Silica reinforcing fillers were generated using the sol-gel approach and their surfaces were modified using either a vinyl alkoxysilane (to provide permanent bonding to a host poly(dimethylsiloxane) elastomer), or a hemiacetal ester (to provide bonding that could be thermally ruptured). The surface areas of the fillers were measured by nitrogen absorption, and their morphologies, interfacial structures, and crosslinking to the elastomer were characterized by ultra small angle and small angle X-ray scattering, scanning electron microcopy, and Fourier-transform infrared spectroscopy. Increasing the amount of the silane coupling agent decreased silica domain sizes, with corresponding increases in surface area and stronger filler-polymer interactions. Vinyltrimethoxysilane had a larger effect than vinylmethyldimethoxysilane. The tensile moduli, tensile strengths, and degrees of toughness of the composites were determined using stress-strain measurements in elongation, both under near-equilibrium conditions and under continuous extension. The permanently bonded modifications gave composites with improved mechanical properties. Rupturing the hemiacetal ester bonding at 120-150degreesC gave some increase in ultimate stress, maximum elongation, and toughness, thus underscoring the importance of interactions or 'networking' between filler particles.