Effect of Ca and B incorporation into silicon oxycarbide on its microstructure and phase composition

Ca- and/or B-modified silicon oxycarbides were synthesized via pyrolysis of suitable polysilsesquioxane-based single-source precursors. Their polymer-to-ceramic transformation was investigated with thermogravimetric analysis, coupled with in situ evolved gas analysis. The prepared silicon oxycarbides were investigated with respect to their crystallization behavior, network architecture, and chemical compositions. The network connectivity in silicon oxycarbides can be affected/tuned upon using two different tools: (a) first, the use of network modifiers, such as Ca in our study, leads to a slight depolymerization of the network via generation of a small amount of Q(3) sites; (b) second, the modification of silicon oxycarbide with B/Ca leads to a decrease of the carbon content in the network and thus to a significant decrease of its connectivity. Using these two different effects, the network connectivity in silicon oxycarbides can be finely tuned.