Crystallization of polyethylene terephthalate

Abstract

A method for following rapid crystallization in polymers using infrared absorption has been devised. The infrared absorption was correlated quantitatively with the density of polyethylene terephthalate for varying degrees of crystallinity and qualitatively with the change in x‐ray diffraction pattern on crystallization of this polymer. This technique has been applied to measure the crystallization–time curves of thin films of polyethylene terephthalate at intervals of 10°C. for temperatures between 120 and 240°C. Half‐times from these curves show a minimum near 190°C. The temperature dependence of the data is discussed in terms of the Volmer‐Becker‐Turnbull theory of nucleation in condensed systems. An activation energy of 20 kcal./mole for short‐range diffusion of chain segments is obtained from the temperature coefficient of the observed induction time. The data on the kinetics of the crystallization are compared with the results of an analysis of Avrami. A constant, A, was introduced into Avrami's equation to give: A is the limiting volume fraction of crystalline material after a long time and was determined from density measurements. The crystallization was found to follow this equation from 2 through 90% transformation for temperatures from 120 to 180°C. Deviation appeared in the region below 10% transformation at higher temperatures. The value of k was interpreted as indicating plate‐like growth at crystallites from 120 to 180°C.