Crosslinking and pyrolysis of a methyl-silsesquioxane: Effect of heating rate on fabrication of polymer derived mullite ceramics using thermoplastic shaping

Poly-silsesquioxanes have been numerously used to produce SiO2 or SixOyCz ceramics through pyrolysis under different atmospheres. In this study, crosslinking and pyrolysis behavior of a commercial methyl-silsesquioxane, was examined using thermogravimetry analysis and a lower SiO2 yield was observed after pyrolysis at low heating rates of 0.3 and 0.6 K/min under air atmosphere, namely 69.1 and 75.0 wt%, respectively. Using ceramic thermoplastic shaping techniques, a low heating rate, below 2 K/min, is usually required to remove processing additive (e.g., binders) gradually and avoid failures like blisters, pores, and cracks. A mixture of SILRES (R) MK and gamma-Al2O3 was prepared to produce a mullite ceramic with Al2O3/ SiO2 ratio of 60/40 wt%. As expected, the stoichiometric ratio of alumina to silica was altered using a heating rate of 0.6 K/min and mullite ceramic with 61.70/37.70 wt% of Al2O3/ SiO2 ratio was obtained. By mixing above the crosslinking temperature of SILRES (R) MK, a constant ratio of alumina to silica could be achieved successfully, even at low heating rates. In addition, microstructure indicated the growth of needle-like mullite crystals with some amount of SiO2-rich ternary amorphous phase (MgO-Al2O3-SiO2) between the needle grains. Elemental analysis revealed that MgO sintering additive was mainly in the amorphous SiO2-rich phase.