No Arabic abstract
In this study we use non-equilibrium thermodynamics to systematically derive a phase-field model of a polyelectrolyte gel coupled to a hydrodynamic model for a salt solution surrounding the gel. The governing equations for the gel account for the free energy of the internal interfaces which form upon phase separation, the nonlinear elasticity of the polyelectrolyte network, and multi-component diffusive transport following a Stefan--Maxwell approach. The time-dependent model describes the evolution of the gel across multiple time and spatial scales and so is able to capture the large-scale solvent flux and the emergence of long-time pattern formation in the system. We explore the model for the case of a constrained gel undergoing uni-axial deformations. Numerical simulations show that rapid changes in the gel volume occur once the volume phase transition sets in, as well as the triggering of spinodal decomposition that leads to strong inhomogeneities in the lateral stresses, potentially leading to experimentally visible patterns.
We analyse the dynamics of different routes to collapse of a constrained polyelectrolyte gel in contact with an ionic bath. The evolution of the gel is described by a model that incorporates non-linear elasticity, Stefan-Maxwell diffusion and interfacial gradient free energy to account for phase separation of the gel. A bifurcation analysis of the homogeneous equilibrium states reveals three solution branches at low ion concentrations in the bath, giving way to only one above a critical ion concentration. We present numerical solutions that capture both the spatial heterogeneity and the multiple time-scales involved in the process of collapse. These solutions are complemented by two analytical studies. Firstly, a phase-plane analysis that reveals the existence of a depletion front for the transition from the highly swollen to the new collapsed equilibrium state. This depletion front is initiated after the fast ionic diffusion has set the initial condition for this time regime. Secondly, we perform a linear stability analysis about the homogeneous states that show that for a range of ion concentrations in the bath, spinodal decomposition of the swollen state gives rise to localized solvent-rich(poor) and, due to the electro-neutrality condition, ion-poor(rich) phases that coarsen on the route to collapse. This dynamics of a collapsing polyelectrolyte gel has not been described before.
We study the thermodynamics of binary mixtures wherein the volume fraction of the minority component is less than the amount required to form a flat interface. Based on an explicit microscopic mean field theory, we show that the surface tension dominated equilibrium phase of a polymer mixture forms a single macroscopic droplet. A combination of elastic interactions that renormalize the surface tension, and arrests phase separation for a gel-polymer mixture, stabilize a micro-droplet phase. We compute the droplet size as a function of the interfacial tension, Flory parameter, and elastic moduli of the gel. Our results illustrate the importance of the rheological properties of the solvent in dictating the thermodynamic phase behavior of biopolymers undergoing liquid-liquid phase separation.
The relevance of anisotropic interactions in colloidal systems has recently emerged in the context of rational design of novel soft materials. Theoretical studies have predicted the possibility of a gas-liquid phase separation confined at low densities and the formation of empty liquids and equilibrium gels in low-valence systems. Here we provide experimental evidence of this scenario in Laponite, a complex colloidal clay with discotic shape and anisotropic interactions. We also report simulations of a patchy model for Laponite platelets, able to reproduce the observed experimental phase diagram and structural properties, confirming the crucial role of the reduced valence.
Using molecular dynamics computer simulations we investigate the aging dynamics of a gel. We start from a fractal structure generated by the DLCA-DEF algorithm, onto which we then impose an interaction potential consisting of a short-range attraction as well as a long-range repulsion. After relaxing the system at T=0, we let it evolve at a fixed finite temperature. Depending on the temperature T we find different scenarios for the aging behavior. For T>0.2 the fractal structure is unstable and breaks up into small clusters which relax to equilibrium. For T<0.2 the structure is stable and the dynamics slows down with increasing waiting time. At intermediate and low T the mean squared displacement scales as t^{2/3} and we discuss several mechanisms for this anomalous time dependence. For intermediate T, the self-intermediate scattering function is given by a compressed exponential at small wave-vectors and by a stretched exponential at large wave-vectors. In contrast, for low T it is a stretched exponential for all wave-vectors. This behavior can be traced back to a subtle interplay between elastic rearrangements, fluctuations of chain-like filaments, and heterogeneity.
We use numerical simulations and an athermal quasi-static shear protocol to investigate the yielding of a model colloidal gel. Under increasing deformation, the elastic regime is followed by a significant stiffening before yielding takes place. A space-resolved analysis of deformations and stresses unravel how the complex load curve observed is the result of stress localization and that the yielding can take place by breaking a very small fraction of the network connections. The stiffening corresponds to the stretching of the network chains, unbent and aligned along the direction of maximum extension. It is characterized by a strong localization of tensile stresses, that triggers the breaking of a few network nodes at around 30% of strain. Increasing deformation favors further breaking but also shear-induced bonding, eventually leading to a large-scale reorganization of the gel structure at the yielding. At low enough shear rates, density and velocity profiles display significant spatial inhomogeneity during yielding in agreement with experimental observations.