Solid-state NMR investigations of the polymer route to SiBCN ceramics

Abstract

Silicon based polymers obtained by ammonolysis of organochlorosilylboranes and their pyrolytic transformation into Si-B-C-N ceramics were studied by a detailed solid-state NMR investigation. Sol–gel polymerisation/pyrolysis routes were applied to form Si-B-C-N materials with exceptional high-temperature stability. The polymer to ceramic conversion was analyzed by 11B, 13C, 15N, and 29Si MAS NMR spectroscopy as well as by thermal analysis measurements coupled with mass spectroscopy (TGA–MS). The results showed that a significant change in the carbon-, silicon-, and boron-coordination environments occurs during pyrolysis. An evolution of cleavage of silcon–carbon–boron bridges and the formation of new BN3 sites was observed. The NMR data obtained suggest the presence of a rather homogeneous dispersion of the boron atoms in the as synthesized silicon carbonitride phase, supporting the high thermal stability with respect to decomposition found in these compounds.Key words: organosilicon polymers, polymer pyrolysis, SiBCN ceramics, solid-state NMR.