Microbially influenced corrosion of stainless steel by manganese oxidizing microorganisms

Based on the corrosion behaviour of stainless steels in fresh water and on the electrochemical properties of higher manganese oxides, the mechanism “Microbially influenced corrosion by manganese oxidizing microorganisms” (MIC by MOMOs) is presented as the consequence of biomineralized manganese oxides in contact with the metal. Localized corrosion may develop at elevated but normally undercritical chloride concentration in the water. The mechanism was found useful in the analysis of certain cases of unexpected failure of stainless steel in fresh water.     

Further studies on the anaerobic corrosion of carbon steel in alkaline media in support of the Belgian supercontainer concept

In the Belgian supercontainer concept, a carbon steel overpack surrounds high-level radioactive waste and spent fuel containers and is encased in a cementitious buffer material. Research has been carried out to characterise the anaerobic corrosion of carbon steel in an anoxic artificial alkaline porewater that simulates the cementitious buffer material and also in solid cement matrices, in the presence of chloride and the sulphur species expected in the groundwater. The current study focuses on recent results. Specifically, it provides an update on the long-term corrosion rates obtained from gas generation measurements (including new data from higher-sensitivity autoclaves) and weight loss measurements and provides results of postmortem analysis of dismantled cells. The behaviour of the system is discussed, focusing on the effects of the solution chemistry, precorrosion treatments and γ radiation on corrosion rates, the electrochemical response of the steel when irradiated, and the morphology of the corrosion product. The corrosion rate was lower in cement than in an aqueous system. Radiation affected the corrosion potential and the morphology of the corrosion product.     

Development of microbially influenced corrosion on carbon steel in a simulated water injection system

Microbially influenced corrosion (MIC) on internal pipeline surfaces has become a severe problem during the water injection process in secondary oil recovery. The formation of a biofilm, normally dominated by sulfate‐reducing bacteria (SRB), is believed to be the critical step of the MIC process. A continuously fed biofilm simulating the water injection process was operated to investigate the influence of biofilm development on MIC behavior in the early phase of corrosion development. The development of the corrosion product film and biofilm was monitored for 5 months with electrochemical impedance spectroscopy, linear polarization resistance, scanning electron microscopy, 3D optical profiling, and direct weight measurement. MIC development was found to comprise three phases: initialization, transition, and stabilization. The initialization phase involved the formation of the corrosion product layer and the initial attachment of the sessile microbes on metal surface. In the transition phase, the MIC process gradually shifted from charge‐transfer‐controlled reaction to diffusion‐controlled reaction. The stabilization phase featured mature and compact biofilm on the metal surface, and the general corrosion rate (CR) decreased due to the diffusional effect, while the pitting CR was enhanced at a lower carbon source level, which supported the mechanism of direct electron uptake from the metal surface by SRB.     

Prediction of corrosion products of iron at a low-level radioactive waste disposal facility in Japan

Estimation of the volumetric expansion ratio due to the corrosion of metals is an essential part of the safety assessment of low-level radioactive waste disposal facilities in Japan, because such volumetric expansion can disrupt the barrier function of these facilities. In the present study, the corrosion products of iron were predicted from potential–pH diagrams and the results of a synthesis test, and the volumetric expansion ratios of the corrosion products were evaluated. Under a basic set of conditions expected at a disposal facility over a storage period of a thousand to tens of thousands of years, Fe₃O₄, Fe₂O₃, and FeOOH were predicted as the major stable corrosion products of iron. The maximum volumetric expansion ratio determined from the true density of these products was 2.9, and the maximum volumetric expansion ratio, assuming the generation of voids in the corrosion products, was 3.7, which is the Pilling–Bedworth ratio of Fe(OH)₂. The volumetric expansion ratio may increase in the presence of carbonate ions in a long-term environment with a reduced pH.     

Stress corrosion cracking susceptibility of P285NH and API 5L X65 steel grades in the high-level radioactive waste repository cell concept

Since 2014, the concept developed for the disposal of high-level radioactive waste in the French deep geological repository project Cigéo includes a cement-based grout material. This cement-based grout material will be injected between the casing and the claystone to neutralize the potential acidity resulting from the claystone oxidation induced by the drilling process of the disposal cell. In these conditions of pH (around 10.5) and temperature (90°C, maximum expected during the disposal), the metallic materials could be sensitive to stress corrosion cracking (SCC). In this project, different environments (aerated or deaerated, at room temperature or at 90°C) and synthetic solutions are considered to reproduce the different periods expected during the long life repository. The project is based on electrochemical measurements (polarization curves to define the SCC critical domain of potentials), slow strain rate tensile tests, and long-term immersion for crack initiation and propagation tests.     

