Terahertz absorption spectra and X-ray diffraction patterns were measured for amorphous poly(ethylene naphthalate) (PEN) while the sample temperature was elevated from 25 to 230°C then lowered back to 25 °C. Before the elevation of the temperature, PEN exhibited broad absorption with a maximum at around 2.6 THz. This absorption seems to originate from amorphous regions. As the sample temperature increases, PEN becomes crystallized in the form of α crystal. With this change in crystallinity, the 2.6 THz absorption becomes smaller, while another absorption peak at 2.05 THz, originating from crystalline regions, becomes larger. Furthermore, in the cooling process to 25°C, the 2.05 THz absorption shifts to 2.15 THz and the lattice constants associated with this absorption become smaller. Therefore, intermolecular vibrations closely related to the crystal growth in PEN at high temperatures seem to be responsible for the THz absorption.
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