Planar nematic anchoring on SiO-coated substrates

Summary The nematic planar anchoring is usually explained by using simple elastic models: the surface easy axis corresponds to the surface direction that minimizes the excess of nematic elastic energy. When anisotropic rough substrates are used to align nematic liquid crystals, due to the complex surface morphology, usual elastic models are not directly applicable. This paper presents quantitative topographical data of rough substrates, obtained with oblique SiO evaporation under vacuum for nematic planar anchoring. Experimental data are obtained by means of Atomic Force Microscopy and they are used to demonstrate the self-affine nature of these substrates and to relate the nematic anchoring with the anisotropy of the local fractal properties of the substrate itself. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Liquid crystal films on curved surfaces: An entropic sampling study

The confining effect of a spherical substrate inducing anchoring (normal to the surface) on rod-like liquid crystal molecules contained in a thin film spread over it has been investigated with regard to possible changes in the nature of the isotropic-to-nematic phase transition as the sample is cooled. The focus of these Monte Carlo simulations is to study the competing effects of the homeotropic anchoring due to the surface inducing orientational ordering in the radial direction and the inherent uniaxial order promoted by the intermolecular interactions. By adopting an entropic sampling procedure, we could investigate this transition with a high temperature precision, and we studied the effect of the surface anchoring strength on the phase diagram for a specifically chosen geometry. We find that there is a threshold anchoring strength of the surface below which uniaxial nematic phase results, and above which the isotropic fluid cools to a radially ordered nematic phase, besides of course expected changes in the phase transition temperature with the anchoring strength. In the vicinity of the threshold anchoring strength we observe a bistable region between these two structures, clearly brought out by the characteristics of the corresponding microstates constituting the entropic ensemble.     

Wetting of a plane with a narrow solvophobic stripe

ABSTRACT

We present a numerical study of a simple density functional theory model of fluid adsorption occurring on a planar wall decorated with a narrow deep stripe of a weaker adsorbing (relatively solvophobic) material, where wall-fluid and fluid-fluid intermolecular forces are considered to be dispersive. Both the stripe and outer substrate exhibit first-order wetting transitions with the wetting temperature of the stripe lying above that of the outer material. This geometry leads to a rich phase diagram due to the interplay between the pre-wetting transition of the outer substrate and an unbending transition corresponding to the local evaporation of liquid near the stripe. Depending on the width of the stripe, the line of unbending transitions merges with the pre-wetting line inducing a two-dimensional wetting transition occurring across the substrate. In turn, this leads to the continuous pre-drying of the thick pre-wetting film as the pre-wetting line is approached from above. Interestingly we find that the merging of the unbending and pre-wetting lines occurs even for the widest stripes considered. This contrasts markedly with the scenario where the outer material has the higher wetting temperature, for which the merging of the unbending and pre-wetting lines only occurs for very narrow stripes.     

Phase transitions, interfacial fluctuations and hidden symmetries for fluids near structured walls

Fluids adsorbed at micro-patterned and geometrically structured substrates can exhibit novel phase transitions and interfacial fluctuation effects distinct from those characteristic of wetting at planar, homogeneous walls. We review recent theoretical progress in this area paying particular attention to filling transitions pertinent to fluid adsorption near wedges, which have highlighted a deep connection between geometrical and contact angles. We show that filling transitions are not only characterized by large scale interfacial fluctuations leading to universal critical singularities but also reveal hidden symmetries with short-ranged critical wetting transitions and properties of dimensional reduction. We propose a non-local interfacial model which fulfills all these properties and throws light on long-standing problems regarding the order of the 3D short-range critical wetting transition.     

Quartic coupling and its effect on wetting behaviors in nematic liquid crystals

Based on the fact that rubbed groove patterns also affect the anchoring of liquid crystals at substrates,a quartic coupling is included in constructing the surface energy for a liquid crystal cell.The phase diagram and the wetting behaviors of the liquid crystal cell,bounded by surfactant-laden interfaces in a magnetic field perpendicular to the substrate are discussed by taking the quartic coupling into account.The nematic order increases at the surface while it decreases in the bulk as a result of the introduction of quartic substrate-liquid crystal coupling,indicating that the groove anchoring makes the liquid crystal molecules align more orderly near the substrate than away from it.This causes a different wetting behavior:complete wetting.     

