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Analysis of macromolecule orientation in hot drawn polyethylene by polarized Raman spectroscopy

A new experimental method for the investigation of structure of oriented polyethylene (PE) by Raman spectroscopy is proposed. The method is based on decomposition into two separate lines the Raman line around 1300 cm-1 assigned to CH2-twisting vibrations. The decomposed lines are associated with polymer chains of crystalline and amorphous regions in structure of PE. It is assumed that the analytical relationships between the second and forth coefficients in the expansion of the orientation distribution function in a series of Legendre polynomials and the depolarization ratios previously obtained for the vibrations with B2g + B3g symmetry are valid for each line. It implies that the orientation parameters can be calculated separately for both crystalline and amorphous regions. The integral intensities of the decomposed liens have been used to estimate crystallinity. To eliminate the effects of orientation and high numerical aperture objective correction procedures were introduced. The structure changes in ultra high molecular weight PE upon draw ratio have been studied by this method. It was shown that valuable information could be obtained concerning the efficiency of fibrillar structure formation.