Crystallization Behaviour of Polytetrafluoroethylene over very Large Cooling Rate Domains

Abstract

Polytetrafluoroethylene (PTFE) is a semi-crystalline polymer that demonstrates a very fast crystallization process on cooling. This study investigates the nonisothermal PTFE ultra-fast crystallization over a wide range of cooling rates via conventional Differential Scanning Calorimetry (DSC), Fast Scanning Calorimetry (FSC) and Ultra-Fast Scanning Calorimetry (UFSC). A new knowledge about crystallization kinetics of PTFE is obtained from the data obtained under very fast cooling rates. The shift of the melting peak to lower temperature shows that the crystals formed under fast cooling rates are slightly less stable than those produced under slower cooling rates. SEM analysis allows to observe these differences in crystal morphologies. According to the results, the crystallization is still present even for the fastest cooling rate employed and in consequences it is impossible to reach a metastable glassy state. The effective activation energy (Eα) displays a variation with the relative extent of crystallization (α) that is characteristic of a transition of PTFE crystallization from regime II to regime III around 312°C. Following the Hoffman-Lauritzen theory the Eα dependency obtained from the crystallizations under the different cooling rates was fitted in order to study the theoretical dependence of the growth rate.