On the strain-induced fibrillar microstructure of polyethylene: Influence of chemical structure, initial morphology and draw temperature

Abstract

The influence of crystalline microstructure and molecular topology on the strain-induced fibrillar transformation of semi-crystalline polyethylenes having various chemical structures including co-unit content and molecular weight and crystallized under various thermal treatments was studied by in situ SAXS at different draw temperatures. The long period of the nascent microfibrils, Lpf, proved to be strongly dependent on the draw temperature but non-sensitive to the initial crystallization conditions. Lpf was smaller than the initial long period. Both findings have been ascribed to the straininduced melting-recrystallization process as generally claimed in the literature. The microfibrils diameter, Df, was shown to depend on the draw temperature and initial microstructure in a different way as Lpf. The evolution of Df was shown to correlate with the interfacial layer thickness that mainly depends on the chemical structure of the chains. It was concluded that, in contrast to Lpf, the microfibril diameter should not be directly sensitive to the strain-induced melting-recrystallization. The proposed scenario is that after the generation of the protofibrils by fragmentation of the crystalline lamellae at yielding, the diameter of the microfibril during the course of their stabilization should be governed by the chain-unfolding and subsequent aggregation of the unfolded chains onto the lateral surface of the microfibrils. The morphogenesis of the microfibrils should therefore essentially depend on the chemical structure of the polymer that governs its crystallization ability, its chain topology and subsequently its fragmentation process at yielding. This scenario is summed up in a sketch.

Keywords

• Mechanical properties
• Semi-crystalline polymers
• Microstructure
• Plastic deformation