to enable the use of the parameter V with the dimension F (Farad). Setting 0 to 1,000 Hz adjusts the transfer function to the impedance of a capacitor with the same (Farad) value in the center of the typical frequency range of a double-layer capacitance (Ct). All capacitance values used in this paper were normalized in this way. Curve 1 (Figure 5) shows a typical set of Bode plots for uninhibited carbon steel electrode in base solution. As we can see, the addition of sodium silicate (SS) to the base solution (Figure 5, curve 2) produced conditions that are very similar to those obtained in the base solution without the inhibitor. The addition of an effective inhibitor such as sodium nitrite (SN) produced passive conditions (Rt increases from 2.2 k cm2 to 6.5 k cm2, i.e., almost three-fold), but only one capacitive time constant was obtained throughout 0.5 h of exposure (Figure 5, curve 3). This

Trade name.

TABLE 2 Electrochemical Parameters for Carbon Steel Obtained from the Polarization Curves
Immersion Time (h) 0.5 0.5 0.5 240 240 240 240 icorr (A cm2) 3.8106 1.7106 2.3107 1.8107 8.1108 7.4108 6.4108 Ecorr (VAg/AgCl) 0.365 0.365 0.171 0.140 0.032 0.025 0.005 Epit (VAg/AgCl) 0.225 0.170 0.225 0.295 0.638 0.705 0.785 (Epit Ecorr) (V) 0.140 0.195 0.396 0.435 0.67 0.73 0.80

Solution 0.1 M NaOH + 1 M NaCl 0.1 M NaOH + 1 M NaCl + 101 M Na2SiO3 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 103 M Na2SiO3 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 102 M Na2SiO3 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 101 M Na2SiO3

IE% 55 94 95.3 97.7 98 98.3

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FIGURE 5. Bode plots of the impedance spectra after immersion of the carbon steel for 0.5 h in the solution: 1- 0.1 M NaOH + 1 M NaCl, 2- 0.1 M NaOH + 1 M NaCl + 0.1 M Na2SiO3, 3- 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 and for 240 h in the solution: 4- 0.1 M NaOH + 1 M NaCl + 1 M NaNO2, 5- 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 0.1 M Na2SiO3.

can be from the presence of a passive film, whose electrical characteristics are described by the parameters Rt and CPE. The fitting parameters are summarized in Table 3. A 10-day (240 h) exposure of carbon steel samples to the base solution with SN led to a great increase in impedance values and a clear appearance of a second capacitive time constant at the low-frequency domain of the phase diagram (Figure 5, curve 4). Curve 4 was modeled by an equivalent circuit consisting of two R-CPE elements and uncompensated R in series (Figure 6[b]). The first in series Rf-CPEf combination should correspond to a passive film adherent to the steel electrode; the second Rt-CPEt is related to the electrochemical properties of the corroding steel electrode. The EIS data in Figure 5 and Table 3 provide information that in the base solution with SN the Rt values increase with the immersion time from 6.5 k cm2 after 0.5 h to 66.9 k cm2 after 240 h. Finally, the co-inhibition of SN and SS inhibitors has been considered. To determine the optimal concentration of inhibitors in the mixture, EIS measurements were carried out after 240 h of exposure to the base solution with the addition of 1 M NaNO2 together with 0.001, 0.01, and 0.1 M Na2SiO3 (Table 3). Although there are some differences in concentrations of inhibitors, all of them correspond well to an equivalent circuit consisting of two R-CPE elements and R in series (Figure 6[b]). As a result of the complexity of the systems, this equivalent circuit only represents a simplified manner to describe the electrochemical interface and fitting results in Figure 5, curves 4 and 5, made by this model. The comparison of the EIS mea-

(a)

(b)
FIGURE 6. Equivalent circuits used for simulation of experimental data.

surements data (Table 3) shows that after 240 h of exposure to the solutions with SN and the mixture of inhibitors SN+SS, the double-layer capacitance, Ct, comprises 63.9 F/cm2 to 97.1 F/cm2, i.e., increases by a factor of 1.5 to 2 as compared to the data obtained after 0.5 h exposure to the solution with one inhibitor SN (Ct = 52.3 F/cm2). Simultaneously Rt values increase from 66.9 k cm2 (in the presence of one inhibitor, NaNO2) to 240.5 k cm2 (in the presence of the mixture of inhibitors), i.e., increase by a factor of 10 to ~37 as compared to the data obtained after 0.5 h exposure in the solution with one inhibitor SN (Rt = 6.5 k cm2). When the electrode exposure to the solution with SN was prolonged from 0.5 h up to 240 h, the IE% increased from 66.2% to 96.7%. In

