Superdrawing of polytetrafluoroethylene nascent powder by solid-state coextrusion

Abstract

A film of nascent powder of polytetrafluoroethylene (PTFE), compacted below the ambient melting temperature (Tm, 335 °C), was drawn by two-stage draw techniques consisting of a first-stage solid-state coextrusion followed by a second-stage solid-state coextrusion or tensile draw. Although the ductility of extrudates was lost for the second-stage tensile draw at temperatures above 150 °C due to the rapid decrease in strength, as previously reported, the ductility of extrudates increased with temperature even above 150 °C when the second-stage draw was made by solid-state coextrusion, reflecting the different deformation flow fields in a free space for the former and in an extrusion die for the latter. Thus, a powder film initially coextruded to a low extrusion draw ratio (EDR) of 6–20 at 325 °C was further drawn by coextrusion to EDRs up to ∼︁400 at 325–340 °C, near the Tm. Extremely high chain orientation (fc = 0.998 ± 0.001), crystallinity (96.5 ± 0.5)%, and tensile modulus (115 ± 5 GPa at 24 °C, corresponding to 73% of the X-ray crystal modulus) were achieved at high EDRs. Despite such a morphological perfection and a high modulus, the tensile strength of a superdrawn tape, 0.48 ± 0.03 GPa, was significantly low when compared with those (1.4–2.3 GPa) previously reported by tensile drawing above the Tm. Such a low strength of a superdrawn, high-modulus PTFE tape was ascribed to the low intermolecular interaction of PTFE and the lack of intercrystalline links along the fiber axis, reflecting the initial chain-extended morphology of the nascent powder combined with the fairly high chain mobility associated with the crystal/crystal transitions at around room temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3369–3377, 2006