Synthesis of a meltable polyzirconosilane precursor for SiZrNC multinary ceramics

Polymeric precursors with refractory metal in the main chain while still possess meltable/soluble characteristics are highly desired for ultra-high temperature ceramics (UHTCs). Herein, we proposed a stepwise synthesis of polyzirconosilane (PZCS) with Zr-C-Si-N polymeric chain. The reaction mechanism was discussed based on the frontier molecular orbital theory and atom transfer radical polymerization , which was initiated and propagated by a low oxidation state active specie of Cp 2 Zr(II). The PZCS precursor has excellent soluble and meltable properties with a softening point of 80.8 ~ 89.2  o C, which could be spun into green fibers by melt spinning technique. The ceramization process of PZCS was studied, and the resulted SiZrNC multinary ceramics were composed of ZrC/SiC nanocrystals embedded by graphitized carbon phase. The excellent mouldable properties, oxygen-free compositions and high Zr content of PZCS make it an ideal precursor for the preparation of UHTCs matrixes and fibers.