Enhanced high-temperature corrosion resistance of Cr-modified phosphate/aluminum powder composite coatings: Mechanisms and thermodynamic insights

[Display omitted] •A high-temperature and salt-spray-resistant Cr-incorporated phosphate/aluminum powder composite coatings were developed.•Cracked surfaces caused by tensile stress were eliminated by Cr involvement.•The selective corrosion of Cr/Mg/Fe oxide in a mixed amorphous oxide contributes to corrosion resistance. Phosphate composite coatings are regarded as one of the tangible solutions for surface protection in salt spray environments, benefiting from their cost-effectiveness and prominent structure stability upon high-temperature exposure. However, rapid curing of these coatings often leads to crack formation, and the underlying corrosion mechanisms in service conditions remain insufficiently understood, limiting their practical applications. In this study, we developed chromium-incorporated phosphate/aluminum powder composite (Cr-P/Al) coatings and evaluated their corrosion resistance under alternating conditions of salt spray corrosion and oxidation at 450 °C. By integrating experimental results, ab initio calculations, and thermodynamic analysis, we demonstrate that the incorporation of Cr significantly enhances the performance of the P/Al coatings. The structural evolution was first revealed that Cr’s modification reduced tensile stress and prevented cracks in the coating. A mixed layer of amorphous oxides and phosphates forms on the surface of the Al powder, providing robust binding strength. A novel corrosion mechanism was identified that Cl2 and volatile chlorides facilitated the removal of Cl-. This process is more ineffective with Cr-P/Al coating, as amorphous Cr oxide has low reactivity at a high log[p(Cl2)] and low log[p(O2)] compared with amorphous Mg and Fe oxide, thereby enhancing the corrosion resistance of the coating. These coating densification methods and corrosion protection mechanisms provide a critical foundation for the future application of phosphate composite coatings.