"Anomalous Solid Solution" in Ultra-High Melting Point Oxides: A New Strategy for Developing Ultra-High Temperature Thermal Protection Coatings

Abstract

The high-temperature performance of ultra-high temperature ceramics (UHTCs) in atmospheric environment is fundamentally governed by their melting points of oxidation products. Typical high-melting-point oxides, such as ZrO2, undergo phase transformations at elevated temperatures, leading to structural instability. Although doping with rare-earth or transition-metal cations can suppress these transformations, it often results in a reduction in melting point, thereby limiting practical service temperature. Here, ytterbia-stabilized zirconia (YbSZ) coatings are prepared via atmospheric plasma spraying, achieving a remarkable increase in the melting point of ZrO2 to approximately 2850 $^\circ\mathrm{C}$ and raising the ultimate plasma and oxyacetylene ablation temperature up to nearly 2780 $^\circ\mathrm{C}$ and 3200 $^\circ\mathrm{C}$, which is the highest temperature resistance property as reported. Notably, this performance enhancement originates from a synergistic mechanism of strengthened ionic-covalent mixed bonding and improved oxygen vacancy stability. Based on these findings, the concept of "anomalous solid solution" is firstly proposed to be used in the area of ultra-high temperature protection, which provides new insights into the compositional design of UHTC systems.