Chain conformations and bound-layer correlations in polymer nanocomposites.

Small angle neutron scattering studies on polystyrene loaded with spherical silica nanoparticles under contrast-matched conditions unequivocally show that chain conformations follow unperturbed Gaussian statistics independent of chain molecular weight and filler composition. Liquid state theory calculations are consistent with this conclusion and also predict filler-induced modification of interchain polymer correlations which have a distinctive scattering signature that is in nearly quantitative agreement with our observations.

Quantitative equivalence between polymer nanocomposites and thin polymer films.

The thermomechanical responses of polymers, which provide limitations to their practical use, are favourably altered by the addition of trace amounts of a nanofiller. However, the resulting changes in polymer properties are poorly understood, primarily due to the non-uniform spatial distribution of nanoparticles. Here we show that the thermomechanical properties of 'polymer nanocomposites' are quantitatively equivalent to the well-documented case of planar polymer films. We quantify this equivalence by drawing a direct analogy between film thickness and an appropriate experimental interparticle spacing. We show that the changes in glass-transition temperature with decreasing interparticle spacing for two filler surface treatments are quantitatively equivalent to the corresponding thin-film data with a non-wetting and a wetting polymer-particle interface. Our results offer new insights into the role of confinement on the glass transition, and we conclude that the mere presence of regions of modified mobility in the vicinity of the particle surfaces, that is, a simple two-layer model, is insufficient to explain our results. Rather, we conjecture that the glass-transition process requires that the interphase regions surrounding different particles interact.