Fe₄₂Mn₂₈Cr₁₅Co₁₀Si₅ is a highly strain-hardenable high-entropy alloy (HEA) that is challenging to machine with traditional metal cutting tools. The electrochemical behavior of this HEA was examined in nitrate- and chloride-based electrolytes to understand the electrochemical machining (ECM) process. Potentiodynamic and potentiostatic tests were conducted on this alloy in 1 M and 2.35 M NaNO₃ solutions, with and without additions of 0.01 M nitric acid and 0.01 M citric acid. A 20% NaCl solution was also tested as an electrolyte. Nitrate solutions caused passivation of the HEA, while no passivation was observed in chloride solutions. Surface analysis with X-ray photoelectron spectrometry (XPS) indicated that adding citric acid helped reduce surface passivation. The Faradaic efficiency of ECM increased with higher applied voltage. The chloride solution showed higher Faradaic efficiency than nitrate-based solutions. Specifically, the Faradaic efficiency of 20% NaCl at 10 V is 57.4%, compared to 21.9% for 20% NaNO₃ + 0.01 M citric acid at 10 V. Electrochemical parameters, including anodic and cathodic exchange current densities, Tafel slopes, and corrosion current densities, were calculated from the experimental data. The corrosion current densities in the 20% nitrate solutions ranged from 2.35 to 3.2 × 10⁻⁵ A/cm², while the 20% chloride solution had a lower corrosion rate at 1.45 × 10⁻⁵ A/cm². These electrochemical parameters can help predict the dissolution behavior of the HEA in nitrate and chloride solutions and aid in optimizing the ECM process.

In this study, cyclic polarization (CP) measurements were conducted on the molybdenum-based titanium–zirconium–molybdenum (TZM) alloy in 3.5% NaCl solutions under varying pH conditions, and the results were compared with those of pure molybdenum. No passivity breakdown was observed during cyclic polarization in acidic and neutral chloride solutions. The surface film formed on the TZM, and pure Mo samples displayed a dual-layered structure, comprising an inner layer of p-type semiconductivity and an outer layer of n-type semiconductivity. The defect density of the n-type layer ranged from 7.5 × 10¹⁷ to 7.5 × 10¹⁹ cm⁻³, while the p-type layer had a carrier density ranging from 2 × 10¹⁸ to 9 × 10¹⁹ cm⁻³. The pure molybdenum samples demonstrated lower passive current densities, lower charge carrier densities, and higher impedance than the TZM alloy. The lower corrosion resistance of TZM alloy could be attributed to the higher dislocation density, which acted as short-circuit paths for Mo diffusion, and the presence of carbides that exhibited a microgalvanic effect. Overall, this study clarified that the localized corrosion reported in the literature was not due to the breakdown of the passive layer but may be linked to the heterogeneous microstructure.

Iodine is produced through nuclear fission reactions in nuclear reactors. Understanding the electrochemistry of iodine species is crucial for reprocessing used nuclear fuels via molten salt electrolysis, deploying next-generation molten salt nuclear reactors, and developing iodide-based molten salt batteries. Cyclic voltammetry (CV) was conducted in LiCl-KCl eutectic molten salts at 450, 500, and 550 °C, both with and without the addition of KI as an iodine source. Based on the CV results, the diffusivities of iodide and triiodide species, as well as the activation energies for diffusion, were determined. Additionally, formal potentials of various iodide and interhalogen complexes were derived, allowing for the calculation of the stability constants for halide exchange reactions. The diffusivities of iodide ranged from 0.14 to 6.9 × 10⁻⁷ cm²/s, while those of triiodide were roughly an order of magnitude lower. Increasing the KI content from 1 wt% to 5 wt% reduced the diffusion coefficient, whereas increasing temperature, as expected, boosted diffusivity. The activation energy for iodide diffusion in LiCl-KCl increased from 46.5 kJ/mol to 112 kJ/mol as KI concentration rose from 1 wt% to 5 wt%.