Abstract
Strain energy of various types of defects caused by chain ends in the polymer crystal is theoretically estimated by using interchain and intrachain potentials of polyethylene. It is concluded that screw dislocations running through chain ends have minimum energy when chain ends are not so close to the crystal surface. For the end close to the surface, on the other hand, a vacancy row from the end to the surface is proved to be the most stable and the minimum distance of the end from the surface for screw dislocation formation is ca. 30 Å for linear polyethylene of usual molecular weight. The crystal is expected to have a mosaic structure owing to screw dislocations and vacancy rows.Transformation of orthorhombic crystal to monoclinic and {110} twinning, both observed in the early stage of plastic deformation of polyethylene, are interpreted in terms of the vacancy rows and screw dislocations described above. The γ-relaxation of as-grown polyethylene crystals is explained by thermal motion of screw dislocations over the Peierls potential and a satisfactory agreement with experiment is attained by the two-state model theory for both relaxation strength and activation energy, by use of reasonable estimates for parameters in the theory.
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Matsui, M., Masui, R. & Wada, Y. Defects Caused by Chain Ends in Polymer Crystals and Interpretation of Plastic Deformation and γ-Relaxation in Terms of Them. Polym J 2, 134–147 (1971). https://doi.org/10.1295/polymj.2.134
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DOI: https://doi.org/10.1295/polymj.2.134
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