Comparison of Swelling and Mechanical Analysis for the Determination of Crosslink Density of Acrylamide Based Hydrogels Prepared by Ionizing Radiation

One of the basic parameters that describes the structure of a hydrogel network is the molecular weight between cross-links or cross-link density of highly swollen network. Several theories have been proposed to calculate the average molecular weight between cross-links. In the highly swollen state, the constrained junction theory indicates that a real network exhibits properties closer to those of the phantom network model and molecular weight between cross-links can be calculated easily by using swelling and polymer-solvent based parameters such as molar volume of the swelling agent, polymer-solvent interaction parameter, functionality, specific volume of the polymer and polymer volume fraction in the relaxed state. Molecular weight between cross-links (Mcaver.) and effective cross-linking density (Ve) of a hydrogel can also be determined from shear modulus data obtained from compression tests. Our previous studies indicated that simple compression analyses and equations derived from Phantom network theory can be used for the determination of effective cross-link density of hydrogels without needing some polymer-solvent based parameters as in the case of swelling based determinations. The Mcaver. and Ve values calculated from mechanical tests were found to be very close to the values obtained from swelling experiments. Slight differences observed were attributed to the uncertainty on the value of the χ parameter used in the expression related to swelling data. In this study the uncertainty in the polymer based parameter χ on the Mcaver. was discussed. Poly(acrylamide/methacrylamide) P(AAm/MAAm) and Poly(acrylamide/hydroxyethylmeth acrylate) P(AAm/HEMA) hydrogels were prepared by gamma rays and used as model hydrogel systems. The uniaxial compression was applied to cylindrical samples using the Universal Testing Instrument in the swollen form at pH 7. Stress-strain curves of hydrogels were evaluated to calculate the shear modulus values. The Mcaver. and Ve obtained from mechanical properties were significantly different than the values obtained from swelling experiments. Large differences were attributed to the uncertainty on the value of the χ parameter used in the Flory-Rehner equations. Only 1 % changing of this parameter doubled or reduced the Mcaver. value of hydrogel to half value