Unveiling the structural relaxation of microgel suspensions at hydrophilic and hydrophobic interfaces

Hypothesis: Poly(N-isopropylacrylamide) (PNIPAM) microgel particles show considerable hydrophilicity below the lower critical solution temperature (LCST) while they become hydrophobic above LCST. We hypothesize that interfacial wettability could tune particle−surface interaction and subsequent structural relaxation of microgel suspensions at interfaces during the volume phase transition. Experiments: The evanescent-wave scattering images of microgels at hydrophilic and hydrophobic interfaces are analyzed by a density-fluctuation autocorrelation function (δACF) over a wide range of particle volume fraction ϕ. The structural relaxation is characterized by the decay behavior of δACF. The scattering images in bulk are also processed as a comparison. Findings: A two-step relaxation decay is observed at both hydrophilic and hydrophobic interfaces. Relative to fast decay, the rate of structural relaxation in slow decay is reduced by a factor of ∼ 500 and ∼ 50 at hydrophilic and hydrophobic interfaces, respectively. The relaxation times obey divergent power-law dependences on intermediate regime of observing length scales at the two interfaces. Besides, the distribution of fluctuation for relaxation time at different local regions reveals that the structural relaxation is much more homogenous at hydrophilic interfaces than that at hydrophobic interfaces, especially at high ϕ.