Order—disorder transitions in polytetrafluoroethylene

Abstract

The phase diagram of polytetrafluoroethylene is enlarged by differential scanning calorimetry to include the concentration of hexafluoropropylene comonomer units. The two transitions near 292 and 303 K in the homopolymer move to lower temperatures and apparently become one at small concentrations. Analysis of the data yields 295 K for the temperature and 13.2 J/g for the heat of transition of an infinitely large homopolymer crystal. The heat of transition associated with the formation of a crystal defect is 0.021 eV. The qualitative features of the transition can be accounted for by a mean-field model which involves two order parameters corresponding to planar units and helix reversals. This model yields two transitions which move closer together and to lower temperatures with increasing comonomer concentration. Decreasing lamella thickness will have a qualitatively similar effect.