Comparison of different approaches to describe the thermotropic volume phase transition of smart microgels

Abstract

AbstractThe description of gel swelling by Flory and Rehner using the original Flory–Huggins interaction parameter for the polymer–solvent interaction cannot be applied to most smart microgels. Here, we compare descriptions of the swelling curves of such microgels using series expansions of the Flory–Huggins parameter $$\chi$$ χ with the results of Hill-like equation for $$\chi$$ χ . We study N-isopropyl-acrylamide particles at different concentrations of the cross-linker N,N-methylenebisacrylamide. The hydrodynamic radius $$R_{\mathrm {H}}$$ R H of the microgel particles is determined using photon correlation spectroscopy. The fits with the series expansion of $$\chi$$ χ nicely follow the experimental data. However, already with the first-order series expansion, the computed $$\Theta$$ Θ temperatures are not physically reasonable. Moreover, the physical meaning of the parameters of the series expansion is not clear. The Hill-like equation, which we recently introduced, yields a good description of all measured microgel swelling curves and provides physically meaningful parameters. For instance, the Hill parameter $$\nu$$ ν corresponds to the number of water molecules per network chain cooperatively leaving the chain at the volume phase transition. Graphical abstract Different approaches to model the Flory-Huggins interaction parameter are explored and compared with respect to the quality of the fit of microgel swelling curves.