Oxygen solubility and specific volume of rigid amorphous fraction in semicrystalline poly(ethylene terephthalate)

The existence of rigid amorphous fraction (RAF) in semicrystalline poly(ethylene terephthalate) (PET) is associated with the lamellar stack crystalline morphology of this polymer, the regions where several crystalline lamellas are separated by very thin (20–40 Å) amorphous layers. In contrast, regular or mobile amorphous fraction is associated with much thicker interstack regions. The oxygen transport properties of PET isothermally crystallized from the melt (melt-crystallization) or quenched to the glassy state and then isothermally crystallized by heating above Tg (cold-crystallization) were examined at 25 °C. Explanation of unexpectedly high solubility of crystalline PET was attributed to the formation of RAF, which in comparison with mobile amorphous phase is constrained and vitrifies at much higher than Tg temperature thus developing an additional excess-hole free volume upon cooling. Measurements of crystallinity and jump in the heat capacity at Tg were used to determine the amount of mobile and rigid amorphous fractions. Overall oxygen solubility was associated with the solubility of mobile and rigid amorphous fractions. The oxygen solubility of the RAF was determined and related to the specific volume of this fraction. The specific volume of the RAF showed a direct correlation with the crystallization temperature. It was shown that upon crystallization from either melt or glassy state, the constrained between crystalline lamellas PET chains consisting of the RAF, vitrify at the crystallization temperature and resemble the glassy behavior despite high temperature. When cooled to room temperature, the RAF preserves a memory about the melt state of polymer, which is uniquely defined by the crystallization temperature.