Corrosion and Materials Degradation

In order to discover how the multiple oxides observed in the final external scales after long exposure of a low-Mn, high-Cr Cantor’s alloy to hot air were formed, oxidation tests in a furnace were performed for seven different durations. Metallographic characterization was carried out concerning the oxidation products obtained after each test duration. The different oxides did not appear one after the other, but simultaneously, early on in the exposure to hot air and after. They all thickened progressively and the chemical composition of each also evolved with time, more or less. Globally, the innermost oxide is almost entirely chromia, much richer in Cr than in Mn, while the outermost one contains principally Mn. The interrupted tests also allowed specifying the mass gain kinetic, which is parabolic and twice as fast as a chromia-forming alloy. Despite the lowered content in Mn, manganese still plays an important role in the oxidation phenomenon, starting very early. Full article

Molecular aromatic corrosion inhibitors are frequently applied to slow down the corrosion of iron, its alloys and numerous other metallic materials. This case study with three representative aromatic inhibitors and a pure iron electrode aims at the verification of the reported conclusions regarding these inhibitors and at the verification and comparison of electrochemical corrosion assessment methods with attention to differences between iron alloys (steels) and pure iron possibly related to the presence/absence of alloying elements and non-iron impurities. Full article

Highly sensitive resistometric sensors were applied for the real-time corrosion monitoring of carbon steel protected with a polyolefin coating with and without an inhibitor under static and dynamic atmospheric and immersion conditions. The results were compared with conventional electrochemical impedance spectroscopy (EIS) data. An increase in the coating thickness from 20 µm to 50 µm and an addition of 1wt.% tannic acid significantly improved the coating corrosion stability. Based on the real-time corrosion data, the drying stage of atmospheric exposure in a chloride-rich environment was found to be the most critical. The highest corrosion rate was detected at 50% relative humidity when the electrolyte corrosiveness in coating defects reached the maximum. Resistometric sensors have the potential to become an interesting alternative for evaluating coating performance and degradation mechanisms in both laboratory and industrial applications. Full article

This study examines the effects of heat treatment on corrosion behavior of equiatomic AlCoCrNiFe high-entropy alloy within a solution treatment temperature range of 800–1100 °C. Experimental observations on phase formation were compared with thermodynamic predictions. The microstructure, mechanical properties, and aqueous corrosion behavior of the as-deposited alloy were analyzed and contrasted with heat-treated samples. The results showed a decline in the corrosion resistance of the AlCoCrNiFe after heat treatment, which was attributed to chemical segregation and Cr depletion in the microstructure matrix. Additionally, post-corrosion analysis revealed a reduced volume fraction of protective oxides in the heat-treated samples. Full article

Molecular inhibitors added to the corrosive medium attacking metallic materials are a well-established way of combating corrosion. The inhibitive action proceeds via adsorption of the inhibitor on the surface to be protected. Aromatic building blocks in the inhibitor play a major role in its protective action, and further details like substituents, heteroatoms, and molecular geometry contribute. An overview focused on aromatic inhibitors is provided, aiming at the identification of particularly promising inhibitors and their mode of action. Directions for further research and development are pointed out in the conclusion. Full article

Anticorrosive organic coatings are usually tested with accelerated weathering methods to assess their anticorrosive performance. The results of lab testing often do not correlate well with results from field testing, which resembles the conditions of actual use more closely. We tested the correlation of the neutral salt spray test (NSS, ISO 9227) and tests for mechanical properties and a 5-year field exposure in four different locations in the atmospheric zone, splash zone and immersion zone using 19 organic coatings for hydraulic steelwork. No correlation was found between the anticorrosive performance under outdoor exposure and the mechanical properties of a coating. The NSS test showed a positive correlation with the results in the field in 6 of 12 cases. For the fresh water testing location in Trier, the correlation proved to be very good. The biggest difference between lab and field testing was observed for zinc-primer-free coatings, which passed in the lab testing and failed in the outdoor testing. This study shows that the NSS test correlates with outdoor exposure only in some cases on a statistically significant level, but the results of NSS testing can be useful in approval testing for protective coating systems using predefined pass/fail criteria. Full article

