Cosolvent-free sol–gel synthesis of macroporous silica gels from tetramethoxysilane–tetraethoxysilane mixtures

Abstract

Abstract Tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and their mixtures were used for the cosolvent-free synthesis of macroporous silica gels as precursors for monolithic silica glasses. The liquid-state 29Si nuclear magnetic resonance (NMR) spectroscopy of precursor solutions indicated that cross-transesterification between TMOS and TEOS was completed in a few hours at 20 °C in the presence of an acid catalyst, whereas it was negligible when the catalyst was absent. In the precursor solutions prepared from TMOS, phase separation occurred after gelation, resulting in translucent gels. In contrast, in the solutions prepared from TEOS or a mixture of TMOS and TEOS at a TMOS mole fraction of 0.8, the phase separation can be induced before gelation, and opaque xerogels were easily obtained without fracture. The average size of macroscopic particles and macroporous structures were uniform over opaque xerogels prepared from TEOS. In contrast, in opaque xerogels prepared from the TMOS-rich mixture of TMOS and TEOS, the average particle size and macroscopic porosity inside them were notably smaller than those of the subsurface, probably because of a large exotherm upon gelation and the resulting temperature gradient in the gelling solutions. Such spatial morphology distribution made the sintering of the opaque gels into clear silica glasses difficult. Opaque gels prepared from TEOS and translucent gels prepared from solutions containing TMOS were transformed to clear silica glasses in high yields of ~99% by sintering in a helium atmosphere at 1050–1350 °C. Graphical abstract