Pyrolyzed preceramic precursors to compositionally complex ceramics

Abstract

Ceramics from chemically distinct preceramic polymers offer unique shaping and microstructural control but face challenges such as shrinkage, uncontrolled porosity, and pyrolysis-sensitive stoichiometry. The high-temperature potential of compositionally complex ceramics is further constrained by precursor scarcity and the low-throughput nature of pyrolysis. Here, we introduce short-chain preceramic precursors crosslinked with group IV–VI transition metals (Zr, Cr, V, Mo, Hf, W, Nb, etc.), which are compatible with additive manufacturing. We explored extrusion and ultrafast pyrolysis with multi-metal precursors to enable enhanced compositional complexity, lower processing temperatures, and rapid screening of oxidation-resistant ceramics. Through ultrafast electrical pyrolysis, these crosslinked precursors convert into dense, multi-phase ceramics in under a minute. The resulting materials exhibit homogeneous composition and oxidation resistance up to 1,873 K, offering a scalable route to protective coatings and bulk ceramics for extreme environments.