TEMPO-oxidized cellulose nanofibril/poly(vinyl alcohol) composite drawn fibers

PVA/TOCN composite fiber with a weight ratio of 100:1 was prepared from a mixture of aqueous poly(vinyl alcohol) (PVA) solution and 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-oxidized cellulose nanofibril (TOCN) dispersion using spinning, drawing, and drying processes. The as-spun PVA/TOCN composite fiber was further drawn, up to a draw ratio of 20 by heating at up to 230 °C. The maximum tensile modulus of the PVA/TOCN composite drawn fiber reached 57 GPa, remarkably higher than that of commercial PVA drawn fibers. Moreover, the PVA/TOCN composite drawn fiber had storage modulus higher than that of the PVA drawn fiber at each temperature in the range from 28 to 239 °C. Structural analyses showed that amorphous PVA regions in the composite drawn fiber were more oriented than those in neat PVA fiber after the addition of the small amount of TOCN used. These results indicate that TOCN elements were individually dispersed in the PVA matrix without aggregation and formed hydrogen bonds with amorphous PVA molecules in the composite drawn fiber.