Hydrogen evolution in aqueous solutions containing dissolved CO2: Quantitative contribution of the buffering effect

The hydrogen evolution reaction (HER) occurring on steel in an oxygen-free aqueous solution containing dissolved CO₂ was investigated. This reaction was modelled by taking into account the two dissociation reactions of dissolved CO₂. The mathematical problem was solved numerically using a finite element method (FEM). A fair agreement between the measurements performed on a steel rotating disc electrode and the theoretical calculations was obtained. Thus, the cathodic behaviour of steel in CO₂-containing solutions can be fully explained by the buffering effect induced by the presence of CO₂. Some interfacial pH measurements performed on a gold electrode also support this conclusion.     

Effect of CO2 and R-ratio on near-neutral pH stress corrosion cracking initiation under a disbonded coating of pipeline steel

This study investigates the role of CO₂ and cyclic stress R-ratio (R = minimum stress/maximum stress) on near-neutral pH SCC initiation mechanism(s) under a disbonded coating of pipeline steel protected by cathodic protection (CP). It was found that depending on CO₂ concentration and level of CP, different localized environments with various pH could be formed under the disbonded coating. When cyclic loading was applied, different SCC initiation mechanisms were involved depending on the pH of the localized environments. Reducing the R-ratio had different effects on the initiation mechanisms.     

Corrosion of N80 carbon steel in oil field formation water containing CO2 in the absence and presence of acetic acid

Corrosion behaviour of N80 carbon steel in formation water containing CO₂ was studied by polarization curve technique, electrochemical impedance spectroscopy, weight loss test, scanning electron microscope, and X-ray diffraction. Effects of temperature and acetic acid concentration on the corrosion behaviour of N80 carbon steel were discussed. The results showed that increasing temperature not only enhanced the dissolution of steel substrate, but also promoted the precipitation of FeCO₃, the addition of acetic acid enhanced localized corrosion attack on N80 carbon steel. FeCO₃ was the main corrosion product. And there was a transition region between CO₂ corrosion control and HAc corrosion control.     

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.     

Corrosion of X65 steel in CO2-saturated oilfield formation water in the absence and presence of acetic acid

Electrochemical corrosion behavior of X65 steel in CO₂-saturated formation water in the absence and presence of acetic acid was studied by electrochemical measurements, scanning vibrating micro-electrode (SVME), localized electrochemical impedance spectroscope (LEIS) and surface analysis techniques. It is found that, when steel is immersed in formation water, the dissolution of Fe dominates the anodic process and the steel is in active dissolution state. Adsorption of intermediate product on the electrode surface results in generation of an inductive loop in the low frequency range of EIS plot. As corrosion proceeds, the concentration of Fe²⁺ in the solution increases. When the product of [Fe²⁺] × [] exceeds solubility product of FeCO₃, FeCO₃ will deposit on the electrode surface, and protects the steel substrate from further corrosion. The steel is in a “passive” state. When the electrode surface is completely covered with FeCO₃ film, the inductive loop in the low frequency range disappears. In the presence of acetic acid in formation water, the cathodic reaction will be enhanced due to the direct reduction of undissociated acetic acid. Addition of acetic acid degrades the protectiveness of corrosion scale, and thus, enhances corrosion of steel by decreasing the FeCO₃ supersaturation in solution.     

Electrochemical characterization and computational fluid dynamics simulation of flow-accelerated corrosion of X65 steel in a CO2-saturated oilfield formation water