Further results on the in situ anaerobic corrosion of carbon steel and copper in compacted bentonite exposed to natural Opalinus Clay porewater containing native microbial populations

Since 2012, a long-term in situ corrosion experiment (IC-A) is being conducted in the Mont Terri Underground Research Laboratory in Switzerland to investigate the corrosion behaviour of candidate canister materials in conditions representative of the Swiss concept for the disposal of high-level waste and spent nuclear fuel. To date, carbon steel and various types of copper coatings have been retrieved after different exposure periods of up to 3 years, and characterised to establish the composition of the corrosion product, the morphology of the corroded surface, the nature of the interaction between the metal and the surrounding bentonite, and the microbial populations in the bentonite and surrounding porewater. For carbon steel specimens, a complex corrosion product was identified, consisting predominantly of magnetite. Much less alteration on either the metal or the bentonite was observed in the case of copper samples. Low average anaerobic corrosion rates were measured for carbon steel and a very modest amount of alteration was identified on copper. The density and the initial form of the bentonite had a small influence on the rate of corrosion, across all materials. This paper summarises the results of the experimental programme obtained to date and discusses the relationship observed between exposure time and the evolution of the metal–bentonite interface for both carbon steel and copper.     

Overview of anaerobic corrosion of carbon steel radioactive waste packages in alkaline media in support of the Belgian supercontainer concept

The so-called supercontainer concept is currently being considered as the reference design for the final disposal of vitrified high-level radioactive waste and spent fuel in Belgium. It comprises a prefabricated Portland cement-based buffer that completely surrounds a carbon steel overpack. In this highly alkaline environment (pH ~13.6), and under normal conditions (i.e., without the ingress of aggressive species), the carbon steel overpack will be protected by a passive oxide film, which is expected to result in very low uniform corrosion rates. Considering the long timescales applicable to waste disposal, determining accurate and reliable estimates of the uniform corrosion rate under anoxic conditions forms a very important part of the safety and feasibility strategy. It is also crucial to demonstrate that no other form of corrosion apart from uniform corrosion takes place. This paper presents the progress of the research that has been made since the LTC2016 Workshop (Toronto, Canada) on uniform corrosion, pitting corrosion and stress corrosion cracking behaviour of P355 QL2 grade carbon steel exposed to an artificial concrete pore water solution.     

Corrosion behaviors of carbon steel induced by life activities of Phaeodactylum tricornutum in a marine environment

Microbiologically influenced corrosion induced by bacteria has been studied for many years. Corrosion is known to be sensitive to the presence of microalgae, such as Phaeodactylum tricornutum. However, the life activity of P. tricornutum that influences the general and localized corrosion of carbon steel is not fully understood. The current study uses a combination of immersion tests and electrochemical experiments with a detailed surface characterization to reveal the naturally formed corrosion products with/without the presence of P. tricornutum. The results show that samples suffer from pitting corrosion and the averaged pit depths are approximately 15 μm under a light–dark cycle condition or a 24-h constant light condition. Meanwhile, the corrosion products are mainly comprised of γ-FeOOH and Fe₃O₄ in a constant light condition. However, γ-FeOOH, Fe₃O₄, and FeCO₃ are found in a light–dark cycle. This study proposes the fundamental mechanisms of the effect of P. tricornutum life activities on the corrosion performance of Q235 carbon steel, to fulfill the knowledge gaps of the presence of microalgae inducing the general and pitting corrosion of carbon steel.     

