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This study presents new experimental data on the thermodynamic stability of SiC(O) and SCN(O) ceramics derived from the pyrolysis of polymeric precursors: SMP‐10 (polycarbosilane), PSZ‐20 (polysilazane), and Durazane‐1800 (polysilazane) at 1200°C. There are close similarities in the structure of the polysilazanes, but they differ in crosslinking temperature. High‐resolution X‐ray photoelectron spectroscopy shows notable differences in the microstructure of all polymer‐derived ceramics (PDCs). The enthalpies of formation (∆H°_{f, elem}) of SiC(O) (from SMP‐10), SCN(O) (from PSZ‐20), and SCN(O) (from Durazane‐1800) are −20 ± 4.63, −78.55 ± 2.32, and −85.09 ± 2.18 kJ/mol, respectively. The PDC derived from Durazane‐1800 displays greatest thermodynamic stability. The results point to increased thermodynamic stabilization with addition of nitrogen to the microstructure of PDCs. Thermodynamic analysis suggests increased thermodynamic drive for forming SiCN(O) microstructures with an increase in the relative amount of SiN_xC_4−xmixed bonds and a decrease in silica. Overall, enthalpies of formation suggest superior stabilizing effect of SiN_xC_4−xcompared to SiO_xC_4−xmixed bonds. The results indicate systematic stabilization of SiCN(O) structures with decrease in silicon and oxygen content. The destabilization of PDCs resulting from higher silicon content may reach a plateau at higher concentrations.

 

Electrospinning is an emerging technique for synthesizing micron to submicron-sized polymer fibre supports for applications in energy storage, catalysis, filtration, drug delivery and so on. However, fabrication of electrospun ceramic fibre mats for use as a reinforcement phase in ceramic matrix composites or CMCs for aerospace applications remains largely unexplored. This is mainly due to stringent operating requirements that require a combination of properties such as low mass density, high strength, and ultrahigh temperature resistance. Herein we report fabrication of molecular precursor-derived silicon oxycarbide or SiOC fibre mats via electrospinning and pyrolysis of cyclic polysiloxanes-based precursors at significantly lower weight loadings of organic co-spin agent. Ceramic fibre mats, which were free of wrapping, were prepared by a one-step spinning (in air) and post heat-treatment for crosslinking and pyrolysis (in argon at 800 °C). The pyrolyzed fibre mats were revealed to be amorphous and a few microns in diameter. Four siloxane-based pre-ceramic polymers were used to study the influence of precursor molecular structure on the compositional and morphological differences of cross-linked and pyrolyzed products. Further thermal characterization suggested the potential of electrospun ceramic mats in high temperature applications.