Microstructural Changes of Aramid Fiber Due to Reaction with Toluene 2,4-diisocyanate under Tension in scCO.

High modulus aramid fiber, such as Kevlar 49, is conventionally prepared by the heat annealing of high strength aramid fiber under a suitable tension at high temperature, especially higher than 500 °C. This enables the mobility of a rigid molecule chain to be rearranged into a more perfect crystalline or orientation structure under tension. However, annealing decreases the tensile strength, since the thermal degradation of the molecular chain at high temperature cannot be avoided. Kevlar 49 fibers treated in supercritical carbon dioxide (scCO) under tension could improve their mechanical properties at a low temperature. The effects of the tension on the mechanical properties and structure of the Kevlar 49 fibers were studied by mechanical testing, wide-angle and small-angle X-ray scattering (WAXS, SAXS), and scanning electron microscopy (SEM). The results show that the mechanical properties, crystallinity and orientation of the fiber can be improved when the tension is less than 0.6 cN/dtex, which may be due to the increasing of the mobility of a rigid segment with the help of the plasticization of scCO and re-arrangement of macromolecular chain into crystalline and orientation structure under tension. What's more, the amorphous region also was enhanced by crosslinking reaction of toluene 2,4-diisocyanate (TDI) with the chain end groups of the macromolecules in the amorphous regions. However, a decrease of tenacity was found when the tension was higher than 0.6 cN/dtex, which is because the tension was so high that the microfibril was broken. The results indicated that treating the Kevlar 49 fiber in scCO under a suitable tension with TDI as a crosslink agent can simultaneously improve both the tenacity and modulus of the fiber.