In the original publication [...]

The growing demand for hydrogen-based energy systems has intensified the need for structural materials with enhanced resistance to hydrogen-induced degradation. This study presents a comparative investigation of hydrogen-induced mechanical behavior and embrittlement susceptibility of laser powder bed fusion (LPBF) manufactured 316L steel and conventionally manufactured (CM) 316H steel. Tensile/Charpy testing, hydrogen charging (up to 115 h), OM, SEM, TEM, and EBSD analysis were employed to assess microstructure, strength, ductility, fracture characteristics, and phase stability. In the uncharged state, LPBF steel exhibited significantly higher strength but lower ductility than CM steel, attributed to its fine cellular sub-grain microstructure. Both steels showed similar hydrogen saturation kinetics, reaching ~9 ppm, with residual hydrogen levels of ~3.3 ppm after 90 days of desorption. Hydrogen exposure led to a more pronounced degradation of the tensile properties of the LPBF steel, with an up to 22% reduction in the ductility-based embrittlement index, while CM steel remained much less affected. Impact toughness in both materials resisted hydrogen embrittlement, retaining over 96% of initial values. Fractographic analysis of tensile specimens revealed subsurface brittle zones consistent with calculated hydrogen diffusion depths. EBSD data indicated that hydrogen-stabilized austenite in LPBF steel was achieved by suppressing deformation-induced martensitic transformation, despite increased dislocation activity. These findings suggest that, while LPBF steel is more vulnerable to hydrogen embrittlement under tensile loading via the HELP mechanism, its microstructure mitigates impact toughness degradation through hydrogen-induced austenite stabilization.

Galvanic corrosion is an electrochemical phenomenon that arises due to the coupling of two different metals in an electrolytic environment, resulting in the deterioration of the less noble metal at an accelerated rate. This phenomenon poses a significant challenge in the economy of mixed-metal assemblies in many industrial applications due to the high maintenance and replacement expenditures that such systems incur. In this study, a stainless steel tube was galvanically coupled with a carbon steel fitting, and both were immersed in a chloride solution to study the galvanic interactions. The electrochemical processes associated with galvanic corrosion were simulated using a finite element multiphysics modeling approach (COMSOL Multiphysics). The simulations reproduced the metal–electrolyte interface potential and current density as well as the preferential anodic dissolution of carbon steel over stainless steel, which was observed during the coupled polarization. The numerical results matched the results predicted using assumptions for the steels’ electrochemical behavior. The results of the study confirmed that finite element simulation is an effective means of modeling galvanic corrosion and optimizing the design and life of metal component assemblies that are subjected to highly aggressive environments such as high-chloride environments. The numerical results matched the trends observed from experimentation and those previously reported in the literature and serve to provide qualitative and semi-quantitative insight regarding galvanic corrosion mechanisms instead of complete corrosion predictions regarding long-term corrosion behavior.

The initial formation of corrosion products in pure humid air on magnesium alloys AZ91 and AZ31 was studied using infrared reflection absorption spectroscopy (IRRAS), infrared spectroscopic imaging, and SEM-EDS. The kinetics of corrosion product formation were monitored in situ with IRRAS during exposure to humid air (95% relative humidity) under two different CO2 concentrations: low (≤1 ppm) and ambient (400 ppm). For low CO2 concentrations, the primary corrosion product detected on both alloys was magnesium hydroxide (Mg(OH)2). In contrast, under ambient CO2 conditions (400 ppm), magnesium hydroxy carbonate was the dominant product. After 16 h of exposure, the amount of magnesium converted into corrosion products was approximately 8–10 times higher under low-CO2 conditions compared to ambient levels. The smaller formation of corrosion products but increased magnesium carbonate formation on AZ91D is attributed to its higher aluminium content compared to AZ31. Corrosion attack and product formation were largely localised to the centre of the α-phase in AZ91D, with the β-phase likely serving as sites for cathodic reactions.

Inspired by the mechanism of ion exchange resins, this study is a first-report in constructing a dual-layer photocathodic protective coating with ionic selectivity to enhance corrosion resistance property. The microstructure, composition, and ion selectivity of the coating are characterized by scanning electron microscopy, Raman spectroscopy, infrared spectroscopy, and membrane potential. It shows that the outer g-C3N4/TiO2 cation-selective layer plays a role in preventing corrosive Cl− ions passing through the coating; the inner g-C3N4-TiO2-CTAB anion-selective layer could prevent Fe2+ ions from diffusing through the coating. Furthermore, the coated carbon steel sample demonstrates a minimum OCP (open circuit potential) value of −770 mV (vs. SCE) under illumination in 3.5% NaCl media. Interestingly, the OCP remains around −720 mV (vs. SCE) even after light deprivation. The synergistic effect between ion selectivity and photocathodic protection is described, in detail, in the following.

