Solid state extrusion dynamics of poly(vinylidene fluoride) and its copolymers have been studied using an Instron capillary rheometer with specially designed die set. At and above the Curie transition temperatures, the copolymers rapidly soften while preserving the semicrystalline structure. This allows them to be solid state extruded between this temperature and melting temperature. The processing windows within which high quality extrudates can be obtained were established for two copolymer compositions and they were found to be much wider than those typically observed in semicrystalline homopolymers such as polyethylene and polypropylene. Extrudate swell under all solid state extrusion condition remains constant and is always less than 1 and it was found to increase above this value as the extrusion temperature increased through the melting region which is typical of melt extrusion of these polymers.

Copolymers of vinylidene fluoride (VF2) and vinyltrifluoride (VF3) exhibit Curie transition temperatures well below their melting points. Above these endothermic transitions, they soften and this behavior helps in their solid state extrudability. In this paper, the effects of extrusion speed, temperature, and draw ratio on structure development in 60/40 and 72/28 VF2/VF3 copolymer compositions are presented. With the increase of extrusion draw ratio the Curie transition temperature of the extrudates decreased and melting temperature increased. This behavior suggested that the chains in the crystalline regions contain higher levels of conformational defects while overall crystallinity is increased. Unoriented polymers were optically opaque and extrudates were found to be transparent as a result of breakdown on the superstructural level which decreases the scattering effects in the visible wavelength range. The micro beam WAXS studies on the samples taken from the entrance of the dies revealed that the unoriented core is surrounded by alternating unoriented and oriented layers close to the core. The remainder of the skin layers are found to be oriented with local symmetry axes and main chain orientation being parallel to the die wall surface. The regions that are found to be oriented were also found to be optically translucent and unoriented regions were optically opaque. This structure turns uniformly transparent–and thus oriented‒as the polymer enters the die. The existence of layered structure suggests that highly localized yielding occurs during early states of deformation at the converging entrance region of the die. Examination of the radial structural variation in extrudates with micro beam X‐ray diffraction technique revealed that the local symmetry axes are tilted away from the extrusion direction and this tilt angle reduces at the sample macro‐symmetry axis at the core of the samples. This indicated that the tilted structure developed at the converging entrance region is partially preserved through the die. While the orientation of local symmetry axes varies from skin to core in the extrudates, the orientation of chains with respect to these local symmetry axes remains relatively unaffected.