The concepts of physical and chemical transformations occurring in cement concrete under conditions of microbiological deterioration can be used to control the processes of the destruction of cement concretes in order to ensure the required durability and to predict the service life of products. The study of changes in the structural and phase composition of cement stone made of Portland cement grade CEM I 42.5N in the process of fungal deterioration for 6 months when moistened, as well as a sample of a concrete wall exposed to fungal microorganisms for 20 years, was carried out. Diffractograms of the studied cement stone samples contain a large number of pronounced narrow peaks and indicate a highly crystalline structure of phases with the presence of an X-ray amorphous phase of calcium hydrosilicates and tobermorite gel in the cement stone. Changes in the structure of cement stone under the influence of fungi are confirmed by the data of a derivatographic analysis. A decrease in the content of calcium hydrosilicates and ettringite, as well as other crystalline phases in cement stone, leads to a decrease in compressive strength by about 15% over 6 months of fungal degradation. Similar changes after 20 years of exposure to microorganisms suggest deterioration in the strength characteristics of concrete. Full article

The potentiostatic, anodic formation of gold oxide at potentials of 0.55 to 0.80 V versus SHE in aqueous KOH (0.1 M) was studied using an impedance-based Point Defect Model (PDM). The film thickness and refractive indices at each formation potential were estimated using spectroscopic ellipsometry. The thickness of the oxide increases linearly with increasing applied voltage within this range. Mott-Schottky (MS) analysis showed that gold oxide formed in KOH (0.1 M) is an n-type semiconductor, and the dominant defect (${Au}_i^{3+}$) density is calculated to be in the order of 10²¹–10²² (1/cm³). The steady-state current density of the oxide formation was independent of voltage, also in agreement with an n-type oxide. Reasonable agreement between PDM predictions and experimental observations of dominant defect density, steady-state current density, and thickness, demonstrates the value of the PDM in this system. Full article

This study investigates the degradation of mechanical properties in CuZr metallic glasses (MGs) under cyclic loading using molecular dynamics simulations. Both as-cast (AC) and cryogenically thermal-cycled (TC) samples with Cu₃₆Zr₆₄ and Cu₆₄Zr₃₆ compositions were analyzed. Results show that cyclic loading significantly degrades Young’s modulus, ultimate tensile stress, and toughness, with most pronounced reductions occurring in the initial cycles. TC samples exhibit improved ductility and stability compared to AC samples. In contrast, AC samples demonstrate greater initial strength but faster degradation. Cu-rich samples maintain higher strength but degrade similarly to Cu-poor samples. The AC Cu-rich sample experiences more localized deformation and delayed degradation, while TC and AC Cu-poor samples quickly reach a steady state. These findings highlight the influence of atomic composition and thermal treatments on the mechanical performance and degradation behavior of MGs. Full article

New environmental regulations have led to major changes in aluminum corrosion protection by prohibiting, for example, Cr(VI). Thus, the assessment of the corrosion behavior of Cr-free systems under atmospheric conditions is a major topic of interest for the aerospace industry. One major difficulty in this task is the lack of robust and reliable accelerated corrosion test(s) in this field. The aim of the present study is to compare the results of various accelerated corrosion standards (ASTM B117, ISO 4623-2, VCS 1027,149) to results obtained after 5 years of exposure at a marine atmospheric site in Brest, France. Additional accelerated corrosion tests were designed by varying several parameters in the VCS 1027, 149, such as the salt concentration, the time of wetness, and the relative humidity. The different modes of failure obtained in accelerated corrosion tests on the painted samples were then compared to field exposures in a marine atmospheric site. The first results obtained showed that the developed tests are more representative of service conditions than standard tests. Full article

This study investigates the fatigue behavior of cold-finished mild steel subjected to electrochemical hydrogen charging under controlled conditions. Samples were subjected to hydrogen charging at constant time in a fixed electrolyte pH, after which the samples underwent fatigue testing under constant loading condition with fixed frequency. The primary objective was to assess the impact of varying hydrogen permeation levels on the number of cycles to failure. The experimental results revealed a complex relationship between hydrogen concentration and fatigue life. Initially, as hydrogen permeation increased, the number of cycles to failure substantially decreased, demonstrating the detrimental effect of diffused hydrogen on the fatigue resistance of samples. This decline in fatigue life was attributed to hydrogen embrittlement (HE) and hydrogen-enhanced decohesion (HEDE) phenomena, which collectively facilitate crack initiation and propagation. However, at high hydrogen concentrations, an unexpected increase in the number of cycles to failure was observed suggesting the existence of a threshold hydrogen concentration beyond which the fatigue mechanisms may be altered, potentially due to a saturation of hydrogen-related defects and mechanisms such as hydrogen-enhanced localized plasticity (HELP). The discovery from this research has significant implications for the material’s application in hydrogen-rich environments, such as those encountered in the energy and transportation industries. Full article

