Effect of Cr–Ni Co-Alloying on Corrosion Behavior and Rust-Layer Evolution of HRB500 Rebar in Chloride-Containing Environments

This study investigated how increased Cr and Ni contents affect the corrosion behavior and rust layer evolution of HRB500 rebar in chloride-containing environments. Corrosion of the Cr- and Ni-alloyed rebars was characterized by distinct stages: in the initial stage, before a stable rust layer formed, the corrosion rate increased; with continued immersion, corrosion products progressively covered the surface and became more compact, and the overall corrosion rate decreased. Higher Cr and Ni contents were found to mitigate overall corrosion damage, markedly suppress localized corrosion, and shift the corrosion morphology toward a more uniform attack. Electrochemical measurements showed a noble shift in corrosion potential, a reduction in corrosion current density, and significant increases in low-frequency impedance and charge transfer resistance, indicating enhanced barrier properties against charge transfer and ionic migration. With corrosion progression, rust layer phases evolved from an Fe₃O₄-dominated assemblage to enrichment in stable iron oxyhydroxides; the fraction of α-FeOOH increased, raising the α/γ* index and suggesting improved rust layer stability and protectiveness. Mechanistically, Cr and Ni enrichment was found to facilitate the conversion of metastable products to α-FeOOH and to promote the formation of compact spinel oxides FeCr₂O₄ and NiFe₂O₄, thereby hindering chloride ion ingress and interfacial corrosion reactions and markedly improving corrosion resistance. Overall, this work elucidated the Cr–Ni co-alloying mechanism for rust layer stabilization and pitting suppression. At 504 h, the high Cr–Ni rebar reduced the maximum pit depth by approximately 61.8% and lowered i_corr to approximately 43% of that of the low Cr–Ni rebar, thereby providing quantitative guidance for marine-grade rebar design.