The spontaneous formation and stability of a protective passive film on a metal surface are crucial for the metal material’s corrosion resistance during its service life. Passive films have been extensively studied, and our understanding of passive films has been significantly improved with the development of advanced analytical techniques. Modern synchrotron X-ray sources offer unprecedented possibilities for detailed analyses of passive films and for in situ and operando studies of passive films in both gaseous/aqueous environments, as well as in electrochemical environments. This mini review presents a short summary of recent studies on passive films, mainly focusing on stainless steels and nickel-base alloys, which utilize state-of-the-art synchrotron X-ray techniques, particularly X-ray photoelectron spectroscopy (XPS), often in combination with other synchrotron techniques such as X-ray adsorption, diffraction, reflectivity, and fluorescence. These reports demonstrate that synchrotron-based techniques greatly improve probing sensitivity and spatial resolution, enabling in situ and operando studies of passive films at solid–liquid interfaces. These studies reveal changes in the passive film and underlying alloy layer, highlighting the important role of hydroxides, as well as the inhomogeneity in passive films associated with the complex microstructures in advanced industrial alloys.

Self-assembled monolayers of alkane thiolate and alkane selenolate have been proven to inhibit atmospheric corrosion, but upon prolonged exposure to the important constituents of indoor atmosphere, namely humidified air with formic acid, the protective layer eventually breaks, but the exact reason is not yet clear. In this paper, we report on an XPS study of co-adsorbed formic acid and hexane selenol on a Cu surface. Adsorption of hexane selenol at room temperature breaks the Se-C bond, leaving a monolayer of Se on the surface, whereas adsorption at 140 K leaves a layer of selenolate. Formic acid exposure to the selenolate-Cu surface leads to adsorbed formate on unprotected areas and absorption of formic acid within the alkane chain network. During heating, the formic acid desorbs and the Se-C bond breaks, but formic acid does not accelerate the Se-C scission, which occurs just below room temperature both with and without formic acid. Thus, formic acid alone does not affect the Se-C bond, but its presence may create disorder and open up the alkane carpet for other species. Selenol removes formate and oxide from the surface at room temperature. The Se-C bond breaks and the alkane chain reacts with surface oxygen to form carbon oxides and volatile hydrocarbons.

In a recent investigation the corrosion-fighting potential of five benzaldehyde derivatives were explored: 4-Formylbenzonitrile (BA1), 4-Nitrobenzaldehyde (BA2), 2-Hydroxy-5-methoxy-3-nitrobenzaldehyde (BA3), 3,5-Bis(trifluoromethyl)benzaldehyde (BA4), and 4-Fluorobenzaldehyde (BA5). Benzaldehyde derivative (BA-2) showed a maximum inhibition efficiency of 93.3% at 500 ppm. Several techniques were used to evaluate these compounds’ ability to protect mild steel from corrosion in a 1 M HCl solution, including potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS), adsorption isotherms, and computational methods. Supporting techniques Fourier transform infrared spectroscopy (FTIR) and ultraviolet–visible (UV-Vis) spectroscopy were also employed to validate the results. Despite sharing a common benzene ring, the molecules differ in their substituents, allowing for a comprehensive examination of the substituents’ impact on corrosion inhibition. PDP analysis disclosed that the inhibitors exhibited mixed-type inhibition behavior, interacting with anodic as well as cathodic reactions, influencing the corrosion process. EIS analysis revealed that benzaldehyde derivatives formed a protective passive film on the metal, exhibiting high corrosion resistance by shielding the alloy from corrosive attacks. The benzaldehyde inhibitors followed the Langmuir adsorption isotherm, with high R² values near one, indicating a monolayer adsorption mechanism. DFT results indicate that BA 2 is the most effective inhibitor. FTIR and UV-vis spectroscopy revealed the molecular interactions between metal and benzaldehyde derivative molecules, providing insight into the binding mechanism. Experimental results support the outcomes obtained from the molecular dynamic (MD) simulations.

Copper has been proposed as a container material for the disposal of used nuclear fuel in a number of countries worldwide. The container materials will be subject to various corrosion processes in a deep geological repository, including radiation-induced corrosion (RIC) resulting from the γ-irradiation of the near-field environment. A comprehensive model is being developed to predict the extent of RIC by coupling a radiolysis model to the interfacial electrochemical reactions on the container surface. An important component of the overall model is a radiolysis model to predict the time-dependent concentration of oxidizing and reducing radiolysis products. As a first step in the model development, various radiolysis models have been validated against experimental measurements of the concentrations of dissolved and gaseous radiolysis products. Experimental data are available for pure H2O- and Cl−-containing solutions, with and without a gas headspace. The results from these experiments have been compared with predictions from corresponding radiolysis models, including the effects of the partitioning of gaseous species (O2 and H2) at the gas–solution interface. Different reaction schemes for the Cl− radiolysis models are also compared. The validated radiolysis model will then be coupled with interfacial reactions on the copper surface and additional processes related to the presence of bentonite clay in Steps 2 and 3 of the overall model, respectively.

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 (θHads) increases with increasing overpotential but the small value of θHads 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 (α1, α2, k10, k−10, and k20) 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−20) does not strongly affect the calculated impedance.