Polymer Dynamics in Polyurethane/clay Nanocomposites Studied by Dielectric and Thermal Techniques

Abstract

Differential scanning calorimetry (DSC), broadband dielectric relaxation spectroscopy (DRS), and thermally stimulated depolarization current (TSDC) techniques were employed to investigate glass transition and polymer dynamics in nanocomposites of polyurethane (PU) and organically modified montmorillonite (MMT) (weight fraction 0%–15%) prepared by solution casting. The PU matrix was obtained from oligo(oxytetramethylene glycol) of molar mass 1000 g/mol, 4,4′-diphenylmethane diisocyanate and 1,1-dimethylhydrazine as chain extender. Wide-angle X-ray scattering confirmed the formation of partly exfoliated structures at low MMT content. DSC, DRS, and TSDC show, in agreement with each other, that a fraction of polymer makes no contribution to the glass transition and to the corresponding α relaxation, whereas the rest exhibits similar glass transition dynamics as the pure matrix. This fraction of immobilized polymer reaches a maximum at about 5 wt% MMT. Effects of MMT on the microphase-separated structure of PU are negligible, as indicated by the study of glass transition and interfacial dielectric polarization/relaxation. No effects of MMT on the local, secondary γ and β relaxations were observed. Mechanical properties show a maximum improvement at about 5 wt% MMT, in good correlation with morphology and dynamics.