Universal motion of mirror-symmetric microparticles in confined Stokes flow.

Comprehensive understanding of particle motion in microfluidic devices is essential to unlock additional technologies for shape-based separation and sorting of microparticles like microplastics, cells, and crystal polymorphs. Such particles interact hydrodynamically with confining surfaces, thus altering their trajectories. These hydrodynamic interactions are shape dependent and can be tuned to guide a particle along a specific path. We produce strongly confined particles with various shapes in a shallow microfluidic channel via stop flow lithography. Regardless of their exact shape, particles with a single mirror plane have identical modes of motion: in-plane rotation and cross-stream translation along a bell-shaped path. Each mode has a characteristic time, determined by particle geometry. Furthermore, each particle trajectory can be scaled by its respective characteristic times onto two master curves. We propose minimalistic relations linking these timescales to particle shape. Together these master curves yield a trajectory universal to particles with a single mirror plane.

Self-thermoelectrophoresis at low salinity.

A locally heated Janus colloid can achieve motion in an electrolyte by an effect known as self-thermo(di)electrophoresis. We numerically study the self-propulsion of such a "hot swimmer" in a monovalent electrolyte using the finite-element method and analytic theory. The effect of electrostatic screening for intermediate and large Debye lengths is charted and we report on the fluid flow generated by self-thermoelectrophoresis. We obtain excellent agreement between our analytic theory and numerical calculations in the limit of high salinity, validating our approach. At low salt concentrations, we employ Teubner's integral formalism to arrive at expressions for the speed, which agree semi-quantitatively with our numerical results for conducting swimmers. This lends credibility to the remarkably high swim speed at very low ionic strength, which we numerically obtain for a fully insulating swimmer. We also report on hot swimmers with a mixed electrostatic boundary conditions. Our results should benefit the realization and analysis of further experiments on thermo(di)electrophoretic swimmers.

Steering particles by breaking symmetries.

We derive general equations of motions for highly-confined particles that perform quasi-two-dimensional motion in Hele-Shaw channels, which we solve analytically, aiming to derive design principles for self-steering particles. Based on symmetry properties of a particle, its equations of motion can be simplified, where we retrieve an earlier-known equation of motion for the orientation of dimer particles consisting of disks (Uspal et al 2013 Nat. Commun. 4), but now in full generality. Subsequently, these solutions are compared with particle trajectories that are obtained numerically. For mirror-symmetric particles, excellent agreement between the analytical and numerical solutions is found. For particles lacking mirror symmetry, the analytic solutions provide means to classify the motion based on particle geometry, while we find that taking the side-wall interactions into account is important to accurately describe the trajectories.

Calculating the motion of highly confined, arbitrary-shaped particles in Hele-Shaw channels.

We combine theory and numerical calculations to accurately predict the motion of anisotropic particles in shallow microfluidic channels, in which the particles are strongly confined in the vertical direction. We formulate an effective quasi-two-dimensional description of the Stokes flow around the particle via the Brinkman equation, which can be solved in a time that is two orders of magnitude faster than the three-dimensional problem. The computational speedup enables us to calculate the full trajectories of particles in the channel. To validate our scheme, we study the motion of dumbbell-shaped particles that are produced in a microfluidic channel using 'continuous-flow lithography'. Contrary to what was reported in earlier work (Uspal et al. in Nat Commun 4:2666, 2013), we find that the reorientation time of a dumbbell particle in an external flow exhibits a minimum as a function of its disk size ratio. This finding is in excellent agreement with new experiments, thus confirming the predictive power of our scheme.

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 and droplet 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.

Tuning the motility and directionality of self-propelled colloids.

Microorganisms are able to overcome the thermal randomness of their surroundings by harvesting energy to navigate in viscous fluid environments. In a similar manner, synthetic colloidal microswimmers are capable of mimicking complex biolocomotion by means of simple self-propulsion mechanisms. Although experimentally the speed of active particles can be controlled by e.g. self-generated chemical and thermal gradients, an in-situ change of swimming direction remains a challenge. In this work, we study self-propulsion of half-coated spherical colloids in critical binary mixtures and show that the coupling of local body forces, induced by laser illumination, and the wetting properties of the colloid, can be used to finely tune both the colloid's swimming speed and its directionality. We experimentally and numerically demonstrate that the direction of motion can be reversibly switched by means of the size and shape of the droplet(s) nucleated around the colloid, depending on the particle radius and the fluid's ambient temperature. Moreover, the aforementioned features enable the possibility to realize both negative and positive phototaxis in light intensity gradients. Our results can be extended to other types of half-coated microswimmers, provided that both of their hemispheres are selectively made active but with distinct physical properties.

Interplay Between Adsorption and Hydrodynamics in Nanochannels: Towards Tunable Membranes.

We study how the adsorption of a near-critical binary mixture in a nanopore is modified by flow inside the pore. We identify three types of steady states upon variation of the pore Péclet number (Pe_{p}), which can be reversibly accessed by the application of an external pressure. Interestingly, for small Pe_{p} the pore acts as a weakly selective membrane which separates the mixture. For intermediate Pe_{p}, the flow effectively shifts the adsorption in the pore, thereby opening possibilities for enhanced and tunable solute transport through the pore. For large Pe_{p}, the adsorption is progressively reduced inside the pore, accompanied by a long-ranged dispersion of the mixture far from the pore.

Nanocapillary electrokinetic tracking for monitoring charge fluctuations on a single nanoparticle.

