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Register a new userLinear and Nonlinear Viscoelasticity of Concentrated Thermoresponsive Microgel Suspensions
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This is an integrated experimental and theoretical study of the dynamics and rheology of self-crosslinked, slightly charged, temperature responsive soft Poly(N-isopropylacrylamide) (pNIPAM) microgels over a wide range of concentration and temperature spanning the sharp change in particle size and intermolecular interactions across the lower critical solution temperature (LCST). Dramatic, non-monotonic changes in viscoelasticity are observed with temperature, with distinctive concentration dependences in the dense fluid, glassy, and soft-jammed states. Motivated by our experimental observations, we formulate a minimalistic model for the size dependence of a single microgel particle and the change of interparticle interaction from purely repulsive to attractive upon heating. Using microscopic equilibrium and time-dependent statistical mechanical theories, theoretical predictions are quantitatively compared with experimental measurements of the shear modulus. Good agreement is found for the nonmonotonic temperature behavior that originates as a consequence of the competition between reduced microgel packing fraction and increasing interpar-ticle attractions. Testable predictions are made for nonlinear rheological properties such as the yield stress and strain. To the best of our knowledge, this is the first attempt to quantitatively understand in a unified manner the viscoelasticity of dense, temperature-responsive microgel suspensions spanning a wide range of temperatures and concentrations.
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We present an integrated experimental and quantitative theoretical study of the mechanics of self-crosslinked, neutral, repulsive pNIPAM microgel suspensions over concentration (c) range spanning the fluid, glassy and putative soft jammed regimes. In the glassy regime we measure a linear elastic dynamic shear modulus over 3 decades which follows an apparent power law concentration dependence G~$c^{5.64}$, followed by a sharp crossover to a nearly linear growth at high concentrations. We formulate a theoretical approach to address all three regimes within a single conceptual Brownian dynamics framework. A minimalist single particle description is constructed that allows microgel size to vary with concentration due to steric de-swelling effects. Using a Hertzian repulsion interparticle potential and a suite of statistical mechanical theories, quantitative predictions under quiescent conditions of microgel collective structure, dynamic localization length, elastic modulus, and the structural relaxation time are made. Based on a constant inter-particle repulsion strength parameter which is determined by requiring the theory to reproduce the linear elastic shear modulus over the entire concentration regime, we demonstrate good agreement between theory and experiment. Theoretical predictions of how quiescent structural relaxation time changes under deformation, and how the yield stress and strain change as a function of concentration has been made. Reasonable agreement with our observations is obtained. To the best of our knowledge, this is the first attempt to quantitatively understand structure, quiescent relaxation and shear elasticity, and nonlinear yielding of dense microgel suspensions using microscopic force based theoretical methods that include activated hopping processes. We expect our approach will be useful for other soft polymeric particle suspensions in the core-shell family.
Recent experiments show a strong rotational-diffusion enhancement for self-propelled microrheological probes in colloidal glasses. Here, we provide microscopic understanding using simulations with a frictional probe-medium coupling that converts active translation into rotation. Diffusive enhancement emerges from the mediums disordered structure and peaks at a second-order transition in the number of contacts. Our results reproduce the salient features of the colloidal glass experiment and support an effective description that is applicable to a broader class of viscoelastic suspensions.
We review recent advances in imaging the flow of concentrated suspensions, focussing on the use of confocal microscopy to obtain time-resolved information on the single-particle level in these systems. After motivating the need for quantitative (confocal) imaging in suspension rheology, we briefly describe the particles, sample environments, microscopy tools and analysis algorithms needed to perform this kind of experiments. The second part of the review focusses on microscopic aspects of the flow of concentrated model hard-sphere-like suspensions, and the relation to non-linear rheological phenomena such as yielding, shear localization, wall slip and shear-induced ordering. Both Brownian and non-Brownian systems will be described. We show how quantitative imaging can improve our understanding of the connection between microscopic dynamics and bulk flow.
We present a comprehensive study of the slip and flow of concentrated colloidal suspensions using cone-plate rheometry and simultaneous confocal imaging. In the colloidal glass regime, for smooth, non-stick walls, the solid nature of the suspension causes a transition in the rheology from Herschel-Bulkley (HB) bulk flow behavior at large stress to a Bingham-like slip behavior at low stress, which is suppressed for sufficient colloid-wall attraction or colloid-scale wall roughness. Visualization shows how the slip-shear transition depends on gap size and the boundary conditions at both walls and that partial slip persist well above the yield stress. A phenomenological model, incorporating the Bingham slip law and HB bulk flow, fully accounts for the behavior. Microscopically, the Bingham law is related to a thin (sub-colloidal) lubrication layer at the wall, giving rise to a characteristic dependence of slip parameters on particle size and concentration. We relate this to the suspensions osmotic pressure and yield stress and also analyze the influence of van der Waals interaction. For the largest concentrations, we observe non-uniform flow around the yield stress, in line with recent work on bulk shear-banding of concentrated pastes. We also describe residual slip in concentrated liquid suspensions, where the vanishing yield stress causes coexistence of (weak) slip and bulk shear flow for all measured rates.
We study the pressure-driven flow of concentrated colloids confined in glass micro-channels at the single particle level using fast confocal microscopy. For channel to particle size ratios $a/bar{D} lesssim 30$, the flow rate of the suspended particles shows fluctuations. These turn into regular oscillations for higher confinements ($a/bar{D} simeq 20$). We present evidence to link these oscillations with the relative flow of solvent and particles (permeation) and the effect of confinement on shear thickening.
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