Deswelling kinetics of polyacrylate gels in solutions of cetyltrimethylammonium bromide.

The deswelling kinetics of single sodium polyacrylate gel beads (radius 40-160 microm) in aqueous solutions of cetyltrimethylammonium bromide under conditions of forced convection are investigated using micromanipulator assisted light microscopy. The purpose of the study is to further evaluate a previously published model (J. Phys. Chem. B 2003, 107, 9203) using a higher homolog surfactant. For gels with expected fast deswelling (small gel size/low surfactant concentration) and/or in low electrolyte concentration, the model is found to correctly predict the deswelling characteristics of the gel beads. However, for some gels with expected slow deswelling, especially in high electrolyte concentration (10 mM NaBr), the model widely underestimates the required deswelling time. The reason for this is argued to be the longer time frame and high bromide concentration allowing the formation of a denser, more ordered structure in the surface phase, which resists the deformation and reorganization of material necessary for deswelling. Unexpectedly long lag times before the start of deswelling are also found for gels in low surfactant concentration, indicating that a relatively high surfactant concentration in the gel, greatly exceeding the critical aggregation concentration, is needed to start formation of a collapsed surface phase. This critical surfactant concentration is found to be dependent on initial gel radius, as small gels require a relatively higher concentration to initiate collapse.