The behaviour of water in poly(dimethylsiloxane)

Experimentally-determined permeation transients do not support the view that the behaviour of water in PDMS is significantly influenced by statistical-mechanical clustering; rather, they suggest that water behaves in a straightforward way. Simple calculations appear to confirm that the incidence of the statistical clustering of water in the polymer is negligible. A diffusion coefficient derived to include the influence of hydrophilic sites within the polymer is partially successful in mathematically reproducing measured quantities. An entropy calculation appears to suggest that the amount of mobile water in PDMS is solely thermally determined; hence the reduction of supposed hydrophilic impurities would probably not lead to a reduction in water permeation. The apparently large difference between the water solubility in PDMS, and that in siloxane liquids, a point of some interest in separation processes, remains unexplained in this paper.