Additive and pyrolysis atmosphere effects on polysiloxane-derived porous SiOC ceramics

Porous silicon oxycarbide (SiOC) is emerging as a much superior ultrahigh surface area material that can be stable up to high temperatures with great tailorability through composition and additive modifications. In this study, bulk SiOCs were fabricated from a base polysiloxane (PSO) system by using different organic additives and pyrolysis atmospheres followed by hydrofluoric acid (HF) etching. The additives modify the microstructural evolution by influencing the SiO2 nanodomain formation. The SiOC ceramics contain significantly less SiC and more SiO2 with Ar + H2O atmosphere pyrolysis compared to Ar atmosphere pyrolysis. Water vapor injection during pyrolysis also causes a drastic increase in specific surface areas. The addition of 10 wt% tetraethyl orthosilicate (TEOS) with Ar + H2O pyrolysis produces a specific surface area of 1953.94 m2/g, compared to 880.09 m2/g for the base PSO pyrolyzed in Ar. The fundamental processes for the composition and phase evolutions are discussed as a novel pathway to creating ultrahigh surface area materials. The ability to drastically increase the specific surface area through the use of pyrolysis atmosphere and organic additives presents a promising processing route for highly porous SiOC ceramics.