Rheological characterization of well-defined tetrafluoroethylene/hexafluoropropylene copolymers

The rheology of tetrafluoroethylene/hexafluoropropylene (TFE/HFP) copolymers, also known as Teflon FEP polymers, having different molecular weight and composition (HFP content) was studied by means of a parallel-plate rheometer. Two groups of polymers having different molecular weights with nearly constant polydispersity (around 2.5) were considered; namely, one group having a relatively low melting temperature (amorphous with a high content of HFP) and a second group having a higher melting point (semi-crystalline with a lower content of HFP). The relaxation time spectrum, H(λ), calculated by use of the BSW model (developed for monodisperse linear polymers) followed a scaling relationship in the terminal zone with scaling exponent of 0.13. However, at higher frequencies the model fails to predict adequately the experimental data. The longest relaxation time calculated from both the BSW model and discrete relaxation spectra (λ _i ,g _i ), which was determined by use of a parsimonious fitting software, depends on the molecular weight in a similar way as the zero-shear viscosity does with the well-established scaling factor of 3.4. The critical molecular weight for the onset of entanglements, M _c , was found to be about 100000, a value much higher than those previously reported in literature for other polymers. The rheology of resins in the second group (higher melting point) was found to exhibit a strong dependence on thermal history during oscillatory-shear measurements. The data obtained in experiments at different temperatures without a preheating to a certain value (330°C) exhibited a violation of the time-temperature superposition principle and no well-defined values of the zero-shear viscosity. This is attributed to residual crystallinity even at temperatures well above their melting point (260°C). However, the same experiments with preheating and subsequent cooling to desired temperature resulted into a very good time-temperature scaling. Received: 13 January 1998 Accepted: 6 April 1998