On the fundamentals of electrochemical corrosion of X65 steel in CO2-containing formation water in the presence of acetic acid in petroleum production

Electrochemical corrosion behavior of X65 steel in CO₂-containing oilfield formation water in the presence of acetic acid (HAc) was investigated by various electrochemical measurements and analyses as well as thermodynamic calculations of ionic concentrations, reaction rate constants and equilibrium electrode potentials. A conceptual model was developed to illustrate corrosion processes of steel in oilfield formation water system. The anodic reactions of the steel contain a direct dissolution of Fe, Fe → Fe²⁺ + 2e, and the formation of corrosion scale, FeCO₃, by Fe + → FeCO₃ + H⁺ + 2e. The cathodic processes contain the reduction of H⁺, , H₂O and HAc, where reduction of HAc has the least negative equilibrium potential and thus dominates the cathodic process. With addition of HAc in the solution, both cathodic and anodic reaction rates increase remarkably. It is attributed to the fact that HAc inhibits or degrades the formation of protective scales due to the decrease of solution pH. Upon electrode rotation, the measured impedance decreases with the increase in HAc concentration. The FeCO₃ scale will not form on electrode surface. When HAc concentration is less than 1000 ppm, the adsorbed intermediate product is not significant, resulting in generation of a low-frequency inductive loop in EIS plots. When HAc concentration is more than 3000 ppm, the adsorption of intermediate product is significant, generating overlapped capacitive semicircles in EIS measurements.     

Characterization of steel corrosion in mortar by various electrochemical and physical techniques

In the study characterization of steel corrosion in concrete at the macro- and micro-level was performed. Physical (electrical-resistance probes) and electrochemical techniques (coupled multi-electrode arrays) were implemented in order to upgrade the general information that conventional electrochemical techniques can provide. Measurements were performed in mortar exposed to periodic wetting and drying. Steel corrosion damage was assessed by micro X-ray computer tomography (CT) and SEM. The results were compared and interpreted. By combined use of micro-CT and electrochemical methods, new insights into the corrosion mechanisms of steel in concrete were obtained.     

Electrochemical corrosion of X65 pipe steel in oil/water emulsion

The electrochemical corrosion behavior of X65 pipeline steel in the simulated oil/water emulsion was investigated under controlled hydrodynamic and electrochemical conditions by rotating disk electrode technique. Results demonstrated that mass-transfer of oxygen plays a significant role in the cathodic process of steel in both oil-free and oil-containing solutions. Electrode rotation accelerates the oxygen diffusion and thus the cathodic reduction. The higher limiting diffusive current density measured in oil-containing solution is due to the elevated solubility of oxygen in oil/water emulsion. The anodic current density decreases with the increase of electrode rotating speed, which is attributed to the accelerated oxygen diffusion and reduction, enhancing the steel oxidation. Addition of oil decreases the anodic dissolution of steel due to the formation of a layer of oily phase on steel surface, increasing the reaction activation energy. The steel electrode becomes more active at the elevated temperature, indicating that the enhanced formation of oxide scale is not sufficiently enough to offset the effect resulting from the enhanced anodic dissolution reaction kinetics. The corrosion reaction mechanism is changed upon oil addition, and the interfacial reaction is activation-controlled, rather than mass-transfer controlled. When sand particles are added in oil/water emulsion, there is a significant increase of corrosion of the steel. The presence of sands in the flowing slurry would impact and damage the oxide film and oily film formed on the steel surface, exposing the bare steel to the corrosive solution.     

Micro-electrochemical characterization of corrosion of pre-cracked X70 pipeline steel in a concentrated carbonate/bicarbonate solution

The electrochemical corrosion behavior of a stressed, pre-cracked X70 pipeline steel was studied in a bicarbonate/carbonate solution by electrochemical and micro-electrochemical measurements, numerical calculation and surface analysis technique. The effects of stress and potential on passivity, corrosion and electrochemical behavior of the steel at crack-tip were mechanistically determined. It was found that the passive film formed at crack-tip was less stable than that formed in the region ahead of the crack. Moreover, the crack-tip is more susceptible to pitting corrosion than other region of the specimen. The applied stress enhances the anodic dissolution of the steel. In particular, the stress concentration at crack-tip further increases the local anodic dissolution rate. The enhancement of the anodic dissolution of the steel at crack-tip is also resulted from the formation of a galvanic couple, i.e., the crack-tip as an anode and the surrounding region as a cathode.     

