Microrheology of thermoresponsive poly(N-isopropylacrylamide) microgel dispersions near a substrate surface

Abstract

HypothesisRelative to the bulk systems, the near-wall (<500 nm) rheological responses of soft poly(N-isopropylacrylamide) (PNIPAM) microgel dispersions may exhibit distinct dependence on the frequency (ω), temperature (T), and effective volume fraction (ϕeff) during the volume phase transitions. The microrheological behaviors are expected to be governed by the near-wall microstructure and its spatial heterogeneity. ExperimentsThe combination of active microrheometry (multipole magnetic tweezers) and total internal reflection microscopy (TIRM) was employed to probe the structure–rheology relationships of microgel dispersions near a substrate surface. The ω, T, and ϕeff-dependences of the storage modulus (G′), loss modulus (G"), and softness (J) were analyzed by power-law and Arrhenius-like scaling theories. The fluctuation of J was further analyzed to give a quantitative description of the inhomogeneity in the near-wall regions. Findings(1) Remarkable differences in the rheological behaviors between the bulk and near-wall cases are revealed, where the latter shows a segmented overlap behavior in ϕeff; (2) Five regimes of ϕeff that correspond to distinct physical states of the microgel dispersions are determined; (3) The near-wall local structures exhibit more heterogeneity in the glass and colloidal gel regimes as compared to the liquid regime.