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The thermal behavior of semirigid-chain semicrystalline polymers is often very complex, exhibiting multiple endothermic and exothermic events related to melting and recrystallization. The origin of the differences between the flexible and semirigid-chain polymers is believed to lie in the higher energy expenditure associated with the formation of adjacent re-entry folds at the crystalline surface in the case of semirigid chains. The effect of constraints imposed by the interlamellar amorphous regions on the neighboring crystals was studied with temperature-resolved synchrotron radiation small-angle X-ray scattering (SAXS) and variable temperature Atomic Force Microscopy [1]. The analysis of SAXS patterns with a generalized paracrystalline lamellar stack model indicates that melting of a semirigid-chain polymer is not a random process but that the crystals grown in the smallest amorphous gaps melt first [2]. This suggests that the hitherto largely neglected geometrical confinement effects may play an important role in determining the thermodynamic stability of semirigid-chain polymer crystals.

Polymer meltingversuscrystallization: a combined small-angle X-ray scattering and atomic force microscopy study