Isothermal reorganization of poly(ethylene terephthalate) revealed by fast calorimetry (1000 K s(-1); 5 ms).

Reorganization of semicrystalline polymers on heating is a fast process. For poly(ethylene terephthalate) (PET) heating rates of several thousand Kelvin per second are needed to prevent reorganization of unstable crystals. Utilizing a thin film vacuum gauge as a fast calorimeter we are able to extend the scanning rate range of commercial DSC's (microK s(-1) to 10 K s(-1)) to rates as high as 10000 K s(-1) on heating and cooling. Because of the fast equilibration time isothermal experiments can be performed after scanning at several thousand Kelvin per second. The dead time after such a quench is in the order of 10 ms and the time resolution is in the order of milliseconds. These ultra fast calorimeters allow us to study the kinetics of extremely fast processes in semicrystalline polymers like reorganization. For PET crystallized at 130 degrees C reorganization needs less than 40 ms between 150 degrees C and 200 degrees C. Isothermal reorganization at 223 degrees C is about two orders of magnitude faster than isothermal crystallization from the isotropic melt at the same temperature. The melt memory for the remaining structures needed for reorganization is removed 25 K above the equilibrium melting temperature of PET.