Corrosion resistance of a cast steel overpack for high-level radioactive waste disposal in Japan

The corrosion rate and stress corrosion cracking (SCC) susceptibility of a cast steel are studied for its application to metal containers (namely overpacks) for geological disposal of high-level radioactive waste. Specimens for corrosion tests are cut from a prototype overpack manufactured by full-scale casting. Casting defects are widely distributed in the prototype overpack; however, the flat-bottom hole equivalent diameters for all defects detected by an ultrasonic test are 3.6 mm or less, which is relatively small. Forged steels and rolled steels are also tested for comparison of their corrosion properties with the cast steel. The corrosion rates are obtained by immersion tests in bentonite saturated with synthetic seawater under anaerobic conditions at 80°C for up to 1 year. The corrosion rate for the cast steel calculated by the weight loss during the experiments is close to that for the forged steels and rolled steels. The SCC susceptibility is examined using slow strain rate tests in a 1.5-mol L⁻¹ carbonate–bicarbonate solution, in which the occurrence of high-pH SCC is often reported for carbon steels. The SCC susceptibility increased with the increase in the carbon content of the products; however, there are no clear differences between casting and forging.     

Outdoor atmospheric corrosion of carbon steel and weathering steel exposed to the tropical-coastal climate of Thailand

This study focuses on atmospheric corrosion of carbon steel and weathering steel exposed at two different locations with dissimilar meteorological parameters and airborne pollutants in Thailand. The samples are subjected to an outdoor atmosphere for up to 36 months at Rayong, close to the Gulf of Thailand, and Phangnga, near the Andaman Sea. Thickness loss (µm), corrosion rate (µm/year) together with corrosion product morphology and composition are systematically analyzed using X-ray diffraction and a scanning electron microscope. Corrosion resistance of the tested steels exposed at both locations is discussed based on the above-mentioned parameters and calculated corrosion kinetics. The results indicate that the total time of wetness, amount of rainfall and chloride deposition rate play an important role in corrosion behavior of the tested steels. Alloying elements, copper, chromium and nickel, are shown to improve corrosion resistance of the samples when exposed at the location with a higher chloride concentration.     

Studies on waterline corrosion processes and corrosion product characteristics of carbon steel in 3.5 wt% NaCl solution

The waterline corrosion behaviors of carbon steel partially immersed in a 3.5 wt% NaCl solution were investigated using the wire beam electrode technique, and the effects of corrosion products on the processes of waterline corrosion were analyzed. The results demonstrated that the initial stage and development stage of waterline corrosion were mainly controlled by the concentration and diffusion of dissolved oxygen, respectively, and the deceleration stage of waterline corrosion was mainly affected by corrosion products. The main component of the yellow corrosion products was γ-FeOOH, and γ-FeOOH that exhibited a high reduction reactivity could be involved in the cathodic reaction. The black corrosion products were mainly composed of Fe₃O₄ with strong thermodynamic stability and the processes of dissolved oxygen diffusion and ion transports were obviously affected due to the continuous accumulation of Fe₃O₄ on the surface of the electrodes. Polarity reversals were observed on the single electrodes below the waterline, but the reasons for the phenomena were different from each other.     

General corrosion of carbon steel in a synthetic concrete pore solution

In this study, we reviewed our recent work on the general corrosion of carbon steel (P355QL2) overpack material for the isolation of high-level nuclear waste in Belgium's supercontainer concept. By using electrochemical impedance spectroscopy and by optimizing the mixed potential model, which incorporates quantum mechanical tunneling of charge carriers across the barrier layer to describe the kinetics of the partial cathodic process, we evaluated all parameters in the model as a function of independent variables such as voltage, temperature, and pH. By delineating the partial anodic and cathodic processes, we found that the corrosion rate (CR) is independent of voltage over the voltage range from 0.2 to −1.0 V_SHE, which is predicted to be experienced in the repository. Furthermore, the CR is found to increase strongly with decreasing pH and increasing temperature.     

Effectiveness of Croton cajucara Benth on corrosion inhibition of carbon steel in saline medium

Application of corrosion inhibitors is one of the most common practices for the protection of steel structures and their alloys in industry. Since metallic corrosion is a major cause of economic losses in the oil industry, the use of natural inhibitors is an alternative for sustainable technological development. In the present study the effectiveness of the hydroalcoholic extract of the plant species Croton cajucara Benth (CC) dissolved in a microemulsion system (MES‐CC) as well as in dimethyl sulfoxide (DMSO‐CC) was evaluated as corrosion inhibitor on carbon steel AISI 1020 in saline medium. Surface tension measurements of the MES‐CC confirmed micelle formation, and rheological data showed that viscosity varies with temperature. According to potentiodynamic technique and Tafel extrapolation, maximum inhibition efficiencies were effective (93.84% for MES‐CC and 64.73% for DMSO‐CC) with predominant control of cathodic reaction. The adsorption of MES‐CC on carbon steel surface obeys Langmuir adsorption isotherm, while DMSO‐CC was found to follow the Frumkin isotherm.     

