Microstructure Development of Oxycarbide Composites during Active-Filler-Controlled Polymer Pyrolysis

The microstructure development of a ceramic composite material fabricated by active-filler-controlled polymer pyrolysis (AFCOP) was investigated. During heating of a polysiloxane precursor mixed with titanium powder in argon atmosphere up to 1400°C, thermally induced decomposition of the polymer phase is combined with simultaneous carburization of the transition metal filler. Precipitation of nanocrystalline titanium carbide at the filler particle surface starts above 400°C, and larger, faceted carbide particles have growth above 800°C. A skeleton of turbostratic carbon is formed above 800°C in the polymer-derived silicon oxycarbide matrix from which b-silicon carbide and cristobalite crystallize above 1000°C. A pronounced reduction in linear shrinkage involved in polymer–ceramic conversion is observed. The shrinkage reduction ranges from more than 25% for the filler-free precursor to less than 10% in the presence of 30 vol% of the titanium filler. Thus, active-filler-controlled pyrolysis offers the possibility of controlling shrinkage and porosity formation during polymer–ceramic conversion in order to fabricate bulk components from organometallic polymer precursor systems.