Front-surface external reflection infrared spectroscopy was used to study a set of samples of poly(ethylene terephthalate) (PET) corresponding to various states of order: highly amorphous, drawn at 80 °C to different draw ratios, and thermally crystallized under different conditions. Kramers-Kronig transformation provided high-quality spectra that included an accurate representation of the most intense bands in the spectrum, which are generally saturated or distorted in transmission and internal reflection spectra. Factor analysis indicated the presence of three principal components in the spectra, and by taking linear combinations of the three principal factors, it was possible to generate three distinct physically meaningful basis spectra designated G, TC, and TX. The G spectrum corresponds to a gauche conformation of the ethylene glycol moiety, which is predominant in the amorphous state, while the other two correspond to a trans glycol conformation. The TC spectrum corresponds to the true crystalline state of PET, in which the carbonyl groups are coplanar with and in an all trans arrangement with respect to the benzene rings. The TX spectrum, on the other hand, corresponds to a less ordered trans structure in which the peaks associated with the terephthaloyl moiety of the molecule resemble those observed for the amorphous phase, where the carbonyl groups are either noncoplanar or cis and trans with respect to the benzene rings. However, the TX spectrum is a major contributor in the spectra of the drawn samples. This indicates that drawing at 80 °C produces a structure in which gauche conformers are converted into extended trans sequences, but the terephthaloyl conformation remains rather disordered. In other words, the development of order involves two processes that do not necessarily occur simultaneously. This provides new insight into the nature of the widely reported "intermediate" phase in PET and into the complex behavior of some of the trans peaks in the infrared spectrum. Detailed analysis of the basis spectra, including curve fitting, has also made it possible to suggest more precise assignments for some of the bands in the IR spectrum.

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In this paper, we study the relaxation behavior of initially amorphous poly(ethylene terephthalate) (PET) films drawn, at 80°C using a draw rate of 2 cm/min, to a draw ratio (A) from 1 to 5 and then quenched to room temperature. These films were then heated at different temperatures from 68 to 80°C for different times and their orientation determined. The orientation measurements were performed by transmission infrared spectroscopy and the bands used for the determination of orientation were those at 1340 and 970 cm-' for the trans conformers, normalized using the 1410 cm-' benzene ring vibration. The crystallinity was determined by thermal analysis. It is shown that when PET is drawn to A values up to 2-2.5 (before stress-induced crystallization), the orientation relaxes rapidly a t temperatures close to the glass transition temperature of PET. For A values of 3 or higher, the orientational relaxation of the amorphous regions is hindered. This effect is ascribed to the development of strain-induced crystallites, which are believed to act as pseudo-crosslinks.

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Crystalline syndiotactic styrene/p-methyl styrene copolymer (SPMS) has been oriented by tensile drawing at various temperatures between the glass transition and crystalline melting point. The microstructural changes resulting from drawing have been studied using differential scanning calorimetry OSC) and wide angle Xray diffraction (WAXD). With increasing draw temperature, both melting temperature and crystalline dimensions of the oriented samples increase. The heat of fusion increases with increasing draw temperature up to -200°C. It also increases with draw ratio and draw rate, while the crystalline width increases only with draw ratio. The amorphous fraction shows a clear glass transition, the temperature of which (Tg) increases with draw ratio. However, Tg decreases somewhat with increasing draw temperature. This is interpreted in terms of the stretching of the randomly coiled amorphous phase molecules.