The inhibition activity of ascorbic acid towards corrosion of steel in alkaline media containing chloride ions

The activity of ascorbic acid towards steel corrosion in saturated Ca(OH)₂ solution containing chloride ions was investigated in this study. Concentration and time dependence of the protective properties of the passive film were acquired by electrochemical impedance spectroscopy. The best inhibitive performance, i.e. the longest pitting initiation time was obtained in the presence of 10⁻³ M ascorbic acid, while both lower and higher concentrations showed shortening of the pitting-free period. The overall behaviour of ascorbic acid was attributed to its ability to form chelates of various solubility having various metal/ligand ratios and oxidation states of the chelated iron. The assumption of ascorbic acid assisted reductive dissolution of the passive layer at higher inhibitor concentrations was confirmed by cyclic voltammetry and ATR FTIR spectroscopy. It is proposed that the overall inhibitive effect at lower concentrations is due to the formation of insoluble surface chelates and the effective blocking of the Cl⁻ adsorption at the surface of passive film. A pronounced inhibitive effect observed after the pitting had initiated was ascribed to the formation of a resistive film at the pitted area.     

The role of some thiosemicarbazide derivatives as corrosion inhibitors for C-steel in acidic media

Corrosion inhibition of C-steel in 2 M HCl was investigated in the absence and presence of different concentrations of some thiosemicarbazide derivatives namely, 1-ethyl-4(2,4-dinitrophenyl) thiosemicarbazide (I), 1,4-diphenylthiosemicarbazide (II), 1-ethyl-4-phenylthiosemicarbazide (III). Weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy techniques were employed. Impedance measurements showed that the double-layer capacitance decreased and charge-transfer resistance increased with increase in the inhibitors concentration and hence increasing in inhibition efficiency. Potentiodynamic polarization study showed that all the inhibitors act as mixed-type inhibitors. Results obtained reveal that the inhibition efficiency (%IE) follows the sequence: I > II > III. The adsorption of these compounds on C-steel surface obeys Temkin’s adsorption isotherm and has a chemisorptions mechanism.     

Experimental and theoretical studies of thiazoles as corrosion inhibitors for mild steel in sulphuric acid solution

The inhibition effects of 2-amino-5-mercapto-1,3,4-thiadiazole (2A5MT) and 2-mercaptothiazoline (2MT) on mild steel corrosion in 1.0 M H₂SO₄ were studied with potentiodynamic polarization, linear polarization resistance and electrochemical impedance spectroscopy techniques. It was shown that both 2A5MT and 2MT act as good corrosion inhibitors for mild steel protection. The high inhibition efficiencies were attributed to the simple blocking effect by adsorption of inhibitor molecules on the steel surface. The effects of the presence of extra NH₂ group and N atom in 2A5MT on the ability to act as corrosion inhibitors were investigated by theoretical calculations.     

The importance of live biofilms in corrosion protection

As observed before, Al 2024 was passive in artificial seawater (AS) in the presence of a protective biofilm of Bacillus subtilis WB600. When antibiotics were added to the AS to kill the bacteria in the biofilm, pitting occurred within a few hours as indicated by characteristic changes in the impedance spectra. The corrosion potential E_corr decreased at the same time to values observed in sterile AS. Addition of the antibiotics to sterile AS had no effect on corrosion behavior.     

N-Phenylcinnamimide and some of its derivatives as inhibitors for corrosion of lead in HCl solutions

The anodic and cathodic polarization behavior of lead electrode was studied galvanostatically in HCl solutions of various concentrations. Increasing the acid concentration enhances the rate of the anodic dissolution of the metal and the rate of hydrogen evolution reaction, with anodic and cathodic Tafel slopes equal to 30 and 115 ± 5 mV decade⁻¹, respectively. The effect of addition of N-phenylcinnamimide and some of its derivatives, N-(p-nitrophenyl)cinnamimide, N-(p-methylphenyl)cinnamimide, and N-(p-methoxyphenyl)cinnamimide, as inhibitors on the kinetic of the anodic and cathodic reactions of lead in 0.1 M HCl solutions was also studied. These compounds inhibit both the rate of anodic dissolution and the rate of hydrogen evolution reactions without affecting the Tafel slopes. This result indicates that the used compounds were of mixed-type. The inhibition efficiency of these additives increases in the order: N-(p-nitrophenyl)cinnamimide < N-phenylcinnamimide < N-(p-methylphenyl)cinnamimide < N-(p-methoxyphenyl)cinnamimide. The equilibrium constant and the free energy of adsorption process have been calculated and discussed.     

