Crystallization kinetics of poly(ethylene terephthalate) : Memory effect of shear history

Abstract

The memory effect of shear history was studied with poly(ethylene terephthalate) (PET) prepared under different shear conditions of 11.7 to 1168 s-1 in a capillary rheometer. The shear history of PET resin led to a memory effect, which in turn affected the crystallization kinetics. The crystallization rate increased with increasing shear rate. Double peaks of heating crystallization exotherms and a low value of Avrami exponent appeared at low shear rates, which was attributed to the existence of crystallization processes with different rates: one was the fast process involving the disentangled molecules that persisted during melting, and the other was the slow process involving the highly entangled molecules. The change of instantanenous Avrami exponent and overall crystallization rate constant was in good agreement with the expected trends assuming coexistence of the two crystallization processes. The crystallization kinetics of PET with shear history could be regarded as a growth rate decrease problem to be interpreted by the modified Avrami equation, 1 - f = exp[-f•ft)"], when the fast process dominated the overall crystallization. The effect of shear history was reduced because of the relaxation process as the holding time in melt state before crystallization was increased.