Relaxations in Copolymers of Tetrafluoroethylene and Hexafluoropropylene

Abstract

The modulus and internal friction of copolymers of tetrafluoroethylene and hexafluoropropylene (HFP) were measured with longitudinal waves at a frequency of 12 Mc between −80° and 260°C. The dielectric dissipation factor was measured at 0.1, 1.0, 10, and 100 kc between −180° and 200°C. Samples included copolymers with compositions ranging from pure polytetrafluoroethylene to pure polyhexafluoropropylene. A relaxation at −10°C (12 Mc) in polytetrafluoroethylene shifts to higher temperatures with increasing HFP content. Data suggest that 5 to 13 main-chain carbon atoms are involved, a size consistent with assigning the relaxation to motions of a small point defect in the crystal lattice. Molecular models indicate that the effects of these defects are reduced by perfluoromethyl groups which enter the lattice as another kind of point defect. Dielectric and mechanical relaxation temperatures agree approximately and yield the same activation parameters. These parameters exhibit no significant variation with HFP content and follow a relation which applies to activated processes in inorganic solids. The relation also obtains for a relaxation at 197°C (12 Mc) in polytetrafluoroethylene. This relaxation shifts to lower temperatures and the activation enthalpy decreases with increasing HFP content. Dielectric data do not exhibit the relaxation, and heating polytetrafluoroethylene near the melting point does not introduce sufficient polar groups to alter this result. Another relaxation observed below −150°C in the dielectric but not in the ultrasonic data is independent of polymer density and HFP content.