Formation and stability of shear-induced shish-kebab structure in highly entangled melts of UHMWPE/HDPE blends

The formation and stability of a shear-induced shish-kebab structure was investigated by in situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide-angle X-ray diffraction) measurements of highly entangled polyethylene melts based on two polymer blends, containing small fractions (2 and 5 wt %) of ultra-high molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE). Immediately after shear, the combined SAXS and WAXD results at 142 degrees C confirmed the sole formation of shish without kebabs, indicating the interplay between the topological deformation of highly entangled UHMWPE chains and the extended-chain crystallization of stretched segments without the participation of coiled segments. The presence of HDPE chains influenced the entanglement of UHMWPE but they were not involved in the shish-kebab formation at the initial stage of crystallization. The final shish lengths in both blends were nearly identical at the same strain (epsilon = 500), even though the UHMWPE concentration was different. When the temperature was cooled to 134 degrees C, both sheared blends exhibited the kebab formation, following the diffusion-controlled growth process. Although the total kebab nucleation was higher in the 5/95 wt % UHMWPE/HDPE blend, the kebab density per shish was higher in the 2/98 wt % UHMWPE/HDPE blend. The thermal stability of the shish-kebab structure was also investigated by constrained melting. Both blends exhibited identical melting behavior of kebabs but different melting behavior of shish that is governed by the entanglement restraints of the stretched-chain network.