화학공학소재연구정보센터
Journal of Polymer Science Part B: Polymer Physics, Vol.34, No.3, 517-526, 1996
Cooperative Relaxations in Semicrystalline Fluoropolymers Studied by Thermally Stimulated Currents and AC Dielectric
Semicrystalline fluoropolymers including poly(tetrafluoroethylene) (PTFE), a 8 mol % hexafluoropropylene (HFP)/92% TFE random copolymer (FEP), and poly(vinyl fluoride) (PVF) were studied using thermally stimulated current depolarization (TSC), ac dielectric, and other thermal analysis techniques. The TSC thermal sampling (TS) technique is emphasized here for the detection of broad and weak "cooperative" relaxations with all three of the polymers studied exhibiting two cooperative (i.e., relatively high apparent activation energy) transitions. The well-studied low-temperature gamma relaxation in PTFE at ca. -100 degrees C is characterized by this method as well as the gamma relaxation in the less crystalline FEP sample. Higher temperature cooperative glass transitions, associated with constrained noncrystalline regions, are found at ca. 100 degrees C in PTFE and ca. 80 degrees C in FEP at TSC frequencies. Comparisons with relaxation studies of linear polyethylene are made, and the effects of crystallinity on the various transitions are discussed. The unique characterization by the TSC-TS technique in the detection of multiple "cooperative" relaxations, even in the case of overlapping transitions, is emphasized here. An example is the low-temperature relaxation in FEP. Two cooperative transitions were detected in PVF. The higher temperature one at ca. 45 degrees C is the glass transition, as is well known in the literature. More information is needed to confirm the molecular origin and the effects of crystallinity and chemical structure on the low-temperature cooperative transition in PVF.