[en] High-performance refractometry and infrared spectroscopy are combined in order to elucidate the gelation process and the glass transition during the network formation of epoxies and epoxy-based nanocomposites. Whereas infrared spectroscopy yields the chemical conversion due to the opening of oxirane rings during the covalent network formation, high-performance refractometry is extremely sensitive to the accompanying changes of the arrangement of the molecular network. In accordance with the Lorentz-Lorenz relationship, the evolution of the refractive index seems to reflect that of the mass density during polymerization of the epoxy-based systems within the limits of a few percent. The slight deviations from the Lorentz-Lorenz relationship, which occur during the gelation of the epoxy-based systems, are attributed to long-ranged dipole-dipole interactions, which respond at optical frequencies. This point of view is supported by the fact that chemically inert silica nanoparticles embedded in the pure epoxy matrix as disturbances for these dipole-dipole interactions are able to diminish or even to suppress totally this excess contribution of the refractive index.
