Etching and the morphology of branched and cross-linked polyethylene

Abstract

A permanganic acid etching technique was used to characterize the genuine morphologies of bulk crystallized samples of linear, branched, and crosslinked polyethylene. Four different kinds of artifacts as large as 15-20 p~a were detected. It was also noted that artifact density could be drastically reduced by proper selection of etching conditions. The morphologies of artifacts were independent of specimen crystallinity and the orientation of lamellar crystals; however, their rate of production was susceptible to the crystallinity of samples. The formation of a fresh surface involved the preferential etching of edge-on and secondary lamellae. As the growth features of cross-linked polyethylene were less than 6 paxa and were mainly sheaf-like structures, growth features could be readily distinguished from the artifacts by transmission electron microscopy. Another type of artifact (globules morphology) produced at angstrom scale was found to depend on the crystallinity and the surface structure of lamellar crystals. It is demonstrated that the fine lamellar details of branched and cross-linked polyethylene can be observed using transmission electron microscopy. Increasing the number of cross-links in polyethylene, modifies the size and nature of supermolecular structures, the periodic twisting of lamellar crystals, and the nature of the nucleation process. The study of a blend of branched and cross-linked polyethylene showed that the structurally dissimilar molecules co-crystallized at low crystallization temperatures, while there is a tendency for molecular fractionation at higher crystallization temperatures.