Two-month experiments were carried out with carbon steel electrodes buried in an artificial sand wetted at 50–55% of saturation with a 0.07 mol L⁻¹ Na₂SO₄·10H₂O solution. Various protection potentials (corrected from the ohmic drop) were applied from −0.60 to −1.13 V/Cu-CuSO₄. In each case, the behavior of the electrode protected by cathodic polarization was compared with that of an unprotected electrode. The electrochemical study was performed using voltammetry, linear polarization resistance measurements, and EIS. Surface characterization of the coupons was carried out using optical microscopy and X-ray diffraction. First, cathodic protection was observed to induce a spreading of the electrolyte on the metal surface because of electrocapillary effects. The active area, or more precisely the wet area, of the electrode increased, leading to a decrease in soil electrolyte resistance R_s measured using EIS. This phenomenon was experimentally confirmed via visual observations of the surface of the coupons at the end of the experiments. Secondly, cathodic protection induced a passivation of the steel surface. The passive state persisted for 35 to 85 h after cathodic protection was stopped and could be studied during various periods of interruption of the protection. In each case, the OCP of the previously polarized coupons reached high values, actually 200–250 mV higher than those measured for the unprotected coupons, and was associated with high polarization resistance R_p values (~40 kΩ cm²). Depassivation of the metal finally occurred, a phenomenon revealed by simultaneous important drops of both OCP and R_p. Full article

In the process of heat treatment of 8620 low alloy steel, the heating rate is a critical parameter that must be carefully controlled to achieve the desired combination of microstructural features, mechanical properties, and corrosion resistance while simultaneously ensuring process efficiency and cost-effectiveness. This study investigates, for the first time, the microstructural evolution and electrochemical properties of 8620 steel under identical quenching and tempering heat treatment routes with slow-rate (SR) and fast-rate (FR) heating rates. Microstructural analysis revealed martensitic phases for SR, while FR exhibited a dual-phase microstructure containing ferrite. Upon tempering, for both samples, the martensite transformed into tempered martensite, with tempered (Temp) FR exhibiting around 50% smaller ferrite grains. Mechanical testing indicated that SR had 17% higher hardness than FR, although hardness decreased after tempering by 22% (SR) and 17% (FR). All electrochemical tests indicated that the as-quenched SR exhibited significantly superior corrosion resistance than FR. For instance, the polarization resistance of SR was 440 Ω higher than that of the FR samples. Tempering resulted in a considerable decrease in corrosion resistance for Temp SR, whereas Temp FR improved. Electrochemical characterization revealed Temp FR displayed close-to-ideal capacitive behavior and low double-layer capacitance, indicating enhanced overall corrosion resistance. Full article

This review examines the impact of various aqueous electrolytes on hydrogen absorption and self-corrosion in magnesium (Mg) anodes. The discussion integrates both historical and recent studies to explore the mechanisms behind self-corrosion and anomalous hydrogen evolution (HE) under conditions of the Negative Difference Effect (NDE) and Positive Difference Effect (PDE). The focus is on the formation and oxidation of magnesium hydride in regions of active dissolution under NDE conditions. In the case of PDE, anodic dissolution occurs through the passive MgO-Mg(OH)₂ film, which shields the metal from aqueous electrolytes, thereby reducing hydrogen absorption and abnormal HE. The NDE conditions showed delayed reduction activity at the surface, attributed to a hydride phase within the corrosion product layer. Hydride ions were quantified through their anodic oxidation in an alkaline electrolyte, measured by the electric charge passed. The review also considers the role of de-passivating halide ions, electrolyte acidity buffering, and the addition of ligands that form stable complexes with Mg²⁺ ions, on the rates of hydride formation, self-corrosion, and anodic dissolution of Mg. The study evaluates species that either inhibit or promote hydrogen absorption and self-corrosion. Full article

We studied the effect of isothermal annealing (600–750 °C, 1 to 1000 min) on the microstructure and mechanical properties of SAF 2205 duplex stainless steel. Impact toughness was found to be significantly more affected than hardness by annealing. Annealing at 750 °C for 1000 min resulted in a more than 90% decrease in impact toughness, while hardness only increased by 25%. Tensile strength increased up to 100 MPa, but elongation decreased by more than 50% under the same conditions. Sigma phase formation was minimal at lower temperatures (650 °C and below) but increased significantly at higher temperatures. At 750 °C and 1000 min of annealing, the ferrite content dropped from 50% to 16%. These findings suggest that annealing temperature and time need to be carefully controlled to avoid a reduction in impact toughness and ductility caused by sigma phase precipitation. The harmful effect of sigma phase precipitation on mechanical properties was directly shown. Full article