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TABLE 3 Electrochemical Impedance Spectroscopy Parameters Obtained by Fitting the Bode Plots Shown in Figure 6 with Equivalent Circuits Shown in Figure 7 for the Carbon Steel
Immersion Time (h) 0.5 0.5 0.5 240 240 240 240 R (cm2) 6.5 6.6 4.1 3.5 3.4 3.6 3.7 Cf (F cm2) 192.2 (n=0.97) 116.8 (n=0.96) 85.7 (n=0.87) 107.6 (n=0.84) Rf (kcm2) 3.2 5.2 5.4 2.9 Ct (F cm2) 49 (n=0.79) 49.9 (n=0.77) 52.3 (n=0.77) 77.6 (n=0.86) 63.9 (n=0.87) 66.2 (n=094) 97.1 (n=0.95) Rt (kcm2) 2.2 2.5 6.5 66.9 197.1 240.5 227.4

Solution 0.1 M NaOH + 1 M NaCl 0.1 M NaOH + 1 M NaCl + 0.1 M Na2SiO3 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 103 M Na2SiO3 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 102 M Na2SiO3 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 101 M Na2SiO3

IE% 14 66.2 96.7 98.9 99.1 99

the solution with the SN+SS mixture, the IE% reached 99%. The passive films on the carbon steel after 240 h of immersion in solution with SN (Cf = 192.2 F/cm2) are thinner in comparison with the film formed in the solution with the inhibitor mixture (Cf = 85.7 116.8 F/cm2). Rf values, which denote the resistance of the passive layer, are 2.9 kcm2 to 5.4 kcm2 (Table 3). As the results demonstrate, the inhibition efficiency increases as a result of the synergistic effect of two co-inhibitors. The total impedance values of carbon steel samples increase with the immersion time in the solution with the SS+SN mixture.

X-Ray Photoelectron Spectroscopy Surface Analysis

The composition and thickness of oxide films formed on the carbon steel surface were examined using XPS measurements. Studies were carried out by exposing samples to the base solution with the SN and SN+SS mixture for 10 days and to the base solution with the SN+SS mixture for 1 year. Fe 2p3/2, O 1s, N 1s, and Si 2p peaks were analyzed after surface sputtering with Ar+ ions for an increasing period of time. Fe 2p3/2 and O 1s spectra of the steel sample exposed to the base solution with 1 M NaNO2 for 10 days are presented in Figures 7(a) and 8(a), respectively. It is evident that both spectra are composed of asymmetric peaks. Fe 2p3/2 spectra prior to Ar+ sputtering exhibit a peak at 710.8 eV and a shoulder at 706.5 eV (Figure 7[a]), which may be assigned to Fe3+ and metallic Fe0 (Table 4). With an increase in sputtering

depth, the intensity of a higher binding energy peak decreases while that of a lower binding energy increases. If the position of the latter peak is constant during the whole sputtering time, the peak at 710.8 eV shifts to 709.3 0.1 eV in the depth range between 1 nm and 2 nm and to 708.2 eV for deeper layers. The obtained data indicate that the inner part of the oxide film contains Fe3O4 (corresponding binding energy of Fe, 708.2 eV), while the outer part of the passive film contains FeO (corresponding binding energy of Fe, 709.3 eV) (Table 4). To determine respective binding energies and relative intensities and to quantify the contribution of each chemical species that comprise the spectra, the deconvolution of Fe 2p3/2 and O 1s peaks was performed and some examples of this procedure are presented in Figure 9. The ratio of the Fe oxides to metallic Fe (Feox/Fe0) at each sputtered depth was determined by proportioning the total intensity of Fe oxides to the intensity of metallic Fe, similarly as it was done earlier.39 The obtained results are presented in Figure 10, curve 1. For the sample exposed to the base solution with SN, the variation Feox/Fe0 below 4 nm is relatively constant, suggesting that the oxide film is approximately 4 nm thick. The obtained data on the film thickness are in agreement with the other studies, which indicated that the thickness of oxide film on the surface of mild steel in a 0.1 M NaOH solution does not exceed 6 nm and the presence of chloride ions decreases the thickness by 14%.39-40 The oxygen O 1s spectra of the same samples exhibited a broad peak, with two components at

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FIGURE 7. XPS spectra for Fe 2p3/2 region for different sputtering times after immersion of sample for 10 days in the solution: (a) 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 and (b) 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 0.1 M Na2SiO3.

(a)

(b)

FIGURE 8. XPS spectra for O 1s region for different sputtering times after immersion of sample for 10 days in the solution: (a) 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 and (b) 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 0.1 M Na2SiO3.

