Media type: E-Article Title: Synthesis of polymeric precursors for the formation of nanocrystalline Ti‐C‐N/amorphous Si‐C‐N composites Contributor: Hering, Nicole; Schreiber, Kai; Riedel, Ralf; Lichtenberger, Olaf; Woltersdorf, Jörg imprint: Wiley, 2001 Published in: Applied Organometallic Chemistry Language: English DOI: 10.1002/aoc.241 ISSN: 0268-2605; 1099-0739 Keywords: Inorganic Chemistry ; General Chemistry Origination: Footnote: Description: <jats:title>Abstract</jats:title><jats:p>The synthesis of trimethylsilyl‐substituted poly(titaniumcarbodiimide) as a novel precursor for titanium carbonitride based ceramic materials is described. The precursor and the subsequent processing steps (cross‐linking and pyrolysis) are characterized by IR and Raman spectroscopy, thermal gravimetric analysis and simultaneous mass spectroscopy, electron microscopy and powder X‐ray diffraction measurements. The novel polymer is formed by the reaction of TiCl<jats:sub>4</jats:sub> or Ti(NEt<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub> with bis(trimethylsilyl)carbodiimide. Subsequent pyrolysis at 1000 °C in argon results in the formation of a ceramic composite material consisting of nanocrystalline TiCN and amorphous SiCN as constituting phases. Using Ti(NEt<jats:sub>2</jats:sub>)<jats:sub>4</jats:sub> as a starting reagent instead of TiCl<jats:sub>4</jats:sub>, chlorine contamination of the ceramic material can be avoided. The different molecular vibration modes of the metal–nitrogen, metal–carbon and nitrogen–carbon bonds in poly(titaniumcarbodiimides) with trimethylsilyl substituents were calculated using quantum mechanical methods, providing a comprehensive understanding of the measured spectra. Copyright © 2001 John Wiley & Sons, Ltd.</jats:p>