Enthalpy relaxation in the cooling/heating cycles of polypropylene/organosilica nanocomposites: II. Melting behavior

Non-isothermally crystallized samples of the neat isotactic polypropylene homopolymer (PP-0) and of a series of nanocomposites (PNC) containing up to 4.68 vol.% of organosilica were characterized by wide-angle and small-angle X-ray diffraction and by the standard DSC, while their melting behavior was studied in the temperature-modulated DSC mode at three underlying heating rates and five modulation frequencies. It was established that the lamellar morphology of PP remained essentially unchanged, whatever the previous cooling rate and/or the organoclay content. The patterns of melting endotherms in both the neat PP sample and the PNC could be semi-quantitatively characterized by a simple Debye model with a single, temperature- and underlying heating rate-dependent characteristic time. The mechanisms of structural rearrangements in the melting intervals of the neat PP sample and the PNC were basically similar; however, the spatial scale of such rearrangements in the latter samples was significantly reduced due to severe steric constraints on the PP chain mobility in the melt state from the infinite cluster of nanoparticles.