Performance of nitrogen ion-implanted supermartensitic stainless steel in chlorine- and hydrogen-rich environments

Modified supermartensitic stainless steel surfaces were investigated as protective means against deterioration in Cl−- and H+-rich media. Nitrogen plasma immersion ion implantation at the 300–400 °C range produced top nitride-rich layers (with mainly γ′-Fe4N and ε-Fe2-3N, but also with α′N, according to the treatment temperature) followed by underneath expanded martensite cases. The 400 °C nitrided sample presented the best performance in potentiodynamic polarization tests with NaCl electrolyte, featured by 4.3 times increase in the corrosion potential and the absence of pits, attributed to the thickest and continuous ε-phase containing nitride-rich layer. The hydrogen embrittlement was assessed through cathodic hydrogenation tests. Both reference and 400 °C nitrided surfaces disclosed the phenomenon of intensified plastic flow under normal and tangential loadings. A decrease in hardness, elastic modulus and scratch resistance featured a ductile-to-brittle transition on the nitrided surface, possibly due to improved hydrogen trapping by nitride species with subsequent effects in plasticity. In summary, while the nitride layer played an advantageous role in protecting SMSS from chlorine attack, it was susceptible against the hydrogen corrosion. •N-PIII produced stratified layers with nitrides and expanded martensite on SMSS.•Corrosion resistance in Cl−-containing medium improved in all the nitrided surfaces.•Modified surfaces with ε-Fe2-3N provided 4.3 times increase in corrosion potential.•H-attack caused intensified surface plastic flow and ductile-to-brittle transition.•The layer's susceptibility against hydrogenation compromises the SMSS bulk protection.