Effect of cross-linking density on swelling behavior of NIPA gel particles

Submicrometer-sized N-isopropylacrylamide(NIPA) gel particles with various composition of cross-linker are prepared by precipitation polymerization and their swelling behaviors are examined by using photon correlation spectroscopy(PCS) technique. Theoretically, Hu et al.'s double-lattice model has been modified by introducing a new universal constant and simplifying the expression of the Helmholtz energy of mixing. The modified double-lattice model(MDL) describes very well the lower critical solution temperature (LCST) behavior of linear PNIPA/water system. For cross-linked NIPA gel particles in water, we have combined MDL theory with Flory and Erman's theory of elasticity, which takes into account the nonaffine displacements of network junctions under high degree of swelling. Energy parameters obtained from the linear PNIPA/water system were directly used to predict swelling equilibria for the NIPA gel/water system. Our results represented that an affine network model explained the swelling behavior at high swelling ratio more accurately than that of the phantom network model. To correct the deviation of the continuous volume transition temperature, we have considered the interaction energy parameter between cross-linker segment and solvent molecule. The corrected model was applied to the swelling equilibria of gel particles with various cross-linking density and agreed well with their experimental data with no adjustable model parameters.