Equilibrium relationships between thermal barrier oxides and silicate melts

The phase equilibria between thermal barrier coating (TBC) materials and calcium–magnesium–aluminosilicate melts (CMAS, representing deposits formed when siliceous debris is ingested into modern turbine engines), were investigated at 1300 °C. The primary goal was to understand the influence of the deposit and thermal barrier oxide compositions on the melt solubility limits and reaction product constitution. Model deposit compositions with SiO₂ to CaO ratios from 1.4 to 4.7 and with or without MgO were reacted with yttria- and gadolinia-zirconia thermal barrier oxides ranging from pure ZrO₂ to the pure yttria and gadolinia. The reactions formed various crystalline silicate phases; rare earth–calcium–silicate apatite and zircon (ZrSiO₄) were observed most frequently. Following the reactions, the residual melts were depleted in SiO₂ and generally enriched in CaO, MgO, and Al₂O₃. The implications of the anticipated changes in the melt viscosity and the cation partitioning between the melt and various solid solution phases on the efficacy of degradation-mitigating crystallization reactions are discussed.