Electrochemical Machining of Highly Strain-Hardenable High-Entropy FeMnCrCoSi Alloy: Role of Passivation and Selective Dissolution

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.