An FTIR/ATR in situ study of sorption and transport in corrosion protective organic coatings: Paper 2. The effects of temperature and isotopic dilution

A detailed temperature variation (18–50 °C) FTIR/ATR study of sorption and desorption of water into a series of cured epoxy resins has been reported. For higher temperatures (35–50 °C) the data were modelled with a single Fickian diffusion equation, giving an increased D as the temperature increased and an activation energy (E_A) in the 55–60 kJ mol⁻¹ region. At lower temperatures (18–35 °C)—well-below the T_g—a two-stage sorption equation was needed and the apparent E_A was negative. This is probably associated with changes in water clustering among the distributed ‘voids’ in the glassy polymer associated with chain relaxation at extended times. The use of D₂O as a penetrant allowed diffusion coefficient measurements for highly dense epoxy matrices, where FTIR/ATR cannot detect the ν(OH) band of water over and above the residual polymer–OH groups (in the dry state). The data for the D₂O studies were notably influenced by isotopic exchange; which was found to be a diffusion controlled process, even in a polymer matrix.