Abstract

A synthetic route to silicon-based composite ceramics that employs organosilicon polymer/metal oxide precursors is described. The precursor materials were obtained by dispersing metal oxides in the poly[(silylene)diacetylenes] 1. Subsequent pyrolysis of the dispersions above 1400 °C under various experimental conditions afforded β-SiC-based metal carbides and metal nitrides, metal silicides and Si₃N₄-based composites of defined compositions, in high ceramic yields. Under atmospheres of argon or of nitrogen, the precursor-to-ceramic conversion involved two critical transformations: i) the thermal cross-linking of 1 leading to an irreversible encapsulation of the oxide particle inside the polymeric matrix and ii) the carbothermal reduction of the oxide constituents by the carbon resulting from the degradation of polymer 1 to produce either the final carbide or the final nitride under the pyrolysis conditions. Moreover, it is shown that the encapsulation of the oxide particles inside a reactive matrix led to the formation of particle-tailored micro-scale reactors in which the reduction process took place with high efficiency.