Morphology and modulus–temperature behavior of semicrystalline poly(ethylene terephthalate) (PET)

The influence of the thermal history on the morphology and mechanical behavior of PET was studied. The degree of crystallinity (density measurements) and the morphological structure (electron microscopy and small-angle x-ray diffraction) depend on the crystallization temperature. The viscoelastic parameters obtained from the modulus–temperature curves are mainly determined by the morphology of the samples. The glass-transition temperature, T_i, is a function of the crystallinity and the crystallization temperature. It is maximum for a crystallinity between 0.34 and 0.39 for a sample crystallized isothermally between 120 and 150°C. This dependence on crystallization conditions is ascribed to the conformation of the amorphous chain segments between the crystalline lamellae as well as the concentration and the molecular weight of the polymer material rejected during isothermal crystallization. Both factors are supposed to be temperature-dependent. The value of the rubbery modulus is a function of both the volume concentration of the crystalline lamellae and the structure of the interlamellar amorphous regions (chain folds, tie molecules, chain ends, and segregated low molecular weight material). Annealing above the crystallization temperature of isothermally crystallized samples has a marked influence on their morphology and mechanical behavior. The morphological structure and the viscoelastic properties of annealed PET samples are completely different from those obtained with samples isothermally crystallized at the same temperature.