Strong shear-driven large scale formation of hybrid shish-kebab in carbon nanofiber reinforced polyethylene composites during the melt second flow
The formation of a hybrid shish-kebab (HSK) structure with different degrees of lamellar orientations was first observed in the solution crystallization of polyethylene (PE) in the presence of carbon nanofibers (CNFs). In this study, PE crystal lamellae were periodically decorated on the surface of CNFs and were aligned approximately perpendicular to the long axes of the CNFs, forming aligned hybrid shish-kebab nanostructures. More importantly, the fascinating structure was directly formed in all regions of the injection molded bars of HDPE/CNF composites, via a gas-assisted injection molding (GAIM), instead of the shell–core structure. In the GAIM process, an intense shear was imposed onto the melt during the melt second flow and drove PE chains to orient along the axes of the CNFs. Then the entropy penalty for PE chains deposited on the CNF surface was drastically decreased. Although the attractive van der Waals interactions were weak, the oriented PE chains could successfully adsorb on the CNF surface due to the decrease of the entropy penalty, therewith the underlayer coating was formed along the axis based on a two-dimensional mode for early nucleation on the CNF surface. Subsequently, subglobules appeared on the ordered structure, which could be regarded as the crystal nucleus. Finally, the oriented PE chains began to epitaxially grow from the subglobules with a folded-chain shape to decrease the polymer surface energy and grew perpendicular to the CNFs long axis, abiding by the “soft epitaxy” crystallization mechanism regardless of strict lattice matching.