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Thermodynamically Stable SixOyCz Polymer-Like Amorphous Ceramics

Authors


  • T. Besmann—contributing editor

  • This work was supported by grants from the Ceramics Program of the Division of Materials Research of the National Science Foundation DMR-0502781 at the University of Colorado, and DMR-0502446 at University of California, Davis. These grants are funded under the MWN (Materials World Network) Program between the National Science Foundation and the Deutsche Forschungsgemeinschaft. The research at Stuttgart is supported by DFG—Mu 1166/12-1.

†Author to whom correspondence should be addressed. e-mail: tvarga@anl.gov

Abstract

Carbon can be used to create unusual nanostructures of Si–C–O by controlled pyrolysis of silsesquioxane organics. Unlike silica, these ceramics resist crystallization at ultrahigh temperatures. Their structure has been compared with that of polymers, where crosslinked chains of polymers in organics are replaced by crosslinked networks of graphene in the ceramics. The network sequesters nanoscale domains of SiO4 tetrahedra. The resistance to crystallization of these nanodomain networks has been attributed to kinetic factors, namely obstruction of long-range diffusion of silica. In this work, we identify a thermodynamic hindrance to crystallization. Calorimetric measurements of heats of dissolution in a molten oxide solvent show that these ceramics possess a negative enthalpy relative to their crystalline constituents (silicon carbide, cristobalite, and graphite). The thermodynamic stability of the nanodomain structure is explained by a low free energy of the graphene–silica interfaces, perhaps related to the presence of mixed bonds of silicon bonded to both carbon and oxygen.

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