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      • Single-Source-Precursor Synthesis of Hafnium-Containing Ultrahigh-Temperature Ceramic Nanocomposites (UHTC-NCs)

        Yuan, Jia,Hapis, Stefania,Breitzke, Hergen,Xu, Yeping,Fasel, Claudia,Kleebe, Hans-Joachim,Buntkowsky, Gerd,Riedel, Ralf,Ionescu, Emanuel American Chemical Society 2014 Inorganic chemistry Vol.53 No.19

        <P>Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt<SUB>2</SUB>)<SUB>4</SUB> and BH<SUB>3</SUB>·SMe<SUB>2</SUB>, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N<SUB>2</SUB>) at temperatures in the range of 1300–1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB<SUB>2</SUB>/SiC (annealing in argon) and HfN/Si<SUB>3</SUB>N<SUB>4</SUB>/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based preparative path toward nanostructured ultrahigh-temperature stable materials with adjusted compositions.</P><P>Amorphous SiHfBCN ceramics were prepared from a suitable single-source precursor. Annealing experiments of the SiHfBCN samples in an inert gas atmosphere at temperatures of 1300−1700 °C led to their conversion nanostructured UHTC-NCs, such as HfC/HfB<SUB>2</SUB>/SiC nanocomposites (in argon) and HfN/Si<SUB>3</SUB>N<SUB>4</SUB>/SiBCN nanocomposites (in nitrogen), thus revealing a convenient preparative approach to nanostructured ultrahigh-temperature stable materials starting from a greatly flexible single-source precursor.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2014/inocaj.2014.53.issue-19/ic501512p/production/images/medium/ic-2014-01512p_0016.gif'></P>

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