The effect of temperature and deformation rate on the hot-drawing behavior of porous high-molecular-weight polyethylene fibers

Abstract

The nature of the deformation process involved in hot drawing of porous high-molecular-weight polyethylene was examined by apparent elongational viscosity measurements at drawing temperatures between 100°C and 150°C and deformation rates in the range of 10−6–10−3 m/s. The temperature dependence of the apparent elongational viscosity revealed three distinguishable intervals with different activation energies. In the range of 100–133°C, the activation energy amounted to 50 kJ/mol, indicating that hot-drawing in this region proceeds by a sliding motion of separate fibrillar units. The interval between 133°C and 143°C was characterized by an activation energy of about 150 kJ/mol. Moreover, the porous character of the polyethylene fibers was found to decrease in the drawing process above 133°C. These observations were ascribed to an aggregation of the elementary fibrils upon hot-drawing due to partial melting at the surface of the fibrils. At temperatures above 143°C the activation energy was strongly affected by the initial morphology and the draw ratio of the fibers and amounted to values in the range of 200–600 kJ/mol. Molecular orientation in this region is accomplished by a slippage of individual chains, with entanglements acting as semipermanent crosslinks. Decreasing of the rate of elongation in the drawing process resulted in premature fiber breakage, indicating that the crosslinking action of the entanglements is limited by the time scale of the process.