Melting-Induced Evolution of Morphology, Entanglement Density, and Ultradrawability of Solution-Crystallized Ultrahigh-Molecular-Weight Polyethylene

The melting-induced change in the density of physical network junctions, which are formed by chain entanglements and network junctions due to anchoring of chain segments to crystals, is studied by 1H NMR T2 relaxometry for solution- and melt-crystallized ultrahigh-molecular-weight polyethylene (UHMWPE), sc-UH, and mc-UH, respectively. The NMR results are complemented by real-time synchrotron wide- and small-angle X-ray scattering (WAXS and SAXS) analyses to extract the sizes of the crystalline lamellae and intercrystalline domains. Below the melting temperature, the network of physical junctions is denser in the amorphous phase of mc-UH than the one in sc-UH owing to a lower entanglement density and a smaller number of physical junctions from polymer crystals in sc-UH. However, the difference in the total density of physical junctions between mc-UH and sc-UH films decreases with decreasing crystallinity during melting. At the end of the melting trajectory, at vanishing crystallinity, the volume-average entanglement density, as characterized by the NMR method, is approximately the same in sc- and mc-UH. This indicates that the entanglement density in sc-UH films increases during melting owing to the fast buildup of local chain entanglements. These entanglements are formed by segments of the same chain, neighboring chains, or both due to a displacement of chain fragments upon lamellar thickening and due to the so-called "chain explosion" that occurs locally in the amorphous domains. The increase in the entanglement density in sc-UH is additionally confirmed by the solid-state drawability of sc-UH films that were annealed in the melting region but below the end of melting. The maximum draw ratio decreases and the drawing stress increases with the increasing annealing temperature.