~530.0 0.3 eV and ~531.9 0.3 eV, indicating two oxide components O2 and OH, respectively. These assignments do not contradict the data of the Fe spectra (Figure 8[a]), indicating that the inner part of the oxide film contains Fe3O4, while the outer part of the passive film contains FeO.

Results of XPS studies performed with the samples exposed for 10 days to the solution with the inhibitor SN+SS mixture have highlighted several differences in the composition of the surface layer as compared with the samples exposed to solution containing only SN. According to the Feox/Fe0 variations

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TABLE 4 X-Ray Photoelectron Spectroscopy Peak Parameters for Carbon Steel After Immersion for 10 Days in the 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 Solution Without/With 0.1 M Na2SiO3
Sputtering Depth (nm) 0 Without Na2SiO3 Element Fe 2p3/2 Fe 2p3/2 O 1s O 1s Fe 2p3/2 Fe 2p3/2 O 1s O 1s Fe 2p3/2 Fe 2p3/2 O 1s O 1s Fe 2p3/2 Fe 2p3/2 O 1s O 1s Fe 2p3/2 Fe 2p3/2 O 1s O 1s Fe 2p3/2 Fe 2p3/2 O 1s O 1s Fe 2p3/2 Fe 2p3/2 O 1s O 1s Peak Position (eV) 706.5 710.8 529.9 531.5 706.5 709.3 530.1 531.7 706.5 709.2 530.1 531.7 706.5 708.2 529.9 531.7 706.5 708.2 530.0 532.0 706.6 708.2 529.9 531.9 706.6 708.2 529.9 531.9 Assignment Fe FeOOH/Fe2O3 O2 OH Fe0 FeO O2 OH Fe0 FeO O2 OH Fe0 Fe3O4 O2 OH Fe0 Fe3O4 O2 OH Fe0 Fe3O4 O2 OH Fe0 Fe3O4 O2 OH
0

With Na2SiO3 Peak Position (eV) 710.6 530.8 532.6 706.5 709.8 531.6 533.2 706.5 709.5 531.6 533.1 706.5 709.1 531.7 533.0 706.6 708.4 530.6 532.3 706.6 708.4 530.7 532.3 706.5 708.5 530.5 532.5 Assignment FeOOH O2 H2O Fe0 FeO OH SiO2 Fe0 FeO OH SiO2 Fe0 Fe3O4 OH SiO2 Fe0 Fe3O4 O2 OH Fe0 Fe3O4 O2 H2O Fe0 Fe3O4 O2 H2O

10

16

(Figure 10, curve 2), the thickness of this layer was detected to be higher than 8 nm. Fe 2p3/2 and O 1s spectra (Figures 7[b] and 8[b]) reveal that the composition of Fe oxide phase was similar to that obtained in the solution without SS (Table 4), with the exception that Fe0 was not detected in the top of the film. In addition, Si was detected at all the depths of the layer (Table 5). The determined Si 2p binding energies in the compounds were 103.1 eV and 103.5 eV, which corresponds to silicon dioxide (SiO2)/Si. The binding energy values of Fe 2p3/2 imply that the outer oxide film can be formed of FeO (709.3 eV), while the inner film contains Fe3O4 (corresponding binding energy of Fe is 708.4 eV). Inclusions of N compounds were detected in the outer layer of the oxide film, and the quantities of that element also depended on the composition of oxide formation solution. In the passive layer formed on the steel surface exposed to the solution without SS, 2 at% to 1.4 at% N was detected at a depth of 1 nm, while the quantity of nitrogen detected on the surface exposed to the solution containing silicate at the same depth was less, namely, 0.4 at% to 0.6 at% (Table 5). The binding energy values N 1s in the compounds dependent on sputtering depth were determined to be 402.0, 400.6, 399.9, and 398.8 eV; however, we failed to identify the corresponding compounds.

Studies of a steel sample exposed to the solution with a mixture of SN+SS for 1 year have shown that the thickness of the surface layer markedly increases and is >350 nm (Table 6). This layer is too thick to be considered a passive film and should be regarded as a precipitated coating. The quantity of Si at all the depths of the passive layer comprises about 16.5 at% to 19.9 at% and Si is detected mainly in the form of SiO2. In the outer part of the layer (depth: 1 nm) the quantity of Fe detected was minor, ~0.13 at%, while at a depth of 350 nm the quantity of Fe enlarged to 6.5 at%. Nitrogen, unlike the data obtained after 10 days of exposure, was detected up to the depth of 350 nm. Its quantity decreased from ~0.4 at% on the surface to 0.13 at% in the inner part of the oxide layer (Table 6). The outer part of oxide layer formed in such solution was composed mainly of SiO2 compounds, while in the inner part of oxide layer Fe3O4 was detected along with SiO2. In a previous paper,30 a transparent silicate coating was formed on the surface of hot-dip galvanized steel by immersing in SS solution. The authors determined that the silicate coatings mainly are composed of zinc oxides/hydroxides, zinc silicate, and SiO2. It is considered that the coatings may be a kind of network structure with cross-linked SiOSi and SiOZn bonds. It can be assumed that in our case a precipi-