The flow-accelerated corrosion (FAC) of an X65 pipeline steel was investigated in a CO₂-saturated formation water by electrochemical measurements and computational fluid dynamics (CFD) simulation on micro-electrodes installed on an impingement jet system. The surface morphology of the electrodes after corrosion test was characterized by scanning electron microscopy. Results demonstrated that the role of fluid hydrodynamics in FAC of the steel depends on its effect on the carbonate corrosion scale formed on the electrode surface. An increasing flow velocity and shear stress would thinner, degrade or even remove completely the scale, increasing corrosion of the steel. An oblique impact of fluid would generally result in a high corrosion rate of the steel. The effect of impact angle on corrosion of the steel is attributed to the distribution of fluid flow field and shear stress on the electrode surface. At the normal impact, a low flow velocity and shear stress and thus a low mass transfer rate would be generated at the centric region. Consequently, a compact corrosion scale can be formed on the electrode surface to protect the steel from corrosion. The highest corrosion rate is observed on micro-electrodes that are adjacent to the center, with the highest flow velocity and shear stress. At the oblique impact angles, the fluid flow velocity and shear stress, and the corrosion rate of the micro-electrodes are higher at the side far away from the nozzle than those at the side close to nozzle. The corrosion activity of the steel electrode located at the center of the sample holder generally increases with the decreasing impact angle due to the enhancing shear effect on the corrosion scale.     

New insight into the pit-to-crack transition from finite element analysis of the stress and strain distribution around a corrosion pit

A finite element (FE) analysis has been undertaken to evaluate the stress and strain distribution associated with a single corrosion pit in a cylindrical steel specimen stressed remotely in tension. A key observation was the localisation of plastic strain to the pit walls (just below the surface of the specimen). Simulation of a growing pit in a static stress field indicated corresponding plastic strain rates that were commensurate with values associated with stress corrosion cracking. This observation introduces a wholly new concept in understanding of the evolution of stress corrosion cracks from pits and correlates with recent X-ray tomography measurements.     

Hydrodynamic measurement of a single corrosion pit

The hydrodynamics of gas evolution plays an important role in the pitting corrosion of metals. A new technique for the measurement of the local hydrodynamics caused by corrosion processes, using the atomic force microscope, has been presented in this work. The hydrodynamics of hydrogen evolution on Al surface due to pitting corrosion was studied. The characteristic features of the hydrodynamics are discussed. To the best of our knowledge this is the first local measurement of pitting corrosion hydrodynamics.     

The growth mechanism of CO2 corrosion product films

Carbon steel usually has high corrosion rate in water with dissolved CO₂ however the steel surface can be covered by protective corrosion product film. Therefore the carbon steel can be widely used in oil and gas industry. This paper discusses the structure, electrochemistry performances, initiation and growth of protective corrosion product films. A duplex layer structure of FeCO₃ films was found by electrochemical impedance spectrum (EIS). The physical and chemical situations of solution near carbon steel surface were investigated by ultraviolet spectrophotometry and chronopotentiometry. According to crystallography the growth mechanisms of protective CO₂ corrosion product films were discussed.     

A generic statistical methodology to predict the maximum pit depth of a localized corrosion process

This paper outlines a new methodology to predict accurately the maximum pit depth related to a localized corrosion process. It combines two statistical methods: the Generalized Lambda Distribution (GLD), to determine a model of distribution fitting with the experimental frequency distribution of depths, and the Computer Based Bootstrap Method (CBBM), to generate simulated distributions equivalent to the experimental one. In comparison with conventionally established statistical methods that are restricted to the use of inferred distributions constrained by specific mathematical assumptions, the major advantage of the methodology presented in this paper is that both the GLD and the CBBM enable a statistical treatment of the experimental data without making any preconceived choice neither on the unknown theoretical parent underlying distribution of pit depth which characterizes the global corrosion phenomenon nor on the unknown associated theoretical extreme value distribution which characterizes the deepest pits.Considering an experimental distribution of depths of pits produced on an aluminium sample, estimations of maximum pit depth using a GLD model are compared to similar estimations based on usual Gumbel and Generalized Extreme Value (GEV) methods proposed in the corrosion engineering literature. The GLD approach is shown having smaller bias and dispersion in the estimation of the maximum pit depth than the Gumbel approach both for its realization and mean. This leads to comparing the GLD approach to the GEV one. The former is shown to be relevant and its advantages are discussed compared to previous methods.     

