Molecular motion in concentrated solutions of spherical polystyrene microgels studied with the pulsed field gradient n.m.r.

Abstract

Results of a pulsed field gradient n.m.r. study of the motion of swollen spherical microgels in solution are presented. We have measured the echo attenuation (or the incoherent dynamic structure function) of the protons in the microgels in the dynamic range from qR≪1 up to qR ≈ 1.8 (where q=scattering vector and R = particle radius), and in the timescale from a few milliseconds up to 100 ms. Rotational diffusion of the microgel spheres could not be detected with certainty. However, restricted diffusion of the spheres within a cage was observed, in particular for the large microgel with R =125 nm, where the short-time diffusion could be monitored. For apparent volume fractions (φ > 0.6, the diffusion is restricted within a space scale of root mean square displacement, 〈z2〉 1 2 120 nm. With increasing volume fraction of the microgels in solution, (φ > 0.6, the diffusion becomes increasingly restricted. This crossover corresponds to the dynamic glass transition observed by Bartsch et al. for a similar system using quasielastic light scattering. © 1994