Localized corrosion behaviour of reinforcement steel in simulated concrete pore solution

The correlation of localized corrosion behavior and microstructure of reinforcement steel in simulated concrete pore solutions was investigated. The SEM/EDS analysis showed that most of ferrite, minor amount of pearlite and some MnS inclusions existed on the steel surface. The SKPFM results indicated a higher corrosion tendency at the ferrite grain boundaries, pearlite grains and MnS inclusions. The EIS and electrochemical polarization measurements demonstrated the influence of pH and chloride concentration on the corrosion behavior. In situ optical observations and AFM images revealed a detail of the localized corrosion behavior, which was in good agreement with the results from the other measurements.     

Employing electrochemical frequency modulation for pitting corrosion

By using the electrochemical frequency modulation (EFM) technique, the non-linear behavior of a corroding system is measured. This non-linear behavior is likely to be different for a system undergoing uniform or pitting corrosion. The implementation of the EFM technique to detect pitting corrosion has been investigated by observing the fluctuations in the so-called causality factors. These causality factors, resulting from an EFM test and in the ideal case having values of 2 and 3, respectively, are normally used for quality and data validation purposes. While investigating pitting corrosion, they show different behavior leading to the CPT (critical pitting temperature) detection.     

Pitting corrosion in low carbon steel influenced by remanent magnetization

A new type of experiment is performed using a closed magnetic circuit configuration in order to study the influence of the magnetic field on pitting corrosion in low carbon pipeline steel. The statistical assessment of the pitting corrosion data shows that the magnetic field in the material under test reduces the extreme pit depths and also the average depth of the pit population. It is proposed that reduction in pit depth under the influence of remanent magnetization can be explained based on the behavior of the paramagnetic corrosion products under the influence of the magnetic field gradient produced inside pits.     

Comparative study on the corrosion behavior of milled and unmilled magnesium by electrochemical impedance spectroscopy

The corrosion behavior of milled Mg prepared by high-energy ball milling for 10 h has been investigated in alkaline solutions by electrochemical impedance spectroscopy and compared with that of unmilled Mg. X-ray powder diffraction indicates a crystallite size of 34 nm for the milled Mg compared to >100 nm for the unmilled powder. Chemical analyses show no significant iron contamination in milled Mg powder, indicating the absence of tools erosion during the milling procedure. In contrast, significant MgO enrichment in the milled powder is observed (6.5 wt.% after 10 h milling compared to 1.0 wt.% before milling). The oxygen contamination is mainly attributed to the powder oxidation occurring during milling. From XPS analyses, no MgO enrichment is detected on milled Mg electrode surface, confirming that MgO is dispersed homogeneously in the bulk of the material rather than to segregate on its surface. Electrochemical impedance spectroscopy demonstrates clearly the better corrosion resistance of milled Mg compared to unmilled Mg in passive conditions (KOH solution, pH=14) and in more active corrosion conditions (borate solution, pH=8.4). This is illustrated by a nobler corrosion potential and by a significant increase of the interfacial resistance related to the film and charge-transfer reaction. Moreover, the variation of the different electrochemical parameters (corrosion potential, interfacial resistance and capacitance) with immersion time is less accentuated and tends more rapidly to a steady state with milled Mg, suggesting an enhancement of the Mg(OH)₂ formation kinetic. The origin of the distinctive passivation behavior of ball-milled Mg is discussed.     

Mechanism of corrosion of cast iron covered by aged corrosion products: Application of electrochemical impedance spectrometry

This work focuses on the corrosion of cast iron in a drinking water network. The study is performed in water and in a sandy soil saturated with the same water. In the presence of corrosion products, the inner wall surface shows a lower corrosion rate than the external wall. In the two media, impedance diagrams are described by a high-frequency loop characteristic of a protective corrosion layer and a diffusion impedance loop at low frequencies associated with oxygen diffusion. Different models involving mass transfer through a porous layer are suggested for the inner and the external corrosion layers.     

