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The temperature dependence of the crystallinity of bulk polyethylene is calculated in terms of branching (methyl or ethyl side groups on the chain). In the model, the chains are approximately parallel and they pass through alternating amorphous and crystalline layers forming a periodic structure. The crystalinity and the thicknesses of the layers are determined by minimization of the free energy. The theory shows that the temperature at which the polymer begins to crystallize is lower than the melting point of pure polyethylene and that the thicknesses of the layers becomes smaller as the temperature decreases.
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J. des Cloizeaux (1970) studied this question.
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