Morphological basis for the complex melting behaviour of isotactic polystyrene

Abstract

Temperature-dependent small-angle X-ray scattering spectroscopy of isothermally cold crystallized isotactic polystyrene revealed considerable morphological reorganization during subsequent heating to the melt. Both the crystalline thickness and the long period increased continuously with increasing temperature before the samples finally melted. The temperature dependence of these changes correlated very well with the melting behaviour observed with differential scanning calorimetry. As the temperature increased during a heating scan, the initial lamellae that formed during isothermal crystallization showed only little reorganization until they started to melt. Then, the molten material recrystallized continuously into increasingly thicker lamellae at increasing temperature until they finally melted. As the crystallization temperature approached the final melting temperature of the recrystallized lamellae, the initial lamellae melted without further recrystallization and no morphological changes were seen in this case.