Corrosion and Materials Degradation

Corrosion is one of the causes of failure in reinforced concrete structures, and forming a passive film on the steel is essential for protection. Although several studies have looked at passive film formation in concrete pore solutions, few have considered its formation in hardened concrete and the influence of silica fume (SF) in the binder composition. This study aims to evaluate the influence of the SF content on passive film formation time in concrete. Periodic measurements assessed the electrical resistivity and corrosion current density of concrete samples containing 5%, 10%, 15%, and 20% SF. The alkalinity of the mixtures and the kinetics of the pozzolanic reaction were also monitored by XRD and titration tests. The control mixtures exhibited susceptibility to corrosion, regardless of the curing age evaluated. In contrast, the partial replacement of cement with SF accelerated the formation of the passive film on the steel surface, suggesting a delayed onset of corrosion due to modifications in the physical properties of the concrete. Also, the portlandite content and pH can predict passive film formation, with SF significantly accelerating this process. Full article

Corrosion investigations of steel-reinforced concrete structures are often based on half-cell potential measurements, in which the diffusion potentials can be a significant source of measurement errors. Therefore, the diffusion potentials must be taken into account in order to enable accurate half-cell potential measurements. This study covers the measurement of the diffusion potentials in cement mortars with pH differences due to carbonation and various mortar moisture conditions. The effect of chloride exposure of the mortars on the diffusion potentials is outside of the scope of this study. The mortars consisted of ordinary Portland cement (OPC) and blast furnace cement (BFC) with water–cement ratios of 0.5–0.7. The use of color indicators allows for the observation of the pH drop around the carbonation front, which propagates as the carbonation progresses. The diffusion potentials in the mortars under study have measurement values between 10 and 240 mV. The measured diffusion potentials seem to correlate with the magnitude of the pH drop rather than the progress of the carbonation depth. The moisture condition of the mortars significantly affects the magnitude of the arising diffusion potentials. Full article

Seawater ballast tanks in vessels are subject to severe service conditions caused by repeated filling/emptying, as well as temperature variation. Consequently, relatively thick, barrier-type coatings are used for corrosion protection of their internals. These are generally formulated with solvent-based epoxy binders and contain a range of flake pigments designed to limit environmental entry. Here, we report on a detailed study of damage processes in order to understand the mechanisms of failure after hygro-thermal cyclic corrosion testing. Similar formulations were cured using variant phenalkamine cross-linkers. Visual observation after corrosion testing shows minimal changes and no sign of corrosion damage. However, high-resolution analytical microscopy and nanoscale tomography reveal the onset of microstructural and chemical damage processes inside the coating. Thus, kaolin and talc pigments in the coating remained stable under hygro-thermal cycling; however, dolomite and barium sulphate dissolved slightly, causing voids. Galvanic protection of the substrate by aluminium flake pigments was disproven as no electrical connection was evident. Vibrational spectroscopy revealed a decrease in residual epoxy functionality after exposure for the coating cured with the more stable phenalkamine. This was correlated with an increase in glass transition temperature (Tg) and no observable corrosion of aluminium flakes. In contrast, the less stable phenalkamine cross-linker caused the binder Tg to decrease and aluminium flakes and substrate corrosion to become evident. Full article

Ti and Ti6Al4V alloy are extensively utilized in structural parts in engineering applications and the production of medical implants due to their excellent mechanical properties, lightweight, and high corrosion resistance. This study comprehensively evaluates their corrosion behavior in three challenging aquatic environments: brackish water, seawater, and seawater bittern. Utilizing open circuit potential (E_OC) measurements with polarization techniques (linear and potentiodynamic) and electrochemical impedance spectroscopy (EIS) measurements, the research highlights distinct environmental influences on corrosion performance. Notably, Ti and Ti6Al4V alloy demonstrated exceptional stability with the highest polarization resistance and lowest corrosion current in brackish water, while seawater bittern presented the most demanding condition for Ti6Al4V. Additionally, the analysis of the electrode surfaces after polarization measurements using optical microscopy, optical profilometry, and SEM/EDS tests revealed minor damage, indicating the high corrosion resistance of these materials. This study advances the understanding of Ti and Ti6Al4V alloy performance in diverse environments and offers valuable insights for optimizing their use in harsh aquatic conditions, particularly for applications requiring durability and longevity. Full article

The objective of this research is to enhance the mechanical and corrosion resistance properties of a cast Ni-Al bronze (NAB). To achieve this, the effect of deep cryogenic treatment (DCT), a process that has shown promise in other alloys, is initially investigated. It is demonstrated that, in the case of NAB, DCT induces only minor microstructural changes, which do not lead to any significant improvement in its properties. Consequently, it is proposed that a combined treatment be employed, involving annealing either before or after DCT. The results indicate that annealing at 675 °C for 2 h following cryogenic treatment at −180 °C increases the yield strength by approximately 11%. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in simulated seawater further confirm that this combination results in the formation of oxide layers with enhanced protective capacity. These improvements are attributed to the significant refinement and homogenization of the microstructure, including the globularization of the kI, kII, and, particularly, kIII phases, and an increase in the precipitation of the kIV phase in a finer and more homogeneous form within the alpha phase. Full article

Ascorbic acid is widely used as an immunity-enhancing and antioxidant supplement for treating influenza and other virus-based illnesses. The lactone ring and the oxygenated groups make this system and derived structures attractive as possible environmentally friendly green corrosion inhibitors. Thus, we investigate the corrosion inhibition influence of ascorbic acid, ascorbate, and dehydroascorbic acid on the $\alpha$-Fe(110) surface using density functional theory calculations. The adsorption, density of states, and charge transfer results indicate that dehydroascorbic acid is this series’s most potent corrosion inhibitor. The projected density of states near the Fermi energy reveals notable hybridization between the iron surface and dehydroascorbic acid adsorbed on it. The calculated structural, electronic, and energetic properties obtained in this work pave the way for understanding the corrosion inhibitory performance of the investigated systems. Full article

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