Melting and reorganization of poly(ethylene terephthalate) on fast heating (1000 K/s)

For poly(ethylene terephthalate) (PET) and other polymers the origin of the multiple melting peaks observed in differential scanning calorimetry (DSC) curves is still controversially discussed. This is due to the difficulty to investigate the melting of the originally formed crystals exclusively. Recrystallization is a fast process and most experimental techniques applied so far do not allow fast heating in order to prevent recrystallization totally. Developments in thin-film (chip) calorimetry allow scanning rates as high as several thousand Kelvin per second. We utilized a chip calorimeter based on a commercially available vacuum gauge, which is operated under non-adiabatic conditions. The calorimeter was used to study the melting of isothermally crystallized PET. Our results on melting at rates as high as 2700 K/s give clear evidence for the validity of a melting-recrystallization-remelting process for PET at low scanning rates (DSC). At isothermal conditions PET forms crystals, which all melt within a few dozens of K slightly above the isothermal crystallization temperature. There is no evidence for the formation of different populations of crystals with significantly different stability (melting temperatures) under isothermal conditions. Superheating of the crystals is of the order of 10 K at 2700 K/s.