Numerical simulation of a single corrosion pit in CO2 and acetic acid environments

The present paper bears on a numerical model of steady-state behaviour of a single corrosion pit in CO₂-containing media in the presence of acetic acid. The kinetics of electrochemical reactions occurring on the electrode surface is described by Tafel equations fitted to experimental data obtained on API 5L X65 pipeline steel. Simulation results provide an interesting insight into both the chemistry and electrochemistry inside the active pit. Particular attention is paid to the effect of HAc on the coupling behaviour between the attack base and the outer surrounding surface and to the comparison with experimental data obtained in similar conditions.     

Quantum chemical study of some cyclic nitrogen compounds as corrosion inhibitors of steel in NaCl media

Corrosion inhibition efficiencies of 3-amino-1,2,4-triazole (3-ATA), 2-amino-1,3,4-thiadiazole (2-ATDA), 5-(p-tolyl)-1,3,4-triazole (TTA), 3-amino-5-methylmercapto-1,2,4-triazole (3-AMTA) and 2-aminobenzimidazole (2-ABA) as corrosion inhibitors on steel in sodium chloride media were investigated by using semiempirical PM3 and density functional theory (DFT) methods. Quantum chemical parameters such as highest occupied molecular orbital energy (E_HOMO), lowest unoccupied molecular orbital energy (E_LUMO), energy gap (ΔE) and dipole moment (μ) have been calculated for these compounds by using semiempirical PM3 and 6-31G(d), 6-311G(d,p) DFT methods. It was found that theoretical data support the experimental results.     

Corrosion of the component phases presents in high copper dental amalgams. Application of electrochemical impedance spectroscopy and electrochemical noise analysis

The corrosion resistance of three of the constituent phases in high copper dental amalgams has been investigated by electrochemical methods in 0.9% NaCl solution. Polarization curves show corrosion potentials most positive for γ₁-Ag₂Hg₃, followed by Ag-Cu, and γ-Ag₃Sn in agreement with the order of corrosion resistance deduced from the corrosion currents. Complex plane impedance plots at the open circuit potential showed distorted semicircles with diffusional components at low frequency for Ag-Hg and Ag-Cu, while for γ-Ag₃Sn a layer of corrosion products is formed, partially or completely covering the surface of the electrode. Impedance and noise spectra have been compared in the frequency domain, and show good agreement.     

Inhibition effect of chromate on the passivation and pitting corrosion of a duplex stainless steel in LiBr solutions using electrochemical techniques

The electrochemical behavior of duplex stainless steel (DSS) in LiBr media was investigated by anodic cyclic polarization curves and AC impedance measurements. The effect of bromide concentration and the presence of chromate in the solutions on the corrosion behavior of AISI 2205 was studied. Cyclic polarization curve analyses showed that there was different pitting susceptibility of passive films depending on the LiBr concentration. Pitting potential decreases with LiBr concentration in a semilogarithmic scale following two different slopes. Chromate presence displaces pitting potentials towards more positive values at low LiBr concentrations but it has no effect when LiBr concentration increases.The comparative analysis carried out in LiBr and LiBr chromate-containing solutions at two different concentrations, 0.016 M and 0.032 M, verifies the assumption that halogen ions facilitate inhibitor adsorption. The addition of halides strongly increased the inhibition efficiency of chromate. The passive film becomes more resistant when bromide concentration increases, although film thickness decreases.     

Electrochemical quartz crystal microbalance and electrochemical impedance spectroscopy study of copper corrosion inhibition by imidazoles

The aim of this work is to obtain deeper insight into the mechanism of the protective action of three imidazole-based corrosion inhibitors. Investigations were performed on copper in 3% NaCl, by electrochemical impedance spectroscopy and electrochemical quartz crystal microbalance measurements. The kinetic changes in the corrosion processes were monitored over time. In spite of similar molecular structure, differences in the inhibiting mechanism of three imidazole compounds were observed. The two inhibitors with a tolyl substituent decreased the copper corrosion rate due to the formation of a thin adsorbate layer; however, slow formation of a thick layer was observed for 4-methyl-1-phenyl imidazole. From electrochemical impedance spectroscopy studies, it was observed that all three inhibitors protected the copper efficiently, and in some cases, the degree of the protection increased with time.