Mobility and solubility of antioxidants and oxygen in glassy polymers. III. Influence of deformation and orientation on oxygen permeability

The mobility of small molecules in a glassy polymer is largely determined by the amount of free volume present in the material. The amount of free volume can be altered by changing the physical state of the polymer. Plastic deformation under compression reduces this amount, whereas the application of a tensile stress increases it. Furthermore, orientation of a polymer introduces an anisotropy in the free volume. The change in free volume was monitored by oxygen permeation experiments. A clear correlation was found between the draw ratio, plastic deformation and stress on the one hand and oxygen permeability on the other. Since the mobility of oxygen is an important parameter for the stabilisation of a polymer against oxidation, the physical state of the polymer can have a significant influence on the service life of the product.