Infrared studies of drawn polyethylene part I. Changes in orientation and conformation of highly drawn linear polyethylene

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Abstract
Infrared spectroscopy is applied to discuss the orientation, the crystallinity, and the conformation of chain segments in the amorphous regions in drawn high-density polyethylene. The orientation of the crystals as well as the crystallinity are derived from the dichroism and the absorbance, respectively, of the band at 1894 cm-1. The orientation and some aspects about the conformation of the chain segments in the amorphous regions can be obtained from the bands in the 1400-1300 cm-1 region (gauche) and at 1078 cm-1 (gauche and trans). The dichroic studies show a high degree of orientation increasing with draw ratio λ for the chain segments in the crystals, but a low orientation reaching saturation at λ between 5 and 10 for those in the amorphous regions. The experiments indicate a change in crystallinity during the drawing process which depends on the thermal treatment of the undrawn sample. In the amorphous regions the number of CH2 groups in gauche conformations decreases up to λ between 10 and 15 and remains nearly constant with further drawing. Since the sum of gauche and trans conformations remains unchanged, it can be deduced that the number of loops decreases and that of tie molecules increases with draw ratio.

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