The effect of electrolyte flow on the performance of 12-aminododecanoic acid as a carbon steel corrosion inhibitor in CO2-saturated hydrochloric acid

The effect of flow and flow pattern of CO₂-saturated HCl on the corrosion inhibition of carbon steel (CS) by 12-aminododecanoic acid (AA) was investigated in a square duct, rotating disk electrode (RDE), and jet impingement cell configuration. 3 mM AA provided high corrosion inhibition efficiency in the square duct and RDE configuration. However, in 1 mM AA the inhibition efficiency decreased with an increase in Re, due to desorption of AA from the CS surface. AA was found to poorly protect CS in the impingement-jet configuration at low Re, while at high Re, acceleration of CS corrosion was recorded.     

Mechanical properties of CO2 corrosion product scales and their relationship to corrosion rates

In order to evaluate the protective ability of CO₂ corrosion scale to steel under flow conditions at various CO₂ partial pressures, the mechanical properties of the scale, i.e., Young′s modulus, fracture toughness, interfacial fracture toughness and adhesion strength between the scale and steel were determined by nano-indentation, Vickers’ indentation and tensile test. The influences of flow rate and CO₂ partial pressure on these mechanical properties as well as the correlations between the properties and corrosion rates were investigated. The interfacial fracture toughness between the scale and steel can evaluate the protective ability of the scale to steel effectively.     

Experimental and theoretical calculations on corrosion inhibition of steel in 1 M H2SO4 by crown type polyethers

The corrosion inhibitive efficiencies of two crown type polyethers, namely dibenzo-bis-imino crown ether (C-1) and dibenzo-diaza crown ether (C-2), which are macrocyclic Schiff base and its reduced form (macrocyclic amine), respectively, for the steel in 1 M H₂SO₄ have been investigated by Tafel extrapolation and linear polarization methods. Corrosion and adsorption isotherm parameters were determined from current-potential curves. The studies show that C-1 and C-2 inhibit the corrosion of the steel in H₂SO₄ solution. Semiempirical AM1 method was used for theoretical calculations. The obtained results of these calculations for the compounds were found to be consistent with the experimental findings.     

A study of 4-carboxyphenylboronic acid as a corrosion inhibitor for steel in carbon dioxide containing environments

4-Carboxyphenylboronic acid (CPBA) has been found to be an efficient carbon dioxide (CO₂) corrosion inhibitor for steel in aqueous media. The results indicate that the addition of CPBA to CO₂ containing sodium chloride solutions at a low concentration is able to retard corrosion anodic reactions, reduce corrosion current densities, increase charge transfer and total resistances, resulting in more uniform and smoother steel surfaces. These effects are attributed to the formation of a barrier layer on steel surface, which provides metal surface protection. The inhibitor was also found to mitigate corrosion by promoting random distribution of minor anodes.     

A numerical study of damage caused by combined pitting corrosion and axial stress in steel pipes

Localized pipe wall damage accounts for many failures. Numerical modelling of pipes under increasing axial load and constant internal pressure when there is corrosion pits on the exterior surface of the pipe is reported herein. It is shown that for the assumed ideal elastic–plastic material the shape and volume of the plastic field depend on pit depth and its geometry. Pipe wall fracture around a pit can be associated with a critical plastic section. The results reported herein should be relevant for estimating of the risk of perforation and of loss of contents for steel pipes under different loading.     

Copper corrosion inhibition in O2-saturated H2SO4 solutions

Corrosion inhibition of copper in O₂-saturated 0.50 M H₂SO₄ solutions by four selected amino acids, namely glycine (Gly), alanine (Ala), valine (Val), or tyrosine (Tyr), was studied using Tafel polarization, linear polarization, impedance, and electrochemical frequency modulation (EFM) at 30 °C. Protection efficiencies of almost 98% and 91% were obtained with 50 mM Tyr and Gly, respectively. On the other hand, Ala and Val reached only about 75%. Corrosion rates determined by the Tafel extrapolation method were in good agreement with those obtained by EFM and an independent chemical (i.e., non-electrochemical) method. The chemical method of confirmation of the corrosion rates involved determination of the dissolved Cu²⁺, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of chemical analysis. Nyquist plots exhibited a high frequency depressed semicircle followed by a straight line portion (Warburg diffusion tail) in the low-frequency region. The impedance data were interpreted according to two suitable equivalent circuits. The kinetics of dissolved O₂ reduction and hydrogen evolution reactions on copper surface were also studied in O₂-saturated 0.50 M H₂SO₄ solutions using polarization measurements combined with the rotating disc electrode (RDE). The Koutecky-Levich plot indicated that the dissolved O₂ reduction at the copper electrode was an apparent 4-electron process.     

