Well-Dispersed Fractal Aggregates as Filler in Polymer−Silica Nanocomposites: Long-Range Effects in Rheology

We are presenting a new method of processing polystyrene−silica nanocomposites, which results in a very well-defined dispersion of small primary aggregates (assembly of 15 nanoparticles of 10 nm diameter) in the matrix. The process is based on the use of a high boiling point solvent, in which the nanoparticles are well dispersed, and a controlled evaporation procedure. The filler’s fine network structure is determined over a wide range of sizes, using a combination of small-angle neutron scattering (SANS) and transmission electronic microscopy (TEM) experiments. The mechanical response of the nanocomposite material has been investigated for both small (ARES oscillatory shear and dynamical mechanical analysis) and large deformations (uniaxial traction) as a function of the concentration of the particles in the matrix. Our findings show that with a simple tuning parameter, the silica filler volume fraction, we can investigate in the same way the structure−property correlations related to the two main reinforcement effects: the filler network contribution and a filler−polymer matrix effect. Above a silica volume fraction threshold, we were able to highlight a divergence of the reinforcement factor, which is clearly correlated to the formation of a connected network built up from the finite-size primary aggregates and is thus a direct illustration of the filler network contribution. For a silica volume fraction lower than this percolation threshold, we obtain a new additional elastic contribution of the material, of longer terminal time than the matrix. This cannot be attributed to the filler network effect, as the filler is well dispersed, each element separated from the next by a mean distance of 60 nm. This new result, which implies the filler−matrix contribution of the reinforcement, must include interfacial contributions. Nevertheless, it cannot be described solely with the concept of glassy layer, i.e., only as a dynamic effect, because its typical length scale extension should be much shorter, of the order of 2 nm. This implies a need to reconsider the polymer−filler interaction potential and to take into account a possible additional polymer conformational contribution due to the existence of indirect long-range bridging of the filler by the chains.