arXiv subjects

René van Roij

Publications and source records attributed to René van Roij.

At least 55 records · Page 3Linked to original sources

arXiv2017

Coulometry and Calorimetry of Electric Double Layer Formation in Porous Electrodes

Coulometric measurements on salt-water-immersed nanoporous carbon electrodes reveal, at a fixed voltage, a charge decrease with increasing temperature. During far-out-of-equilibrium charging of these electrodes, calorimetry indicates the production of both irreversible Joule heat and reversible heat, the latter being associated with entropy changes during electric double layer (EDL) formation in the nanopores. These measurements grant experimental access --for the first time-- to the entropic contribution of the grand potential; for our electrodes, this amounts to roughly 25% of the total grand potential energy cost of EDL formation at large applied potentials, in contrast with point-charge model calculations that predict 100%. The coulometric and calorimetric experiments show a consistent picture of the role of heat and temperature in EDL formation and provide hitherto unused information to test against EDL models.

physics.chem-ph↗

arXiv2017

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

We combine theory, numerical calculations, and experiments 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 test 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., Nature communications 4 (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.

cond-mat.soft↗

arXiv2017

Rational design and dynamics of self-propelled colloidal bead chains: from rotators to flagella

The quest for designing new self-propelled colloids is fuelled by the demand for simple experimental models to study the collective behaviour of their more complex natural counterparts. Most synthetic self-propelled particles move by converting the input energy into translational motion. In this work we address the question if simple self-propelled spheres can assemble into more complex structures that exhibit rotational motion, possibly coupled with translational motion as in flagella. We exploit a combination of induced dipolar interactions and a bonding step to create permanent linear bead chains, composed of self-propelled Janus spheres, with a well-controlled internal structure. Next, we study how flexibility between individual swimmers in a chain can affect its swimming behaviour. Permanent rigid chains showed only active rotational or spinning motion, whereas longer semi-flexible chains showed both translational and rotational motion resembling flagella like-motion, in the presence of the fuel. Moreover, we are able to reproduce our experimental results using numerical calculations with a minimal model, which includes full hydrodynamic interactions with the fluid. Our method is general and opens a new way to design novel self-propelled colloids with complex swimming behaviours, using different complex starting building blocks in combination with the flexibility between them.

cond-mat.soft↗

arXiv2017

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.

cond-mat.soft↗

arXiv2017

Colloid-oil-water-interface interactions in the presence of multiple salts: charge regulation and dynamics

We theoretically and experimentally investigate colloid-oil-water-interface interactions of charged, sterically stabilized, poly(methyl-methacrylate) colloidal particles dispersed in a low-polar oil (dielectric constant $ε=5-10$) that is in contact with an adjacent water phase. In this model system, the colloidal particles cannot penetrate the oil-water interface due to repulsive van der Waals forces with the interface whereas the multiple salts that are dissolved in the oil are free to partition into the water phase. The sign and magnitude of the Donnan potential and/or the particle charge is affected by these salt concentrations such that the effective interaction potential can be highly tuned. Both the equilibrium effective colloid-interface interactions and the ion dynamics are explored within a Poisson-Nernst-Planck theory, and compared to experimental observations.

cond-mat.soft↗

arXiv2017

Reversible heating in electric double layer capacitors

A detailed comparison is made between different viewpoints on reversible heating in electric double layer capacitors. We show in the limit of slow charging that a combined Poisson-Nernst-Planck and heat equation, first studied by d'Entremont and Pilon [J. Power Sources {\bf 246}, 887 (2014)], recovers the temperature changes as predicted by the thermodynamic identity of Janssen, Härtel, and van Roij [Phys. Rev. Lett. {\bf 113}, 268501 (2014)], and disagrees with the approximative model of Schiffer, Linzen, and Sauer [J. Power Sources {\bf 160}, 765 (2006)] that predominates the literature.

cond-mat.soft↗

arXiv2017

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.

physics.flu-dyn↗

arXiv2017

Efficient shapes for microswimming: from three-body swimmers to helical flagella

We combine a general formulation of microswimmmer equations of motion with a numerical bead-shell model to calculate the hydrodynamic interactions with the fluid, from which the swimming speed, power and efficiency are extracted. From this framework, a generalized Scallop Theorem emerges. The applicability to arbitrary shapes allows for the optimization of the efficiency with respect to the swimmer geometry. We apply this scheme to `three-body swimmers' of various shapes and find that the efficiency is characterized by the single body friction coefficient in the long-arm regime, while in the short-arm regime the minimal approachable distance becomes the determining factor. Next, we apply this scheme to a biologically inspired swimmer that propels itself using a rotating helical flagellum. Interestingly, we find two distinct optimal shapes, one of which is fundamentally different from the shapes observed in nature (e.g. bacteria).

cond-mat.soft↗

arXiv2016

Interplay between adsorption and hydrodynamics in nanochannels: towards tunable membranes

