FTIR-ATR STUDIES OF THE STRUCTURE AND DYNAMICS OF WATER-MOLECULES IN POLYMERIC MATRICES - A COMPARISON OF PET AND PVC

We report a systematic FTIR study of the perturbation of water ''sorbe d'' into the polymers PET and PVC as a function of crystallinity (PET) or plasticizer content (PVC). Band shapes of the composite v(OH) band of H2O obtained by the ATR technique have been fitted to individual c omponents,corresponding to those recently found for pure water itself. A detailed quantitative analysis of the frequency shifts and relative intensties has led to conclusion that these component bands show dire ct evidence for the breaking of the water network in the polymer matri x and that this process depends on the polymer chemical and/or physica l properties, Evidence is also found for interactions of water with th e polymer at the lower end of the hydrogen bond interaction scale. The component band relative intensities (compared with those of pure wate r) have been used to compute an intensity enhancement parameter, P, wh ich is a measure of the perturbation of a particular water distributio n due to dissolution in the polymer matrix. For PET, P varies systemat ically with density, reflecting the ability of water to penetrate the polymer microstructure. For PVC the plasticizer content (and hence T-g ) has considerable influence on the sorption (and swelling) process an d on the equilibrium content and state of water. Thus, ATR-FTIR has be en used for the first time to demonstrate, via intensity enhancement, the extent of electronic perturbation at a polymer/water interface.