Temperature and rate dependent finite strain behavior of poly(ethylene terephthalate) and poly(ethylene terephthalate)-glycol above the glass transition temperature

Abstract

Poly(ethylene terephthalate) is widely used for consumer products such as drawn fibers, stretched films, and soda bottles. Much of its commercial success lies in the fact that it crystallizes at large strains during warm deformation processing. The imparted crystallinity increases its stiffness and strength, improves its dimensional stability, and increases its density. The crystallization process and the stress-strain behavior above the glass transition depend strongly on temperature, strain rate, strain magnitude, and strain state. A robust constitutive model to accurately account for this stress-strain behavior in the processing regime is highly desirable in order to predict and computationally design warm deformation processes to achieve desired end product geometries and properties. This thesis aims to better understand the material behavior above the glass transition temperature in the processing regime. It examines the strain rate, strain state, and temperature dependent mechanical behavior of two polymers: PET and PETG, an amorphous non-crystallizing copolymer of PET, in order to isolate the effects of crystallization on the stress-strain behavior. Experiments over a wide range of temperatures and strain rates were performed in uniaxial and plane strain compression. A constitutive model of the observed rate and temperature dependent stress-strain behavior was then developed. The model represents the material's resistance to deformation with two parallel elements: an intermolecular resistance to flow and a resistance due to molecular network interactions.

(cont.) The model predicts the temperature and rate dependence of many stress-strain features of PET and PETG very well, including the initial modulus, flow stress, initial hardening modulus, and dramatic strain hardening. The modeling results indicate that the large strain hardening behavior of both materials can only be captured by including a critical orientation parameter to halt the molecular relaxation process once the network achieves a specific level of molecular orientation. This suggests that much of the strain hardening in PET is due to molecular orientation and not to strain-induced crystallization. An example blow molding process is simulated to demonstrate the industrial applicability of the proposed model.