Understanding the swelling of poly (N-isopropyl acrylamide) gels through the study of free volume hole size distributions using positron annihilation spectroscopy

Poly (N-isopropyl acrylamide) gels were prepared by UV polymerization with different degree of cross-linking in different solvents. Ethylene glycol dimethacrylate and penta-erythritol tetra-acrylate were used as cross-linkers, and methanol and dimethyl formamide (DMF) were used as solvents for gel preparation. The free volume fraction and hole size distribution in the dry gels were measured using positron annihilation lifetime spectroscopy. The equilibrium swelling of the samples in water was measured at room temperature. Both swelling properties of gels and the free volume distributions were seen to be sensitive to the amount, type, and functionality of cross-linkers as well as solvent medium used for synthesis. The gels prepared in DMF showed poor swelling properties than those prepared in methanol. The mean free volume hole size was higher while the variance of hole size distribution was smaller in the gels prepared in DMF medium compared to those prepared in methanol. The free volume fractions in the gels were found to be inversely correlated to the extent of equilibrium swelling for similar chemical compositions. The possible reasons are discussed.