The disposal of high-level radioactive waste (HLW) and spent nuclear fuel (SF) presents a unique challenge for the prediction of the long-term performance of corrodible structures since the HLW/SF canisters are expected, in some cases, to have lifetimes of one million years or longer. Various empirical and deterministic models have been developed over the past 45 years for making predictions of the long-term corrosion behaviour, including models for uniform and localized corrosion, environmentally assisted cracking and microbiologically influenced corrosion. As well as process models focused on specific corrosion mechanisms (described in Part 1 of this review), there is also a need for performance assessment models as part of the overall analysis of the safety of a deep geological repository (DGR). Performance assessment models are often based on simplified or abstracted process models. The manner in which various international waste management programs have predicted the long-term performance of HLW/SF containers with copper, steel, Ni and Ti alloy corrosion barriers is discussed. Performance assessments are repeated periodically during the development and implementation of a DGR, and the corrosion models are constantly updated in light of new mechanistic understanding and/or more information about the deep geological environment. Two examples of how the container performance assessment models evolve over time are also described. Performance assessment models cannot easily be validated, so it is important to build confidence in the long-term predictions using other methods, including natural analogues and large-scale in situ tests and the use of complementary models. Full article

This paper addresses the interplay between electrical fields in the human body and the corrosion behavior of Ti-6Al-4V alloy, a prevalent orthopedic material. The study investigates the impact of alternative electrical signals at different frequencies on the alloy’s electrochemical behavior in a simulated body environment. The human body always has natural sinusoidal potential due to, e.g., heart palpitations and brain/nervous system activities. Ignoring such natural activities may lead to underestimating the corrosion performance of the Ti-6Al-4V alloy in the body. By analyzing anodic and cathodic responses and the net faradaic current induced by alternating current potential, the research sheds light on the influence of electrical fields on corrosion rates. Understanding these dynamics could lead to improved implant materials, mitigating corrosion-related challenges and enhancing implant performance over the long term. Results of this work indicated that frequent oxidation and reduction at certain frequencies may induce corrosion and hinder biomimetic apatite formation, impacting osseointegration. Natural alternative currents in the body affect the corrosion performance of Ti-based implant alloys, highlighting the need for consideration in biomedical applications. Full article

With escalating global regulatory pressure for countries to adhere to emission laws, repurposing existing natural gas pipelines for hydrogen-based commodities stands to be an economical solution. However, the effects of hydrogen embrittlement must be thoroughly considered for this application to avoid the unexpected catastrophic failure of these pipelines. The literature proposes several physicochemical embrittlement models. This paper reports one aspect of hydrogen embrittlement that remains to be quantified: the recovery of ductility (embrittlement) of mild steel specimens subjected to artificially accelerated hydrogen absorption via electrochemical charging as a function of time. The effects of charging duration and particularly the delay period between charging and mechanical tensile testing were investigated. Unsurprisingly, longer charging time shows a greater loss of elongation; however, a more extensive recovery of ductility correlated with longer charging time in the first few days after charging. The data also show that while the uncharged mild steel met all minimum required values for strength and elongation for the specified grade, there was a substantial variability in the elongation to failure. The same trends in variability of elongation translated to the hydrogen-charged specimens. Due to this extensive variability, failure to meet the elongation specification of the grade is reported based on the worst-case scenario obtained for a given set of samples for each exposure condition. These results have practical implications for the monitoring and testing of infrastructure exposed to hydrogen, particularly as this relates to industry planned operational shutdown schedules. Full article

An impedance model based on the Volmer–Heyrovsky–Tafel mechanism was developed to study the kinetics of the hydrogen evolution reaction on polycrystalline gold electrodes at moderate overpotentials in aqueous H₂SO₄ (0.5 and 1.0 M) solutions. The model was optimized on data from potentiodynamic polarization and electrochemical impedance spectroscopy, and model parameters were extracted. Consistent with expectations, the magnitude of the impedance data indicated a higher rate of hydrogen evolution at lower pH. Also, the fractional surface coverage of adsorbed hydrogen (${\theta }_{Hads}$) increases with increasing overpotential but the small value of ${\theta }_{Hads}$ indicates only weak adsorption of H on gold. Tafel slopes and exchange current densities were estimated to be in the range of 81–124 mV/dec, and 10⁻⁶ and 10⁻⁵ A/cm² in H₂SO₄ (0.5 and 1.0 M), respectively. The results show that the model accounts well for the experimental data, such as the steady-state current density. Sensitivity analysis reveals that the electrochemical parameters (${\alpha }_1, {\alpha }_2, k_1^0, k_{-1}^0, {\mathrm{a}\mathrm{n}\mathrm{d} k}_2^0)$ associated with the kinetics of the hydrogen evolution reaction have a major impact on the calculated impedance but the standard rate constant for hydrogen oxidation reaction ($k_{-2}^0)$ does not strongly affect the calculated impedance. Full article