It has long been suspected that physical chain entanglements in the amorphous phase affect the strain hardening behavior of polyethylene. The precise number of chain entanglements in solid polyethylene cannot be measured using any current techniques. Since entanglements in the melt state are known to be preserved in the polymer upon solidification, determination of the molecular weight between entanglements (Me) is used as a measure of chain entanglements for polyethylene. A decrease in molecular weight between entanglements means an increase in the number of entanglements in the polymer. As the Me value decreases, increasing tensile strain hardening of polyethylene is observed. In addition to experimental work, parallel micromechanical modeling was carried out to study the entanglement effect in uniaxial tensile deformation. The model was able to shed more light over the earlier empirical speculations. By combining experimental observations and modeling results, the presence of physical chain entanglements in the amorphous phase was demonstrated to be the controlling factor in strain hardening behavior of polyethylene.

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