Morphology and Plastic Yielding of Ultrahigh Molecular Weight Polyethylene

Macromolecules. 2020 Jul 28;53(14):6063-6077. doi: 10.1021/acs.macromol.9b02154. Epub 2020 Jul 17.

Abstract

The structure, morphology, and mechanical properties of two compression-molded grades of ultrahigh-molecular-weight polyethylene (UHMWPE) and, for comparison, one conventional linear polyethylene (HDPE) were studied. Compression molding resulted in some preferred orientation of lamellae in the compression direction in UHMWPE samples, while no preferred orientation in HDPE. The mean crystal thickness estimated from the size distribution agrees better with those obtained from small-angle X-ray scattering (SAXS) and mechanical yield data than the thickness determined from the melting peak temperature. Microscopic examination of microtomed and etched UHMWPE samples showed that the lamellae are in the form of platelets with the width and length in the range of 300-700 nm. The lamellae radiate from primary nuclei forming small embryonal spherulites; their radial growth ends at 0.3-0.7 μm from the center. There is no evidence of branching and secondary nucleation from those primary lamellae. Because the lamellae are radially ordered, there is no parallel stacking of lamellae. Samples were subjected to deformation by plane-strain compression at a constant true strain rate. In axial UHMWPE samples, where lamellae were preferentially oriented along the loading direction, the second yield was clearly observed. The second yield was found to be related to the deformation instability leading to kinking of lamellae oriented initially along the loading direction. Kinking was clearly shown by SAXS and microscopic observation of microtomed and etched samples. No cooperativity of kinking was observed because the lamellae are arranged in small spherulites and not parallel in stacks. The stress-strain curves were fitted with model curves assuming crystal plasticity and network elasticity in the amorphous component. The effective density of the molecular network within the amorphous phase depended on the molecular weight of UHMWPE.