Use of a 3D optical measurement technique for stochastic corrosion pattern analysis of reinforcing bars subjected to accelerated corrosion

The 3D corrosion patterns of 23 reinforcing bars subjected to accelerated corrosion are characterised using an optical surface measurement technique. A stochastic signal processing methodology is employed for corrosion pattern analysis of the measured data. The statistical analysis of corrosion pattern data shows that a lognormal distribution model can represent the non-uniform distribution of pitted sections along the corroded bars. It was observed that the frequency of corrosion is independent from the mass loss ratio and the length of the bars. Finally, a set of probabilistic distribution models for the geometrical properties of corroded bars is developed.     

Numerical simulation of corrosion process with two-step charge transfer mechanism in the Cu/CuSO4 + H2SO4 system

The corrosion process in the Cu/CuSO₄ + H₂SO₄ system is considered as the sum of two coupled single-electron electrochemical reactions that occur simultaneously and independently on the surface of the copper electrode. Our numerical model incorporates diffusion and migration of solution species including cuprous ions, as well as the chemical equilibria for copper sulphate and sulphuric acid dissociation. Numerical simulations are compared with the trends discovered during experimental investigation of copper corrosion in similar systems.     

Initial NaCl-particle induced atmospheric corrosion of zinc—Effect of CO2 and SO2

Initial corrosion and secondary spreading effects during NaCl particle induced corrosion on zinc was explored using in situ and ex situ FTIR microspectroscopy, optical microscopy, and SEM/EDAX. The secondary spreading effect which occurs upon introduction of humid air on NaCl deposited zinc surfaces was strongly dependent on the CO₂ and SO₂ content of the introduced air. Ambient level of CO₂ (350 ppm) resulted in a relatively low spreading effect, whereas the lower level of CO₂ (<5 ppm) caused a much faster spreading over a larger area. In the presence of SO₂, the secondary spreading effect was absent which could limit the cathodic process in this case. At <5 ppm CO₂, the corrosion is more localized, with the formation of simonkolleite (Zn₅(OH)₈Cl₂ · H₂O), zincite (ZnO) and sodium carbonate (Na₂CO₃), and a larger effective cathodic area. At 350 ppm CO₂, the corrosion is more general and formation of simonkolleite, hydrozincite (Zn₅(OH)₆(CO₃)₂) and sodium carbonate was observed. Sodium carbonate was mainly formed in more alkaline areas, in the inner edge of the electrolyte droplet and in the secondary spreading area. Oxidation of sulphur and concomitant sulphate formation was enhanced in the presence of NaCl particles, due to the formation of a droplet, the separation of the anodic and cathodic areas and the accompanying differences in chemical composition and pH in the surface electrolyte.     

Impact of oxyfuel atmospheres H2O/CO2/O2 and H2O/CO2 on the oxidation of ferritic–martensitic and austenitic steels

In future power plant technologies, oxyfuel, steels are subjected to steam rich and carbon dioxide rich combustion gases. The effect of simulated combustion gases H₂O/CO₂/O₂ (30/69/1 mol%) and H₂O/CO₂ (30/70 mol%) on the corrosion behavior of low alloyed steels, 9–12% chromium steels and an austenitic steel were studied. It was discovered that the formation of protective chromium rich oxides is hampered due to the carburization of the base material and the formation of chromium rich carbides. The kinetics of corrosion and carburization are quantified. The effect of temperature and the effect of gas pressure are analyzed statistically.