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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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Polymer‐derived SiOC/HfO2 ceramic nanocomposites were prepared via chemical modification of a commercially available polysilsesquioxane by hafnium tetra (n‐butoxide). The ceramization process of the starting materials was investigated using thermal analysis and in situ Fourier‐transformed infrared spectroscopy and mass spectrometry. Furthermore, solid‐state NMR, elemental analysis, powder X‐ray diffraction, and electron microscopy investigations were performed on ceramic materials pyrolyzed at different temperatures ranging from 800° to 1300°C, in order to obtain information about the structural changes and phase evolution thereof. The hafnium alkoxide‐modified precursor was shown to convert into an amorphous single‐phase SixHfyOzCw ceramic at temperatures up to 800°C. By increasing the temperature to 1000°C, amorphous hafnia begins to precipitate throughout the silicon oxycarbide matrix; thus, monodisperse hafnia particles with a diameter of <5 nm are present in the ceramic, indicating a homogeneous nucleation of HfO2. At temperatures ranging from 1100° to 1300°C, crystallization of the hafnia nanoprecipitates as well as phase separation of the SiOC matrix occur. The chemical modification of the preceramic precursor with hafnium alkoxide can be considered as a promising method for the preparation of SiOC/HfO2 nanocomposites with well‐dispersed hafnia nanoparticles.