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(a)

(b)

FIGURE 9. Decomposition of peaks for (a) Fe 2p3/2 and (b) O 1s regions for the carbon steel after immersion of sample for 10 days in the 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 solution (1 nm depth).

tated coating of analogous structures, SiOSi and SiOFe, can be formed; however, the structure was not investigated.

CONCLUSIONS
v The inhibition effect of NaNO2, Na2SiO3, and their mixture was evaluated after different immersion times of carbon steel samples in chloride-contaminated solutions, which simulated the pore solution in concrete. Electrochemical test results obtained have shown that the breakdown potential values were more positive and corrosion currents were the lowest ones for the steel electrodes exposed to the solutions containing NaNO2 and the NaNO2 + Na2SiO3 mixture. v EIS measurements have shown that prolongation of steel exposure to solution containing NaNO2 from 0.5 h up to 240 h leads to an approximately tenfold increase in Rt values. After 240 h of exposure to the solution with the NaNO2 + Na2SiO3 mixture, Rt values were about threefold higher as compared to those obtained in the solution containing only one inhibitor, NaNO2. v Analysis of the XPS data obtained shows that in the 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 solution, a passive layer up to 4 nm in thickness is formed after 10 days on the surface of carbon steel. An additional introduction of 0.1 M Na2SiO3 into this solution increased the thickness of the oxide layer to more than 8 nm. At all depths of the oxide layer formed, Si was detected as SiO2. In both cases, Fe was detected in the form of FeO in the outer part and as Fe3O4 in

FIGURE 10. Comparison of the Feox/Fe0 at the selected sputtered depths after immersion of carbon steel sample for 10 days in the solution: (a) 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 and (b) 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 0.1 M Na2SiO3.

the inner part of the oxide layer. When the duration of steel exposure to the solution with the NaNO2 + Na2SiO3 mixture was prolonged up to 1 year, the thickness of the passive layer increased markedly and was >350 nm. The outer part of the oxide layer formed

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TABLE 5 Data of X-Ray Photoelectron Spectroscopy Depth Analysis of the Passive Layer, Which was Formed on the Carbon Steel Surface After 10 Days Exposure to the 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 Solution Without/With 0.1 M Na2SiO3
Sputtering Depth (nm) 0 1 2 4 6 10 16 Without Na2SiO3 Fe (at%) 10.4 27.9 34.3 51.5 61.2 67.5 76.9 O (at%) 48.1 58.1 56.9 39.5 31 23 16.6 N (at%) 2 1.3 Fe (at%) 0.39 3.1 5.2 10 25.8 50.2 77.6 With Na2SiO3 O (at%) 52.5 63.5 68.8 69 58.9 37.9 13.7 N (at%) 0.55 0.39 Si (at%) 6.9 11.4 11.2 10.6 6.2 4.1

TABLE 6 Data of X-Ray Photoelectron Spectroscopy Depth Analysis of the Passive Layer, Which was Formed on the Carbon Steel Surface After 1 Year Exposure to the 0.1 M NaOH + 1 M NaCl + 1 M NaNO2 + 0.1 M Na2SiO3 Solution
Sputtering Depth (nm) 0 50 150 250 350

Fe (at%) 0.13 0.6 0.9 6.5

O (at%) 77.2 79.2 77.4 74.8 71.1

Si (at%) 18.7 19.9 19.9 19.9 16.5

N (at%) 0.51 0.39 0.32 0.36 0.13

in such solution is composed mainly of the SiO2 compound, while in the inner part of the oxide layer, Fe3O4 was detected along with SiO2. v To summarize the results of electrochemical and XPS measurements, the mixture of NaNO2 + Na2SiO3 inhibitors ensured the most pronounced inhibition of the carbon steel corrosion in the investigated solution 0.1 M NaOH + 1 M NaCl. The inhibition efficiency increases as the result of the synergistic effect of two co-inhibitors.

ACKNOWLEDGMENTS
This research was supported by the Research Council of Lithuania under Grant no. MIP 77/2010. The authors thank A. Sudavi ius (Institute of Chemc istry, Vilnius, Lithuania) for his assistance performing XPS measurements.
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