Long-Term Steam Oxidation and Microstructural Evolution of Sanicro 25 Steel After 30,000 h at 700 °C

This study investigates the oxidation behavior and microstructural evolution of Sanicro 25 steel (X7NiCrWCuCoNb25-23-3-3-2) after long-term exposure to water vapor at 700 °C for 30,000 h. Particular attention was paid to the relationship between protective oxide-scale formation, chromium depletion in the near-surface region, and the possible changes in secondary-phase stability in the steel substrate. FIB-SEM tomography was applied to characterize the oxide scale and the underlying affected zone, enabling three-dimensional visualization of oxide morphology, interfacial voids, and microstructural reconstruction beneath the scale. Long-term exposure resulted in the formation of a continuous Cr-rich oxide scale with a thickness of approximately 2.6 µm and local Mn enrichment. The scale exhibited a complex multilayered morphology, consisting of outer Cr-rich oxide crystallites, fine-grained chromium oxides, and an inner heterogeneous Mn-enriched region, suggesting the possible formation of mixed spinel-type oxides. Si-enriched regions were observed near the oxide/metal interface; however, no continuous Si oxide layer was detected. Despite the presence of interfacial voids, no scale spallation was observed in the investigated regions. SEM-EDX analysis revealed a chromium-depleted subsurface zone extending to approximately 6.5 µm below the oxide scale. CALPHAD calculations suggest that local chromium depletion may reduce the thermodynamic stability of Cr-rich M23C6 carbides and the Nb–Cr–N-type Z phase. This possible reduction in phase stability may contribute to the formation of a precipitate-depleted region and local microstructural reconstruction beneath the oxide scale. In the bulk region, where oxidation effects were negligible, the microstructure consisted of an austenitic matrix containing M23C6 carbides, σ phase, Cr–Ni–Fe nitride with an A13-type structure, ε-Cu precipitates, Z phase, and W-rich Cu-containing TCP precipitates. The simulations further suggest that most secondary phases form during the early stage of annealing, whereas prolonged exposure is dominated by diffusion-controlled coarsening. Overall, Sanicro 25 shows good resistance to long-term steam oxidation at 700 °C due to the formation of a continuous Cr-rich protective scale. However, this protection is accompanied by chromium depletion and local near-surface microstructural changes, which should be considered when assessing the long-term stability and service performance of this steel under high-temperature steam conditions.