Electrochemical corrosion and product formation mechanism of M42 high-speed steel in NaH2PO4-Na2SO4 passivating electrolyte

High-speed steel (HSS) rolls operate in harsh conditions, making them vulnerable to surface degradation. Material removal technology for repairing defective HSS roll surfaces is the most effective way to maintain their integrity and reduce production costs. Electrochemical corrosion machining, with its excellent machining capabilities, offers a promising method for repairing HSS roll surfaces. However, the outer working layer of these rolls is made of premium HSS containing passivating metallic elements, complicating its corrosion behavior, particularly in passivating electrolytes. To elucidate the corrosion behavior and uncover the underlying mechanisms of corrosion and product formation of HSS during electrochemical corrosion machining, this study investigates the electrochemical corrosion process and behavior of M42 HSS used in rolls within a NaH₂PO₄-Na₂SO₄ passivating electrolyte. Metallographic etching experiments indicated that M42 HSS comprises a tempered martensitic matrix along with M₂C and M₆C eutectic carbides. Characteristics of oxidative reactions for M42 HSS in the electrolyte were observed in cyclic voltammetry. By conducting anodic polarization tests, along with thermodynamic analysis and characterization techniques, the entire electrode system was thoroughly examined, including corrosion phenomena, varying processes, and underlying mechanisms of corrosion and product formation. Notably, this study is the first to construct a Pourbaix diagram for the M42 HSS-H₂PO₄⁻-SO₄²⁻–H₂O system. The thermodynamic analysis revealed that the applied potential variation significantly influences corrosion behavior of M42 HSS, confirming by the characterization results. The adsorption phenomenon on the cathodic surface requires a higher potential (such as 6 V) to occur. Electrochemical reactions primarily occur on the anodic surface, while the cathodic surface (or in the electrolyte) mainly engages in chemical reactions with no electronic participation. Furthermore, the electrochemical corrosion process of HSS is driven by one or more corrosion mechanisms, such as galvanic corrosion, pitting, or intergranular corrosion. Therefore, these findings from this study contribute to the development of repairing HSS roll surfaces based on electrochemical corrosion machining in future engineering applications.