Alloys of Ni–25Cr–(2Mn–1Si) under mixed deposits of ash + (0, 10, 50 and 90) wt% sulphate were exposed to an Ar–60CO2–20H2O gas at 650 and 750 °C for up to 300 h, forming both protective chromia and regions of Ni-rich oxide. The presence of ash + sulphate mixtures improved Ni–25Cr alloy protection, increasing surface coverage by thin, protective chromia compared with the deposit-free condition. Increasing sulphate proportions in these mixtures led to an accelerated chromia scale growth and reduced internal oxidation zone (IOZ). These beneficial effects were more significant at 750 °C, where surface coverage by the protective scale was increased, and a chromia band was formed beneath nonprotective regions at the IOZ-substrate interface. Alloy additions of Mn and Si generally slowed the growth of outer NiO and IOZ but did not lead to exclusive chromia scale formation.