Melting temperature versus crystallinity: new way for identification and analysis of multiple endotherms of poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) materials with different molecular weights were isothermally crystallized from melt by systematically varying the temperature and duration of the treatment performed in the differential scanning calorimeter (DSC). Multiple endotherm peaks were observed on the subsequent heating thermograms that were separated from each other on the basis of their melting temperature versus crystallization temperature and melting temperature versus crystallinity function. By this new approach five sub-peak sets were identified and then comprehensively characterised. Wide-Angle X-Ray Diffraction (WAXD) analyses revealed that the identified sub-peak sets do not differ in crystalline forms. By analysing the crystallinity and the melting temperature of the sub-peak sets as a function of crystallization time, crystallization temperature and intrinsic viscosity, it was concluded that below the crystallization temperature of 460 K the sub-peak sets that were formed during primary or secondary crystallization transform partially or completely to a third sub-peak set during the heating run of the measurement, while above this temperature, the sub-peak set formed during primary crystallization gradually transforms to a more stable structure, with higher melting temperature. These formations and transformations are described with mathematically defined parameters as well.