Chemically and physically crosslinked chitosan membranes were prepared by treating chitosan (Ch) with glutaraldehyde (GA) and sulfuric acid (SA). FTIR and XRD results were employed to confirm the formation of covalent and ionic crosslinks between Ch, GA, and SA. The states of water in non-crosslinked and covalently and ionically crosslinked chitosan membranes containing different amount of water were investigated by low temperature differential scanning calorimetry measurements. The equilibrium swelling in water was examined gravimetrically. Two types of water were found in the polymer samples, i.e., freezing water and nonfreezing water. The effect of crosslinking process on water state and water uptake was analyzed. The water uptake decreased after chitosan crosslinking with GA, but significantly increased after later crosslinking with SA. The amount of non-freezing water was generally smaller in crosslinked membranes. An impact of molecular and supermolecular structure on water uptake and state of water in non-crosslinked and crosslinked chitosan membranes was discussed.

pH-responsive membranes prepared by treating chitosan (Ch) with glutaraldehyde (GA) or with GA and sulfuric acid (SA) were studied. The structure and properties of the membranes were characterized by Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and elemental analysis. The effect of the cross-linking process both on the dynamic swelling behaviour of the hydrogel membranes and on the mechanism of water transport through those membranes was investigated in buffer solutions of different pH (1.2-9.5). The mechanism of water transport through the hydrogel chitosan membranes was affected by membrane composition and pH of the swelling medium. Non-cross-linked Ch membrane showed a non-Fickian swelling behaviour in the pH range 6.5-9.5. Chitosan membrane cross-linked with GA (Ch/GA) showed less-Fickian or Fickian swelling behaviour in all buffer solutions. In the case of chitosan membrane cross-linked with GA and SA (Ch/GA/SA), at low pH (lower than the pK a of the hydrogel) the water transport was controlled more by polymer relaxation than by penetrant diffusion. The experimental data clearly suggested that the swelling process in all buffer solutions obeyed second-order kinetics. Values of an apparent swelling rate constant for Ch/ GA and Ch/GA/SA membranes were of the same order of magnitude for acidic and neutral swelling media but they increased for alkaline solutions.