Experimental and DFT investigation of surface degradation of polyvinylidene fluoride membrane in alkaline solution

The degradation processes of polyvinylidene fluoride (PVDF) membranes in alkaline solutions were studied using FTIR, FT-Raman, XPS and density functional theory (DFT) simulations. The activation energies for the degradation paths were calculated by LST/QST search methods. The corresponding Gibbs free energies were calculated using a continuum solvation model. The analysis of the spectra indicates the presence of C=C bonds, hydroxyl and carbonyl groups on PVDF membranes. It can be inferred, from DFT calculations, that defluorination is the energetically favorable path, followed by the formation of C=C bonds. The subsequent hydroxylation and carbonyl formation experience higher activation barriers than the formation of C=C bonds. The results indicate that the theoretical calculations are in accordance with the experimental data.