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, car-bides (M₂₃ C₆), and nitrides (Cr₂ N), 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.