Free volume in PEP-silica nanocomposites with varying molecular weight

The influence of confinement in polymer-nanocomposites on free volume and glass transition of the polymer chains was studied. The molecular weight (Mw) of poly(ethylene-alt-propylene) (PEP) was varied from 3k to 200k and so the end-to end distance of the chains at fixed diameter (∼15 nm) and concentration (15%) of the silica nanoparticles increased. Thus the topological confinement increases with increasing Mw. Using hydrophobic PEP and particles functionalized with short organic molecules, we can rule out contributions of permanent adsorption of the chains. DSC showed no change in glass transition temperature. The decrease in the specific heat capacity could be explained by a simple mixing rule. By positron annihilation lifetime spectroscopy, taking properly into account contributions of the silica particles, we rule out an influence of the geometrical confinement on the free volume in the PEP nanocomposites studied here. © 2013 Elsevier Ltd. All rights reserved