AbstractVitrification and devitrification of the rigid amorphous fraction (RAF) of poly(ethylene terephthalate) (PET), analyzed during development and disappearance of the three phase structure, are detailed in this contribution. Upon cooling from the melt at a constant rate, the rigid amorphous fraction starts to vitrify when the crystallization process is almost finished, and continues on further cooling. The rigid amorphous fraction is formed in the same temperature range of the secondary crystal growth. Analysis of the low melting endotherm that is observed in isothermally crystallized PET a few degrees above the crystallization temperature reveals a joint contribution of melting and devitrification of the rigid amorphous fraction. The results confirm a link between secondary crystallization and vitrification of the rigid amorphous fraction in semicrystalline polymers. Secondary crystallization takes place in geometrically restricted areas, in which the polymer chains undergo large constraints, so that the mobility of the amorphous chain portions coupled with the crystal phase is reduced. Similarly, the gain in mobility upon partial melting of thinner and/or more defective crystals allows an increase in mobility of the coupled amorphous regions, which results in concurrent mobilization of the rigid amorphous fraction.
