The role of attractive interactions in rod-sphere mixtures

We present a computer simulation study of binary mixtures of prolate Gay-Berne particles and Lennard-Jones spheres. Results are presented for three such rod-sphere systems which differ from each other only in the interaction between unlike particles. Both the mixing-demixing behavior and the transitions between the isotropic and any liquid crystalline phases are studied for each system, as a function of temperature and concentration ratio. For systems which show macroscopic demixing, the rod-sphere interaction is shown to give direct control over interfacial anchoring properties, giving rise to the possibility of micellar phase formation in the case of homeotropic anchoring. Additionally, it is shown that on incorporating high concentrations of spheres into a system of rods with weak demixing properties, microphase-separated structures can be induced, including bicontinuous and lamellar arrangements.</p

Incorporation of excluded volume correlations into Poisson-Boltzmann theory

We investigate the effect of excluded volume interactions on the electrolyte distribution around a charged macroion. First, we introduce a criterion for determining when hard-core effects should be taken into account beyond standard mean field Poisson-Boltzmann (PB) theory. Next, we demonstrate that several commonly proposed local density functional approaches for excluded volume interactions cannot be used for this purpose. Instead, we employ a non-local excess free energy by using a simple constant weight approach. We compare the ion distribution and osmotic pressure predicted by this theory with Monte Carlo simulations. They agree very well for weakly developed correlations and give the correct layering effect for stronger ones. In all investigated cases our simple weighted density theory yields more realistic results than the standard PB approach, whereas all local density theories do not improve on the PB density profiles but on the contrary, deviate even more from the simulation results.Comment: 23 pages, 7 figures, 1 tabl

Friction phenomena and their impact on the shear behaviour of granular material

In the discrete element simulation of granular materials, the modelling of contacts is crucial for the prediction of the macroscopic material behaviour. From the tribological point of view, friction at contacts needs to be modelled carefully, as it depends on several factors, e.g. contact normal load or temperature to name only two. In discrete element method (DEM) simulations the usage of Coulomb’s law of friction is state of the art in modelling particle–particle contacts. Usually in Coulomb’s law, for all contacts only one constant coefficient of friction is used, which needs to reflect all tribological effects. Thus, whenever one of the influence factors of friction varies over a wide range, it can be expected that the usage of only one constant coefficient of friction in Coulomb’s law is an oversimplification of reality. For certain materials, e.g. steel, it is known that a dependency of the coefficient of friction on the contact normal load exists. A more tribological tangential contact law is implemented in DEM, where the interparticle friction coefficient depends on the averaged normal stress in the contact. Simulations of direct shear tests are conducted, using steel spheres of different size distributions. The strong influence of interparticle friction on the bulk friction is shown via a variation of the constant interparticle friction coefficient. Simulations with constant and stress-dependent interparticle friction are compared. For the stress-dependent interparticle friction, a normal stress dependency of the bulk friction is seen. In the literature, measurements of different granular materials and small normal loads also show a stress dependency of the bulk friction coefficient. With increasing applied normal stress, the bulk friction coefficient reduces both in the experiments and in the simulations

Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids

Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid–solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure

Superionic lithium transport via multiple coordination environments defined by two-anion packing

Fast cation transport in solids underpins energy storage. Materials design has focused on structures that can define transport pathways with minimal cation coordination change, restricting attention to a small part of chemical space. Motivated by the greater structural diversity of binary intermetallics than that of the metallic elements, we used two anions to build a pathway for three-dimensional superionic lithium ion conductivity that exploits multiple cation coordination environments. Li 7 Si 2 S 7 I is a pure lithium ion conductor created by an ordering of sulphide and iodide that combines elements of hexagonal and cubic close-packing analogously to the structure of NiZr. The resulting diverse network of lithium positions with distinct geometries and anion coordination chemistries affords low barriers to transport, opening a large structural space for high cation conductivity. </jats:p

Towards an understanding of induced-charge electrokinetics at large applied voltages in concentrated solutions

The venerable theory of electrokinetic phenomena rests on the hypothesis of a dilute solution of point-like ions in quasi-equilibrium with a weakly charged surface, whose potential relative to the bulk is of order the thermal voltage (kT/e ≈ 25 mV at room temperature). In nonlinear electrokinetic phenomena, such as AC or induced-charge electro-osmosis (ACEO, ICEO) and induced-charge electrophoresis (ICEP), several V ≈ 100 kT/e are applied to polarizable surfaces in microscopic geometries, and the resulting electric fields and induced surface charges are large enough to violate the assumptions of the classical theory. In this article, we review the experimental and theoretical literatures, highlight discrepancies between theory and experiment, introduce possible modifications of the theory, and analyze their consequences. We argue that, in response to a large applied voltage, the “compact layer” and “shear plane” effectively advance into the liquid, due to the crowding of counterions. Using simple continuum models, we predict two general trends at large voltages: (i) ionic crowding against a blocking surface expands the diffuse double layer and thus decreases its differential capacitance, and (ii) a charge-induced viscosity increase near the surface reduces the electro-osmotic mobility; each trend is enhanced by dielectric saturation. The first effect is able to predict high-frequency flow reversal in ACEO pumps, while the second may explain the decay of ICEO flow with increasing salt concentration. Through several colloidal examples, such as ICEP of an uncharged metal sphere in an asymmetric electrolyte, we show that nonlinear electrokinetic phenomena are generally ion-specific. Similar theoretical issues arise in nanofluidics (due to confinement) and ionic liquids (due to the lack of solvent), so the paper concludes with a general framework of modified electrokinetic equations for finite-sized ions.National Science Foundation (U.S.) (contract DMS-0707641

Computer simulation of rod-sphere mixtures

Results are presented from a series of simulations undertaken to investigate the effect of adding small spherical particles to a fluid of rods which would otherwise represent a liquid crystalline (LC) substance. Firstly, a bulk mixture of Hard Gaussian Overlap particles with an aspect ratio of 3:1 and hard spheres with diameters equal to the breadth of the rods is simulated at various sphere concentrations. Both mixing-demixing and isotropic-nematic transition are studied using Monte Carlo techniques. Secondly, the effect of adding Lennard-Jones particles to an LC system modelled using the well established Gay-Berne potential is investigated. These rod-sphere mixtures are simulated using both the original set of interaction parameters and a modified version of the rod-sphere potential proposed in this work. The subject of interest is the internal structure of the binary mixture and its dependence on density, temperature, concentration and various parameters characterising the intermolecular interactions. Both the mixing-demixing behaviour and the transitions between the isotropic and any LC phases have been studied for four systems which differ in the interaction potential between unlike particles. A range of contrasting microphase separated structures including bicontinuous, cubic, and micelle-like arrangement have been observed in bulk. Thirdly, the four types of mixtures previously studied in bulk are subjected to a static magnetic field. A variety of novel phases are observed for the cases of positive and negative anisotropy in the magnetic susceptibility. These include a lamellar structure, in which layers of rods are separated by layers of spheres, and a configuration with a self-assembling hexagonal array of spheres. Finally, two new models are presented to study liquid crystal mixtures in the presence of curved substrates. These are implemented for the cases of convex and concave spherical surfaces. The simulation results obtained in these geometries in