Influence of pH on corrosion behavior of carbon steel in simulated cooling water containing scale and corrosion inhibitors

In this paper, the influence of pH on the corrosion behavior of AISI 1020 carbon steel in simulated cooling water was investigated by using electrochemical and surface analysis methods. The results of polarization showed that the corrosion resistance of carbon steel increased with an increase in pH of the simulated water, and the corrosion control process changed from cathodic polarization to anode polarization control. The scale and corrosion inhibitor 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) had a certain anodic corrosion inhibition effect on carbon steel, whereas Zn²⁺ acted as a cathodic inhibitor for carbon steel in simulated water with pH 7–9. In simulated water containing both PBTCA and Zn²⁺, a good synergistic corrosion inhibition was found between PBTCA and Zn²⁺, and their corrosion inhibition effect on carbon steel was the best at pH 8. This was attributed to the formation of Zn(OH)₂ precipitate film in the cathode region and the formation of Zn–PBTCA complex film in the anode region at this pH.     

合金钢与碳钢渗氮层的耐蚀性对比

在不同温度下对碳钢Q235和42CrMo钢进行气体渗氮,利用光学显微镜、扫描电镜、能谱仪及X射线衍射仪对比分析了Q235和42CrMo钢渗氮层的微观组织及相结构,并用电化学方法测试了样品的耐腐蚀性。经过渗氮处理后的样品的耐腐蚀性都较原材有大幅提高,而相同温度渗氮后42CrMo钢的自腐蚀电位较Q235钢的低,42CrMo钢渗氮层电阻小于Q235钢,碳钢渗氮层的耐蚀性优于合金钢。采用热力学和第一性原理计算探讨了42CrMo钢的合金元素对渗氮层的抗腐蚀性的影响。结果表明合金元素Cr、Mo通过降低Fe-N化合物稳定性从而降低渗氮层的抗腐蚀性。     

Atmospheric corrosion of carbon steel at marine sites in Saudi Arabia

Atmospheric corrosion tests, according to ASTM G50‐76, have been carried out in Saudi Arabia, at eight marine sites representing different environmental conditions. Environmental factors such as average temperature, average relative humidity, and deposition rates of atmospheric pollutants (Cl^? and SO₂) was investigated. X‐ray diffraction has been used to determine the composition of the corrosion products. Corrosion rates have been determined for each sample at each of the exposure sites via loss of weight. The obtained data were used for the classification of atmospheric aggressivity, according to ISO 9223. The results obeyed well with the empirical kinetics equation of the form C = Ktⁿ, where K and C are the corrosion losses in mg/cm² after 1 and t years of the exposure respectively, and n is constant. Based on n values, the corrosion mechanism of carbon steel is predicted. The major constituent of the rust formed in marine environment is goethite (α‐FeOOH). Samples also show the presence of a large proportion of lepidocrocite (γ‐FeOOH) and small amounts of ferrihydrite and maghemite (α‐Fe₂0₃).     

Investigation of the effect of CrO and MoO on carbon steel corrosion using AFM and electrochemical techniques

The effect of chromate ( ) and molybdate ( ) ions on the corrosion of carbon steel in 0.5 M NaCl solution has been studied using electrochemical measurements and atomic force microscopy (AFM) technique. Potentiodynamic polarization data suggest that both and have inhibition effect on carbon steel corrosion, and the inhibition efficiency increases with increase in concentrations of and ; at the same concentration, the inhibition efficiency of is higher than that of . The increase in concentrations of and anions causes a shift of the breakdown potential (E_b) in the positive direction, indicating the inhibitive effect of the added anions on the pitting attack. At the same concentrations, the breakdown potential of is higher than that of . Electrochemical impedance spectroscopy (EIS) tests reveal that the charge transfer resistance and passive film resistance increase with increase in concentrations of or ; at the same concentrations, as for the charge transfer resistance and passive film resistance were bigger than those of . AFM imaging technique shows that local corrosion was inhibited obviously after the addtion of or , and passive film of was much more compact than that of . AFM force–distance curves indicate that the passive film of is much stiffer than that of .