Time series Fourier transform infrared spectroscopy for characterization of water vapor sorption in hydrophilic and hydrophobic polymeric films

This work investigates the nature of the molecular interactions between water vapor and polymers using time series Fourier transform infrared (FTIR) spectroscopy. A detailed analysis of the frequency shifts and relative peak intensities led to the conclusion that polyvinyl alcohol (PVOH) sorbed a large quantity of water vapor molecules, resulting in swelling and dissolving of polymer crystallites. Difference spectra were calculated to investigate spectral changes occurring upon sorption by dividing the spectra of polymers during the sorption time series by the spectrum of the dry sample and subsequently subtracting the water vapor spectrum. Based on the absorbance area of the OH stretching vibration region (4000-3000 cm^-1) in difference spectra, the amount of water sorbed was significantly higher in poly-L-lactic acid (PLLA) and polyvinyl chloride (PVC) than in polyethylene (PE) and polytetrafluoroethylene (PTFE), increasing with the hydrophilicity of the surface. The OH stretching band of difference spectra shifted from 3499 cm^-1 for PVC, to 3416 cm^-1 for PE and finally to 3387 cm^-1 for PTFE, indicating a more strengthened hydrogen-bonding network in the PTFE matrix upon water vapor sorption.