By differential scanning calorimetry (DSC), the thermal behavior of polytetrafluoroethylene (PTFE) and random fluorinated copolymers of tetrafluoroethylenecontaining hexafluoropropylene (FEP copolymers) or perfluoroalkylvinylether (PFA copolymers) as comonomers was investigated. Rapid-melt crystallization was employed to provide new data about the problem of inclusion/exclusion of co-units from the homopolymer crystal lattice. Equilibrium melting points were determined and tested in light of random copolymer predictions. Both nonequilibrium and equilibrium behaviors seem to point to the inclusion of OCF 3 side groups and the exclusion of larger ones. Finally, a new value of the equilibrium melting point of PTFE is given, in good agreement with those present in the literature.

Through differential scanning calorimetry, isothermal crystallization from the melt of polytetrafluoroethylene (PTFE) has been investigated. PTFE was regarded as one of the polymers for which crystallization is so rapid that the samples crystallize during the cooling from the melt to the selected crystallization temperature. By contrast, we now report that a stochastic behavior is observed for isothermal melt-crystallization of PTFE. In fact, on cooling very quickly the samples from the molten state to the selected crystallization temperature, crystallization during the cooling is randomly observed. Therefore, repeating the experiments until crystallization on cooling was absent, it was possible to investigate isothermal melt-crystallization of PTFE. However, crystallization is very fast; in fact, crystallization kinetics can be followed just for very low undercoolings, while as the undercooling becomes as large as about 15°C, only secondary crystallization is observed. In both cases, the data have been examined through the well-known Avrami analysis, taking into account the different physical meaning of the obtained parameters. For the first cases (actual crystallization kinetics) very low, noninteger Avrami exponents have been obtained. They have been related to the fractal dimension of the crystallites and their values to the morphological observations on PTFE. For the second cases, the typical low values of Avrami exponents of secondary crystallization are obtained. Moreover, isothermal melt-crystallization of random fluorinated copolymers of tetrafluoroethylene with either hexafluoropropylene or perfluoromethylvinylether as comonomers has been studied and compared with that of PTFE.

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By differential scanning calorimetry (DSC), the thermal behavior of polytetrafluoroethylene (PTFE) and random fluorinated copolymers of tetrafluoroethylenecontaining hexafluoropropylene (FEP copolymers) or perfluoroalkylvinylether (PFA copolymers) as comonomers was investigated. Rapid-melt crystallization was employed to provide new data about the problem of inclusion/exclusion of co-units from the homopolymer crystal lattice. Equilibrium melting points were determined and tested in light of random copolymer predictions. Both nonequilibrium and equilibrium behaviors seem to point to the inclusion of OCF 3 side groups and the exclusion of larger ones. Finally, a new value of the equilibrium melting point of PTFE is given, in good agreement with those present in the literature.