In polymer nanocomposites, interactions between filler particles and matrix material play a crucial role for their macroscopic properties. Nanocomposites consisting of varying amounts of silica nanoparticles and an epoxy resin based on diglycidyl ether of bisphenol-A (DGEBA) have been studied before and during network formation (curing). Rheology and mainly temperature modulated differential scanning calorimetry (TMDSC) have been used to investigate interactions between the silica nanoparticles and molecules of the epoxy oligomer or molecules of the growing epoxy network. Measurements of the complex specific heat capacity before curing showed that interactions between the nanoparticles and DGEBA molecules are very weak. An expression for an effective specific heat capacity of the silica nanoparticles could be deduced. Examination of the isothermal curing process after addition of an amine hardener yielded evidences for a restricted molecular mobility of the reactants in the cause of network formation. These restrictions could be overcome by increasing the curing temperature. No evidences for an incorporation of the silica nanoparticles into the epoxy network, i.e. for a strong chemical bonding to the network, were found. Interactions between the silica nanoparticles and the epoxy resins under study are assumed to be of a physical nature at all stages of network formation. (C) 2009 Elsevier Ltd. All rights reserved.