Silicon Carbide Precursor: Structure Analysis and Thermal Behavior from Polymer Cross-Linking to Pyrolyzed Ceramics

The Silres H62C methyl-phenyl-vinyl-hydrogen polysiloxane is a promising candidate as a SiC precursor for 3D printing based on photopolymerization reaction. An in-depth nuclear magnetic resonance spectroscopy analysis allowed us to determine its structure and quantify its functional groups. The polysiloxane was found to have a highly branched ladder-like structure, with 21.9, 31.4 and 46.7% of mono-, di- and tri-functional silicon atoms. The polysiloxane cross-links from 180 °C using hydrosilylation between silyl groups (8.4% of the total functional groups) and vinyl groups (12.0%) and contains a non-negligible ethoxy content (2.4%), allowing cross-linking through a hydrolyze/condensation mechanism. After converting the polymer into ceramic and thus releasing mainly hydrogen and methane, the ceramic yield was 72.5%. An X-ray diffraction analysis on the cross-linked and pyrolyzed polysiloxane showed that the ceramic is amorphous at temperatures up to 1200 °C and starts to crystallize from 1200 °C, leading into 3C-SiC carbon-rich ceramic at 1700 °C in an argon atmosphere.