M. Shimizu et al., DEVELOPMENT OF HIGH-MODULUS AND HIGH-STRENGTH POLY(TETRAFLUOROETHYLENE) FIBERS BY ELONGATION AT A LIQUID-CRYSTALLINE STATE, Macromolecules, 29(21), 1996, pp. 6724-6729
Raw filaments of ultrahigh molecular weight poly(tetrafluoroethylene)
(PTFE) (8.4 x 10(6)) were prepared by the paste extrusion of fine powd
er. The raw filaments with a sag ratio of 25% were annealed at 360 deg
rees C, higher than the apparent melting point of 330 degrees C estima
ted by differential scanning calorimetry (DSC), at a heating rate of 1
0 degrees C/min. After annealing for 30 min, they were cooled to room
temperature at desired rates. The resultant monofilaments were anneale
d for 30 min at 388 degrees C and were elongated up to 100 times at th
e same temperature. Young's modulus and the tensile strength were sens
itive to the sag ratio of raw filaments under heating and cooling proc
esses. The maximum values of Young's modulus and the tensile strength
of drawn fibers reached 57.6 and 2.31 GPa, respectively, at 25-26 degr
ees C associated with the crystal transition at room temperature, when
the sag ratio was 25% corresponding to the intrinsic shrinkage of the
raw filaments. This indicates that a suitable level of the entangleme
nt mesh to assure the maximum values of the tensile strength and Young
's modulus was formed by the drastic shrinkage (25%) of the raw filame
nts, leading to molecular motion without constraints. This phenomenon
is discussed in terms of the morphology of the monofilaments and drawn
fibers as studied by optical microscopy (crossed-polarized), differen
tial scanning calorimetry, and X-ray diffraction techniques. The produ
ction of high-strength PTFE fibers is attributed to the appearance of
thermotropic liquid crystals at temperatures higher than the apparent
melting point, reflecting the chain rigidity of PTFE.