Oxygen-barrier properties of oriented and heat-set poly(ethylene terephthalate)

Abstract

The improvement in the oxygen-barrier properties of poly(ethylene terephthalate) (PET) by orientation and heat setting was examined. Orientation was carried out at 65 °C by constrained uniaxial stretching to a draw ratio of about 4. Heat setting was performed at temperatures from 90 to 160 °C with the specimen taut. Orientation decreased the permeability of PET to almost one-third that of the unoriented, amorphous polymer because of decreases in both the diffusion coefficient and the solubility coefficient. The proposed two-phase model for oriented PET consisted of a permeable isotropic amorphous phase (density = 1.335 g/cm3) with ethylene linkages predominately in the gauche conformation and an impermeable oriented phase (density = 1.38 g/cm3) with ethylene linkages that had transformed from the gauche conformation to the trans conformation during stretching. Chain segments in the trans conformation did not possess crystalline order; instead, they were viewed as forming an ordered amorphous phase. Crystallization by heat setting above the glass-transition temperature did not dramatically affect the permeability. However, a decrease in the diffusion coefficient, offset by an increase in the solubility coefficient, indicated that crystallization affected the barrier properties of the permeable amorphous phase. Analysis of the barrier data, assuming a two-phase model with variable density for both the permeable and impermeable phases, revealed that the impermeable phase density increased during crystallization, approaching a value of 1.476 g/cm3. This value is consistent with previous measurements of the density of the defective crystalline phase in PET. The density of the permeable amorphous phase decreased concurrently to about 1.325 g/cm3, indicating the appearance of additional free volume. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1679–1686, 2000