Viscous and elastic properties of poly(methyl methacrylate) melts filled with silica nanoparticles

In this paper it is shown that elastic properties of a poly(methyl methacrylate) melt in the linear range of deformation are more significantly influenced by the addition of silica nanoparticles than viscous ones. The effect is the strongest in the steady-state which is reached at several thousand seconds. That is the reason why the often used dynamic-mechanical experiments are not a very suitable method for investigations of that kind. Therefore, creep and creep-recovery tests were applied for the characterisation of the filled materials. The linear steady-state recoverable compliances following from the recovery experiments increase by a factor of 6 at the highest measured volume content of 2.1%. This finding is explained by the existence of long retardation times in the filled materials resulting from interactions between the fillers and matrix molecules attached to their surfaces which reduce their molecular mobility. Retardation spectra calculated from the recovery curves quantify these assumptions. The model is supported by the experimental finding that the recoverable compliance becomes smaller above a certain stress applied and approaches that of the matrix as such a behaviour could be explained by a detachment of the molecules from the particle surface. The paper demonstrates that investigations of elastic properties of nanoparticle filled polymers in the molten state at long experimental times are a very sensitive tool to get an insight into interactions between particles and macromolecules of such systems.