Annealing effects in poly(vinylidene fluoride) as revealed by specific volume measurements, differential scanning calorimetry, and electron microscopy

Abstract

Specimens of poly(vinylidene fluoride), crystal form II, annealed at different temperatures between 130 and 180°C were characterized by specific volume measurements, differential scanning calorimetry (DSC), and electron micróscopy. The degree of crystallinity calculated from the specific volume changed only by 15% i.e., from 50% to 65%. On the other hand, the melting behavior changed with annealing conditions. When a specimen was annealed above 170°C, two endothermic peaks appeared on either side of the annealing temperature. Results from DSC measurements made at different heating rates and electron microscopy showed that the two endotherms were caused by a bimodal distribution of lamellar thicknesses. The equilibrium melting point was found to be 210°C from the linear relation of the melting point and the annealing temperature. The equilibrium enthalpy and entropy of fusion were found to be 1.6 keal/mole and 3.3 eu/mole of repeat units by measurement on polymer–diluent mixtures. The surface free energy was found to be 5.1 kcal/mole of lamellar sequences from the plot of melting point versus reciprocal lamellar thickness obtained by electron microscopy. From a plot of enthalpy of fusion versus reciprocal lamellar thickness the surface enthalpy was found to be 20 keal/mole of lamellar sequences. These data lead to the estimate that a chain fold consists of about 30 repeat units.