Gradient of molecular dynamics at the glass transition of PETg–Montmorillonite nanocomposites

Abstract

Temperature Modulated Differential Scanning Calorimetry (TMDSC) is used to estimate Cooperative Rearranging Region (CRR) average sizes for polymer/clay nanocomposites, obtained by mixing polyethylene 1,4-cyclohexylenedimethylene terephthalate glycol (PETg) filled and organically modified nanoclay (C15A) following a master-batch process. Two different basal distances are obtained. It is shown that the greater the basal distance and the nanofiller content, the lower the heat capacity step at the glass transition temperature Δ Cp( T g ), and the lower the CRR volume. It is also shown that the evolution of the CRR volume is consistent with the evolution of the fragility index obtained by DSC and Broadband Dielectric Spectroscopy (BDS) when the nanofiller content changes. The fragility index and the CRR size decreases can be correlated to nanofiller presence, hindering the molecular movements. From the Vollenberg and Heikens [34] approach, this behaviour can also be interpreted through the existence of an interfacial bilayer. This interfacial bilayer is composed by a zone, which is next to the nanofiller, with a density higher than the matrix one, followed by a more expanded zone with a density lower than the matrix one.