Effect of film thickness on auto-oxidation in cobalt-catalyzed 1,4-polybutadiene films

Oxygen mass uptake was measured in 1,4-polybutadiene (PB) films undergoing cobalt-catalyzed oxidation in air. Films thicker than approximately 50 μm showed an increase in oxygen uptake per unit polymer mass as film thickness increased, while oxygen uptake per unit film area remained independent of thickness, suggesting that oxidation was heterogeneous and proceeded essentially as an oxidized front penetrating into the film from the surfaces exposed to oxygen. In contrast, oxidation in films thinner than about 28 μm proceeds homogeneously, with oxygen uptake per unit mass being essentially independent of thickness. In oxidized samples, oxygen and nitrogen permeability decreased by more than two orders of magnitude relative to permeability values in unoxidized samples. In thicker films, a two-phase model, based upon high levels of oxidation in a thin skin at the surface of PB and relatively low levels of oxidation in the core of the films, was used to describe gas permeability data and estimate the oxygen and nitrogen permeability in fully oxidized PB.