We study how 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 (${\rm Pe}_p$), which can be reversibly accessed by the application of an external pressure. Interestingly, for small ${\rm Pe}_p$ the pore acts as a weakly selective membrane which separates the mixture. For intermediate ${\rm Pe}_p$, the flow effectively shifts the adsorption in the pore thereby opening possibilities for enhanced and tunable solute transport through the pore. For large ${\rm Pe}_p$, the adsorption is progressively reduced inside the pore, accompanied by a long ranged dispersion of the mixture far from the pore.

cond-mat.soft↗

arXiv2016

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.

cond-mat.soft↗

arXiv2016

Alternating strings and clusters in suspensions of charged colloids

We report the formation of alternating strings and clusters in a binary suspension of repulsive charged colloids with double layers larger than the particle size. Within a binary cell model we include many-body and charge-regulation effects under the assumption of a constant surface potential, and consider their repercussions on the two-particle interaction potential. We find that the formation of induced dipoles close to a charge-reversed state may explain the formation of these structures. Finally, we will touch upon the formation of dumbbells and small clusters in a one-component system, where the effective electrostatic interaction is always repulsive.

cond-mat.soft↗

arXiv2016

Sedimentation stacking diagrams of binary mixtures of thick and thin hard rods

We use Onsager theory and the local density approximation to study sedimentation-diffusion equilibrium density profiles of binary mixtures of thick and thin hard rods. We construct stacking diagrams for three diameter ratios, and find that even a simple spindle-shaped phase diagram with only isotropic-nematic demixing can lead to counter-intuitive stacking sequences such as an isotropic phase sandwiched between two nematic phases. For the most complex phase diagram considered here, we find sixteen distinct stacking sequences, including several with five sedimented layers. By adding sedimentation paths to composition-pressure and density-density phase diagrams and calculating density and composition profiles, we show that conclusions about bulk phase diagrams of binary mixtures on the basis of sedimentation-diffusion equilibria should be drawn warily.

cond-mat.soft↗

arXiv2016

A Landau-de Gennes theory for hard colloidal rods: defects and tactoids

We construct a phenomenological Landau-de Gennes theory for hard colloidal rods by performing an order parameter expansion of the chemical-potential dependent grand potential. By fitting the coefficients to known results of Onsager theory, we are not only able to describe the isotropic-nematic phase transition as function of density, including the well-known density jump, but also the isotropic-nematic planar interface. The resulting theory is applied in calculations of the isotropic core size in a radial hedgehog defect, the density dependence of linear defects of hard rods in square confinement, and the formation of a nematic droplet in an isotropic background.

cond-mat.soft↗

arXiv2016

Density-induced reentrant melting of colloidal Wigner crystals

Electrostatic repulsions can drive crystallization in many-particle systems. For charged colloidal systems, the phase boundaries as well as crystal structure are highly tunable by experimental parameters such as salt concentration and pH. By using projections of the colloid-ion mixture to a system of (soft) repulsive spheres and the one-component plasma (OCP), we study the hitherto unexplained experimentally observed reentrant melting of electrostatically repelling colloids upon increasing the colloid density. Our study shows that the surface chemistry should involve a competition between adsorption of cations and anions to explain the observed density-induced reentrant melting.

cond-mat.soft↗

arXiv2016

Harvesting vibrational energy with liquid-bridged electrodes: thermodynamics in mechanically and electrically driven RC-circuits

We theoretically study a vibrating pair of parallel electrodes bridged by a (deformed) liquid droplet, which is a recently developed microfluidic device to harvest vibrational energy. The device can operate with various liquids, including liquid metals, electrolytes, as well as ionic liquids. We numerically solve the Young-Laplace equation for all droplet shapes during a vibration period, from which the time-dependent capacitance follows that serves as input for an equivalent circuit model. We first investigate two existing energy harvesters (with a constant and a vanishing bias potential), for which we explain an open issue related to their optimal electrode separations, which is as small as possible or as large as possible in the two cases, respectively. Then we propose a new engine with a time-dependent bias voltage, with which the harvested work and the power can be increased by orders of magnitude at low vibration frequencies and by factors 2-5 at high frequencies, where frequencies are to be compared to the inverse RC-time of the circuit.

physics.comp-ph↗

arXiv2016

Phase diagrams of charged colloidal rods: can a uniaxial charge distribution break chiral symmetry?

We construct phase diagrams for charged rodlike colloids within the second-virial approximation as a function of rod concentration, salt concentration, and colloidal charge. Besides the expected isotropic-nematic transition, we also find parameter regimes with a coexistence between a nematic and a second, more highly aligned nematic phase including an isotropic-nematic-nematic triple point and a nematic-nematic critical point, which can all be explained in terms of the twisting effect. We compute the Frank elastic constants to see if the twist elastic constant can become negative, which would indicate the possibility of a cholesteric phase spontaneously forming. Although the twisting effect reduces the twist elastic constant, we find that it always remains positive. In addition, we find that for finite aspect-ratio rods the twist elastic constant is also always positive, such that there is no evidence of chiral symmetry breaking due to a uniaxial charge distribution.

cond-mat.soft↗

arXiv2015

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.

cond-mat.soft↗

arXiv2015

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 surface 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.

cond-mat.soft↗