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DOI: 10.1039/A603181A (Paper) Reference Section for: J. Mater. Chem., 1997, 7, 117-126

Pyrolysis chemistry of polysilazane precursors to silicon carbonitride

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Corine Gérardin, Francis Taulelle and Djamila Bahloul

Abstract

The chemistry of pyrolytic conversion has been studied for three polysilazanes, (ViSiHNH)n, (ViSiHNMe)nand [(ViSiHNH)0.5–(MeSiHNH)0.5 ]n, precursors to silicon carbonitride ceramics.13C and 29Si MAS and CPMAS NMR spectroscopies were used to clarify the processes leading to the formation of the silicon-based mineral network as well as the segregation of a free carbon phase. The assignment of 29Si NMR signals corresponding to SiCnN4-nsites was essential to follow the number of Si–C and Si–N bonds that are cleaved or formed. It was shown that at the organic–mineral transition temperature (ca. 900 °C) the final amount of free carbon as well as the final composition of the silicon-based network were already reached. Above this temperature, redistribution reactions around silicon atoms inside the amorphous silicon-based matrix take place in order to favour nitrogen-rich environments, i.e. crystallized Si3N4 regions. Above 1400 °C, all ceramics contain a similar amorphous silicon carbonitride structure, whose composition is close to SiN0.85C0.35 and which coexists with a crystallizing Si3N4 phase. Finally, the relative amounts of the three possible final carbon states, at 1400 °C, i.e. gas products, carbon incorporated in the silicon-based network and free carbon, could be related to the nature of the carbon-containing substituents in the precursor backbones and to the occurrence of the cross-linking reactions below the mineral transition temperature.

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