Nanocomposites consisting of an epoxy network matrix and a silica reinforcing phase were produced from a resin mixture functionalized with alkoxysilane coupling agents. Particulate nanocomposites were obtained by dispersing silica-organosol particles in the resin, while bicontinuous phase nanocomposirtes were obtained by the in-situ hydrolysis and condensation of tetraethoxysilane containing minor amounts of gamma-glycidoxyl trimethoxysilane. Functionalization of the epoxy resin with an amine silane coupling agent was found to be more effective in aiding the dispersion of silica sol particles in the resin than the corresponding resin functionalized with a mercaptan silane coupling agent. Similar differences in the efficiency of coupling agent grafted on to the epoxy resin were observed for bicontinuous phase nanocomposites. The amine silane functionalization produces denser silica domains, which results in a higher rubber-plateau modulus and higher resistance to solvent penetration. The study also showed that the particulate nanocomposites are very ineffective in improving the solvent resistance of the base resin, even when the resin is grafted with a very efficient amine silane coupling agent, which promotes interfacial bonding. The different types of morphology were characterized by transmission electron microscopy and small angle X-ray scattering analysis. (c) 2006 Springer Science + Business Media, Inc.