Attraction Between Like-Charge Surfaces in Polar Mixtures

We examine the force between two charged surfaces immersed in aqueous mixtures having a coexistence curve. For a homogeneous water-poor phase, as the distance between the surfaces is decreased, a water-rich phase condenses at a distance $D_t$ in the range 1-100nm. At this distance the osmotic pressure can become negative leading to a long-range attraction between the surfaces. The osmotic pressure vanishes at a distance $D_e<D_t$, representing a very deep metastable or globally stable energetic state. We give analytical and numerical results for $D_t$ and $D_e$ on the Poisson-Boltzmann level.Comment: 6 pages, 6 figure

Solvo-osmotic flow in electrolytic mixtures

We show that an electric field parallel to an electrically neutral surface can generate flow of electrolytic mixtures in small channels. We term this solvo-osmotic flow, since the flow is induced by the asymmetric preferential solvation of ions at the liquid-solid interface. The generated flow is comparable in magnitude to the ubiquitous electro-osmotic flow at charged surfaces, but for a fixed surface charge density, it differs qualitatively in its dependence on ionic strength. Solvo-osmotic flow can also be sensitively controlled with temperature. We derive a modified Helmholtz-Smoluchowski equation that accounts for these effects.Comment: 11 pages, 4 figure

Self-propulsion mechanism of active Janus particles in near-critical binary mixtures

Gold-capped Janus particles immersed in a near-critical binary mixture can be propelled using illumination. We employ a non-isothermal diffuse interface approach to investigate the self-propulsion mechanism of a single colloid. We attribute the motion to body forces at the edges of a micronsized droplet that nucleates around the particle. Thus, the often-used concept of a surface velocity cannot account for the self-propulsion. The particle's swimming velocity is related to the droplet shape and size, which is determined by a so-called critical isotherm. Two distinct swimming regimes exist, depending on whether the droplet partially or completely covers the particle. Interestingly, the dependence of the swimming velocity on temperature is non-monotonic in both regimes.Comment: 5 pages, 3 figure

Dense ionic fluids confined in planar capacitors: in- and out-of-plane structure from classical density functional theory

The ongoing scientific interest in the properties and structure of electric double layers (EDLs) stems from their pivotal role in (super)capacitive energy storage, energy harvesting, and water treatment technologies. Classical density functional theory (DFT) is a promising framework for the study of the in- and out-of-plane structural properties of double layers. Supported by molecular dynamics simulations, we demonstrate the adequate performance of DFT for analyzing charge layering in the EDL perpendicular to the electrodes. We discuss charge storage and capacitance of the EDL and the impact of screening due to dielectric solvents. We further calculate, for the first time, the in-plane structure of the EDL within the framework of DFT. While our out-of-plane results already hint at structural in-plane transitions inside the EDL, which have been observed recently in simulations and experiments, our DFT approach performs poorly in predicting in-plane structure in comparison to simulations. However, our findings isolate fundamental issues in the theoretical description of the EDL within the primitive model and point towards limitations in the performance of DFT in describing the out-of-plane structure of the EDL at high concentrations and potentials

Tuning colloid-interface interactions by salt partitioning

We show that the interaction of an oil-dispersed colloidal particle with an oil-water interface is highly tunable from attractive to repulsive, either by varying the sign of the colloidal charge via charge regulation, or by varying the difference in hydrophilicity between the dissolved cations and anions. In addition, we investigate the yet unexplored interplay between the self-regulated colloidal surface charge distribution with the planar double layer across the oil-water interface and the spherical one around the colloid. Our findings explain recent experiments and have direct relevance for tunable Pickering emulsions.Comment: 5+4 pages, 3+4 figures, V2: improved text and figures, more detailed supplementar

Microphase separation in oil-water mixtures containing hydrophilic and hydrophobic ions

We develop a lattice-based Monte Carlo simulation method for charged mixtures capable of treating dielectric heterogeneities. Using this method, we study oil-water mixtures containing an antagonistic salt, with hydrophilic cations and hydrophobic anions. Our simulations reveal several phases with a spatially modulated solvent composition, in which the ions partition between water-rich and water-poor regions according to their affinity. In addition to the recently observed lamellar phase, we find tubular, droplet, and even gyroid phases reminiscent of those found in block copolymers and surfactant systems. Interestingly, these structures stem from ion-mediated interactions, which allows for tuning of the phase behavior via the concentrations, the ionic properties, and the temperature.Comment: 5 pages, 4 figure

Phase-Separation Transition in Liquid Mixtures Near Charged Objects

We study the thermodynamic behavior of nonpolar liquid mixtures in the vicinity of curved charged objects, such as electrodes or charged colloids. For small enough charge on the object, or equivalently, small potential, the dielectrophoretic force leads to enrichment of the more polar liquid close the colloid. However, there is a critical value of charge (or potential), above which a phase-separation transition occurs, and the interface between high- and low-dielectric constant components becomes sharp. Analytical and numerical composition profile are given, and the equilibrium front location as a function of charge or voltage is found. We further employ a simple Cahn-Hilliard type equation to study the dynamics of phase-separation in spatially nonuniform electric fields. We find an exponential relaxation of the composition front location, with a characteristic time depending on the charge, mixture composition and ambient temperature.Comment: final version, includes small changes and typo correction