Ultra-high temperature ceramics: Aspiration to overcome challenges in thermal protection systems

Ultra-high temperature ceramics (UHTCs) have played a significant role in fulfilling demands for the thermal protection system (TPS) in the aerospace sector, however, a promising candidate has not emerged yet. This critical review provides typical inconsistencies and new perspectives related to UHTCs in terms of: (i) material and processing: i.e., sinterability, reinforcements, microstructural evolution, (ii) properties and performance correlation with the processing conditions and resulting microstructure, and (iii) outlook on the most promising ZrB₂-HfB₂-SiC-based composites as potential candidates for hypersonic leading edge and re-entry structures. An optimal selection of the content, size and reinforcing phase (such as silicides, refractory carbides, and carbon-based, etc.) is mandated in upgrading the thermo-mechanical performance of UHTCs to sustain elevated temperature (1700 °C), exhibiting flexural/fracture strength of >300 MPa, high thermal conductivity >14.5 Wm^?1K^?1, and high oxidation resistance (<80 gm^?2 over 2 h at 1400 °C). From emphasis on the powder purity, and sintering additives on affecting the densification, mechanical properties and high temperature oxidation, improvements in the functional performance of UHTCs are carried forward with emphasis mainly on borides and carbides. Emergence of SiC as most promising sintering additive with optimal content of ～20 vol%, and with supplemented HfB₂ addition in ZrB₂-HfB₂-SiC based UHTCs have exhibited higher oxidation resistance and may serve as conceivable entrants for hypersonic vehicles. Further, the review leads the reader to developing new materials (including silicides, MAX phases, and high entropy UHTCs), incorporating novel strategies like designing layered structures or functionally graded materials (FGM), and effective joining to allow the integration of smaller components into scaled up structures. On one hand, where plasma arc-jet exposure mimics high heat-flux exposures, the utilization of multi-length-scale computational modeling (such as finite element methods, density functional theory, ab initio etc.) allows assessing the material performance under dynamic changes (of variable partial pressure, temperatures, gradation, etc.) towards perceiving new insights into the structural stability and thermo-mechanical properties of UHTCs. This review critically underlines the present state of the art and guides the reader towards the futuristic development of new class of high-temperature materials for TPSs.