We introduce nanoCapillary Electrokinetic Tracking (nanoCET), an optofluidic platform for continuously measuring the electrophoretic mobility of a single colloidal nanoparticle or macromolecule in vitro with millisecond time resolution and high charge sensitivity. This platform is based on using a nanocapillary optical fiber in which liquids may flow inside a channel embedded inside the light-guiding core and nanoparticles are tracked using elastic light scattering. Using this platform we have experimentally measured the electrophoretic mobility of 60 nm gold nanoparticles in an aqueous environment. Further, using numerical simulations, we demonstrate the underlying electrokinetic dynamics inside the nanocapillary and the necessary steps for extending this method to probing single biomolecules, which can be achieved with existing technologies. This achievement will immensely facilitate the daunting challenge of monitoring biochemical or catalytic reactions on a single entity over a wide range of timescales. The unique measurement capabilities of this platform pave the way for a wide range of discoveries in colloid science, analytical biochemistry, and medical diagnostics.

State behaviour and dynamics of self-propelled Brownian squares: a simulation study.

We study the state behaviour of self-propelled and Brownian squares as a function of the magnitude of self-propulsion and density using Brownian dynamics simulations. We find that the system undergoes a transition from a fluid state to phase coexistence with increased self-propulsion and density. Close to the transition we find oscillations of the system between a fluid state and phase coexistence that are caused by the accumulation of forces in the dense phase. Finally, we study the coarsening regime of the system and find super-diffusive behaviour.

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.

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 nonisothermal 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 nonmonotonic in both regimes.

Fundamental measure theory for the electric double layer: implications for blue-energy harvesting and water desalination.

Capacitive mixing (CAPMIX) and capacitive deionization (CDI) are promising candidates for harvesting clean, renewable energy and for the energy efficient production of potable water, respectively. Both CAPMIX and CDI involve water-immersed porous carbon (supercapacitors) electrodes at voltages of the order of hundreds of millivolts, such that counter-ionic packing is important for the electric double layer (EDL) which forms near the surfaces of these porous materials. Thus, we propose a density functional theory (DFT) to model the EDL, where the White-Bear mark II fundamental measure theory functional is combined with a mean-field Coulombic and a mean spherical approximation-type correction to describe the interplay between dense packing and electrostatics, in good agreement with molecular dynamics simulations. We discuss the concentration-dependent potential rise due to changes in the chemical potential in capacitors in the context of an over-ideal theoretical description and its impact on energy harvesting and water desalination. Compared to less elaborate mean-field models our DFT calculations reveal a higher work output for blue-energy cycles and a higher energy demand for desalination cycles.

Vapor-liquid coexistence of the Stockmayer fluid in nonuniform external fields.

We investigate the structure and phase behavior of the Stockmayer fluid in the presence of nonuniform electric fields using molecular simulation. We find that an initially homogeneous vapor phase undergoes a local phase separation in a nonuniform field due to the combined effect of the field gradient and the fluid vapor-liquid equilibrium. This results in a high-density fluid condensing in the strong field region. The system polarization exhibits a strong field dependence due to the fluid condensation.

Stabilization of charged and neutral colloids in salty mixtures.

We present a mechanism for the stabilization of colloids in liquid mixtures without use of surfactants or polymers. When a suitable salt is added to a solvent mixture, the coupling of the colloid's surface chemistry and the preferential solvation of ions leads to a repulsive force between colloids that can overcome van der Waals attraction. This repulsive force is substantial in a large range of temperatures, mixture composition, and salt concentrations. The increased repulsion due to addition of salt occurs even for charged colloids. This mechanism may be useful in experimental situations where steric stabilization with surfactants or polymers is undesired.

The interaction between colloids in polar mixtures above Tc.

We calculate the interaction potential between two charged colloids immersed in an aqueous mixture containing salt near or above the critical temperature. We find an attractive interaction far from the coexistence curve due to the combination of preferential solvent adsorption at the colloids' surface and preferential ion solvation. We show that the ion-specific interaction strongly depends on the amount of salt added as well as on the mixture composition. The calculations are in good agreement with recent experiments. For a highly antagonistic salt of hydrophilic anions and hydrophobic cations, a repulsive interaction at an intermediate inter-colloid distance is predicted even though both the electrostatic and adsorption forces alone are attractive.

Vapor-liquid equilibrium in electric field gradients.

We investigate the vapor-liquid coexistence of polar and nonpolar fluids in the presence of a nonuniform electric field. We find that a large enough electric field can nucleate a gas bubble from the liquid phase or a liquid droplet from the vapor phase. The surface tension of the vapor-liquid interface is determined within squared-gradient theory. When the surface potential (charge) is controlled, the surface tension increases (decreases) compared to the zero-field interface. The effect of the electric field on the fluid phase diagram depends strongly on the constitutive relation for the dielectric constant. Finally, we show that gas bubbles can be nucleated far from the bounding surfaces.

Stability of binary mixtures in electric field gradients.

We consider the influence of electric field gradients on the phase behavior of nonpolar binary mixtures. Small fields give rise to smooth composition profiles, whereas large enough fields lead to a phase-separation transition. The critical field for demixing as well as the equilibrium phase-separation interface are given as a function of the various system parameters. We show how the phase diagram in the temperature-composition plane is affected by electric fields, assuming a linear or nonlinear constitutive relations for the dielectric constant. Finally, we discuss the unusual case where the interface appears far from any bounding surface.

Phase-separation transition in liquid mixtures near curved charged objects.

We study the thermodynamic behavior of nonpolar liquid mixtures in the vicinity of curved charged objects, such as electrodes or charged colloids. 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 profiles 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 temporal relaxation of the demixing front location. We give the dependence of the steady-state location and characteristic time on the charge, mixture composition and ambient temperature.