Crystallization kinetics and morphology of poly(trimethylene terephthalate)

In this work, the isothermal crystallization kinetics of polytrimethylene terephthalate (PTT) was first investigated from two temperature limits of melt and glass states. For the isothermal melt crystallization, the values of Avrami exponent varied between 2 and 3 with changing crystallization temperature, indicating the mixed growth and nucleation mechanisms. Meanwhile, the cold crystallization with an Avrami exponent of 5 indicated a character of three-dimensional solid sheaf growth with athermal nucleation. Through the analysis of secondary nucleation theory, the classical regime I→II and regime II→III transitions occurred at the temperatures of 488 and 468 K, respectively. The average work of chain folding for nucleation was ca. 6.5 kcal mol−1, and the maximum crystallization rate was found to be located at ca. 415 K. The crystallite morphologies of PTT from melt and cold crystallization exhibited typical negative spherulite and sheaf-like crystallite, respectively. Moreover, the regime I→II→III transition was accompanied by a morphological transition from axialite-like or elliptical-shaped structure to banded spherulite and then non-banded spherulite, indicating that the formation of banded spherulite is very sensitive to regime behavior of nucleation.