Advances in Understanding of Secondary Phases and Their Corrosion Implications in Stainless Steel Alloys—A Review

The formation and evolution of secondary phases, such as sigma (σ), chi (χ), Laves, carbides (M23C6), and nitrides (Cr2N), have a fundamental impact on the corrosion resistance of stainless steels. These stages alter the matrix’s local chemistry, compromise the passive film’s quality, and promote micro-galvanic interaction, which enhances localized corrosion issues. The thermodynamic stability, precipitation kinetics, and corrosion consequences of secondary phases in austenitic, ferritic, duplex, and lightweight (Fe–Mn–Al–C) stainless-steel systems are thoroughly reviewed and discussed in this paper. Advances in high-resolution characterization techniques, such as TEM, EBSD, atom-probe tomography, and in situ synchrotron techniques, have made it possible to map corrosion problems caused by secondary phases at the nanoscale. Computational thermodynamics (CALPHAD, DICTRA, TC-PRISMA) and emerging machine-learning models now provide quantitative prediction of phase formation and dissolution. Strategies for mitigation through alloy design, thermal treatment, and surface engineering are summarized, together with additive-manufacturing approaches for microstructural tailoring. Finally, this review highlights the integration of multi-scale modeling and sustainable alloy design to ensure phase-stable, corrosion-resistant stainless steels that enhance asset integrity and infrastructure reliability as per Sustainable Development Goals.