Vibrational Spectroscopic Study on the Origin of Stress Oscillation during Step-Wise Stretching in Poly(Ethylene Terephthalate)

Abstract

The origin of the phenomenon of stress oscillation during step-wise stretching at room temperature for amorphous poly(ethylene terephthalate) (PET) was investigated using vibrational spectroscopy. For the first time, transmission Fourier transform infrared (FT-IR), attenuated total reflection (ATR) FT-IR, and micro-Raman spectroscopies were used in order to investigate the correlation of the orientation of the molecular chains, their conformational transformations, and the appearance of stress-induced crystallization to the phenomenon of stress oscillation during the step-wise stretching procedure. The phenomenon of stress oscillation occurs when amorphous PET is exposed to mechanical stress during which the extension rate is increased in a step-wise manner. This phenomenon leads to the formation of a pattern of opaque and transparent stripes (“striated” or oscillating region), clearly distinguished from the unstretched (“bulk”) and the “necking” regions. Both infrared and Raman spectroscopic investigations revealed that the main conformational transformations and a significant increase of the crystallinity occur simultaneously in the “striated” region. Polarized infrared experiments showed the presence of increased molecular orientation, which is more profound for the “intense striated” region. Finally, micro-Raman spectroscopy allowed the study of opaque and transparent stripes individually and showed that the opaque stripes are more crystalline. Thus, our findings provide conclusive experimental support for the theory, which directly correlates the appearance of the stress-oscillation phenomenon with the induction of crystallinity and heat release and is based on Barenblatt's model. Our study also provides new conformational assignments for the infrared bands in PET for the high-frequency region from 3200 to 3800 cm−1. Specifically, the bands at 3336 cm−1 and at 3298 cm−1 have been attributed to the trans and gauche conformations, respectively.