Non-Gaussian elasticity and charge density-dependent swelling of strong polyelectrolyte poly(N-isopropylacrylamide-co-sodium acrylate) hydrogels

Abstract

The mechanical properties and charge density-dependent swelling of strong polyelectrolyte poly(N-isopropylacrylamide-co-sodium acrylate) P(NIPA-co-NaA) hydrogels prepared at a fixed total monomer concentration and crosslinker ratio, but at various charge densities, i.e. NaA content in the feed between 0 and 90 mol%, were investigated. The elasticity results were discussed to explain the relationship between the elastic free energy ΔG_el and the swelling ratio α as well as to fit the existing theories to the swelling data. The implications of the obtained results for the deviation from the Gaussian chain statistics were considered. Given the swollen elastic modulus and the dependence of charge density on the equilibrium gel volume, it would seem that the latter factor is an important determinant of non-Gaussian elasticity of polyelectrolyte P(NIPA-co-NaA) hydrogels containing strongly dissociated groups. The dependence of the reduced modulus on the equilibrium gel volume was found to be G_r ≈ (V_eq)^−0.47 at low swelling degree and G_r ≈ (V_eq)^0.64 at high swelling degree and the deviation was interpreted as the non-Gaussian elasticity of equilibrium swollen P(NIPA-co-NaA) hydrogels. The detailed theoretical treatments of non-Gaussian elasticity of P(NIPA-co-NaA) hydrogels and, in particular, the influence of the charge density on the elasticity showed that the knowledge of several swollen state parameters and the effective charge density distribution of hydrogels were strongly required to explain the variation of the elastic properties depending on the ionic group content. Within this framework, the dominant mechanism responsible for the deviation from Gaussian elasticity and the finite chain extensibility of ionic P(NIPA-co-NaA) hydrogels was described and the results were used to explain the dependence of the elastic modulus on the equilibrium gel volume.