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Isothermal crystallization and subsequent melting behavior for three different types of linear aromatic polyester, namely poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poly(butylene terephthalate) (PBT), were investigated (with an emphasis on PTT in comparison with PET and PBT). These polyesters were different in the number of methylene groups (i.e. 2, 3, and 4 for PET, PTT, and PBT, respectively). Isothermal crystallization studies were carried out in a differential scanning calorimeter (DSC) over the crystallization temperature range of 182-208• C. The wide-angle X-ray diffraction (WAXD) technique was used to obtain information about crystal modification and apparent degree of crystallinity. The kinetics of the crystallization process was assessed by a direct fitting of the experimental data to the Avrami, Tobin, and Malkin macrokinetic models. It was found that the crystallization rates of these polyesters were in the following order: PBT > PTT > PET, and the melting of these polyesters exhibited multiple-melting phenomenon. Lastly, the equilibrium melting temperature for these polyesters was estimated based on the linear and non-linear Hoffman-Weeks (LHW and NLHW) extrapolative methods.

The kinetics of nonisothermal crystallization of three different types of linear aromatic polyester, namely poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), and poly(butylene terephthalate) (PBT), which are different in their number of methylene groups (i.e. 2, 3, and 4 for PET, PTT, and PBT, respectively), was investigated using differential scanning calorimetry (DSC). Analysis of the data was carried out based on the Avrami, Tobin, Ozawa, and Ziabicki models. It was found that the Avrami model provided a more satisfactorily good fit to the experimental data for these polyesters than did the Tobin model. The Ozawa model was found to describe the experimental data fairly well. The Ziabicki's kinetic crystallizability parameter G for these polyesters was found to be of the following order: PBT > PTT > PET. The effective energy barrier for nonisothermal crystallization process of these polyesters, determined by the Friedman method, was found to be an increase function with the relative degree of crystallinity.

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The effects of crystalline and orientational memory phenomena on the subsequent isothermal crystallization and subsequent melting behavior of poly(trimethylene terephthalate) (PTT) were investigated by studying the effect of prior melt‐annealing temperature, Tf, on the subsequent isothermal crystallization kinetics, crystalline structure and subsequent melting behavior of neat and sheared PTT samples. On partial melting, choices of the Tf used to melt the samples played an important role in determining their bulk crystallization rates, in which the bulk crystallization rate parameters studied were all found to decrease monotonically with increasing Tf. The decrease in the values of these rate parameters with Tf continued up to a critical Tf value (ie ca 275 °C for neat PTT samples and ca 280 °C for PTT samples which were sheared at shear rates of 92.1 and 245.6 s−1). Choices of the Tf used to melt neat PTT samples had no effect on the crystal structure formed. The subsequent melting behavior suggested that the Tf used to melt both neat and sheared samples had no effect on the peak positions of the melting endotherms observed and that the observed peak values of these endotherms for all sample types studied were almost identical. Copyright © 2004 Society of Chemical Industry