Molecular Mobility of Polymers at the Melting Transition

Melting of crystals is an archetypical first order phase transition. Albeit extensive efforts, the molecular origin of this process in polymers is still not clear. Experiments are complicated by the tremendous change in mechanical properties and the occurrence of parasitic phenomena masking the genuine material response. Here, we present an experimental procedure permitting to circumvent these issues by investigating the dielectric response of thin polymer films. Extensive measurements on several commercially available semicrystalline polymers allowed us to identify a genuine molecular process associated with the newly formed liquid phase. In line with recent observations of amorphous polymer melts, we show this mechanism─known as the slow Arrhenius process (SAP)─involves time scales longer than those characteristics of segmental mobility and has the same energy barrier of the flow of the melt.