Wetting transitions of simple liquid films adsorbed on self-assembled monolayer substrates: an ellipsometric study

We report on an ellipsometric experimental study designed to explore the relevance of the wetting phase diagram predicted by liquid state physics of basic models, to the wide class of simple organic liquid films that adsorb from saturated vapour onto planar substrates at room temperature. The wetting properties are explored by measuring adsorption isotherms in the approach to saturation, in particular, for adsorption of n-hexane on a variety of specially constructed substrates (self-assembled monolayers) spanning a wide range of surface energy, and by carrying out the microscopic equivalent of contact angle experiments at saturation. We locate a wetting transition, which in our case is continuous, and then study its properties in detail. The general prediction of the wetting phase diagram, that wetting transitions should be ubiquitous in nature and readily located via control over the substrate field, is supported by our data, but the quantitative nature of the thick film adsorption regime is not in agreement with Lifshitz theory. This conclusion supports the work of a variety of earlier related studies, but contrasts with recent results for adsorption onto the surface of water. In addition, the correlation length determined from our complete wetting adsorption isotherms is mesoscopic, suggesting that equilibrium statistical mechanics of simple models of inhomogeneous fluids cannot explain the data.     

Temperature dependence of the nematic anchoring energy: mean field analysis

In the mean field approximation, we evaluate the temperature dependence of the anchoring energy strength of a nematic liquid crystal in contact with a solid substrate due to thermal fluctuations. Our study is limited to the weak anchoring case, where the microscopic surface energy is small with respect to the mean field energy due to the nematic phase. We assume furthermore that the physical properties of the substrate can be considered temperature independent in the range of the nematic phase. According to the thermodynamical perturbative approach, the macroscopic surface energy is deduced by averaging the microscopic one, with a density matrix containing only the nematic mean field. We show that the thermal renormalization of the anchoring energy coefficients is proportional to the generalized nematic order parameters. Our analysis shows also that the thermal renormalization of the anchoring energy coefficients predicted by means of Landau-like theories is a first and rather rough approximation in the whole nematic temperature range.     

Phase diagram of hard colloidal platelets: a theoretical account

We construct the complete liquid crystal phase diagram of hard plate-like cylinders for variable aspect ratio using Onsager's second virial theory and employing the Parsons–Lee decoupling approximation to account for higher-body interactions in the isotropic and nematic fluid phases. The stability of the solid (columnar) state at high packing fraction is included by invoking a simple equation of state based on a Lennard–Jones–Devonshire cell model which has proven to be quantitatively reliable over a large range of packing fractions. By employing an asymptotic analysis based on the Gaussian approximation we are able to show that the nematic–columnar transition is universal and independent of particle shape. The predicted phase diagram is in qualitative agreement with simulation results.     

Complete wetting of pits and grooves

For one-component volatile fluids governed by dispersion forces an effective interface Hamiltonian, derived from a microscopic density functional theory, is used to study complete wetting of geometrically structured substrates. Also the long range of substrate potentials is explicitly taken into account. Four types of geometrical patterns are considered: i) one-dimensional periodic arrays of rectangular or parabolic grooves and ii) two-dimensional lattices of cylindrical or parabolic pits. We present numerical evidence that at the centers of the cavity regions the thicknesses of the adsorbed films obey precisely the same geometrical covariance relation, which has been recently reported for complete cone and wedge filling. However, this covariance does not hold for the laterally averaged wetting film thicknesses. For sufficiently deep cavities with vertical walls and close to liquid-gas phase coexistence in the bulk, the film thicknesses exhibit an effective planar scaling regime, which as a function of undersaturation is characterized by a power law with the common critical exponent -1/3 as for a flat substrate, but with the amplitude depending on the geometrical features.     

Rigorous Generalization of Young's Law for Heterogeneous and Rough Substrates

We consider a SOS type model of interfaces on a substrate which is both heterogeneous and rough. We first show that, for appropriate values of the parameters, the differential wall tension that governs wetting on such a substrate satisfies a generalized law which combines both Cassie and Wenzel laws. Then in the case of an homogeneous substrate, we show that this differential wall tension satisfies either the Wenzel's law or the Cassie's law, according to the values of the parameters.     

Morphology and structure of thin liquid-crystalline films at nematic-isotropic transition

We review the main features of very thin nematic liquid-crystalline films on solid substrates, focusing on 5CB on oxidized silicon wafers. By discussing the theoretical aspects of the observed structures, we show that the phenomena at work include isotropic capillary condensation and that the coexistence of isotropic and nematic terraces in thin films is a result of the interplay of several mechanisms. Further theoretical as well as experimental efforts are needed to completely understand the wetting behavior of these systems.Received: 1 August 2003PACS: 68.08.Bc Wetting - 68.15. + e Liquid thin films - 61.30.Hn Surface phenomena in liquid crystals including anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions     

The mean-field adsorption on a sinusoidally corrugated substrate revised

The fluid system at the bulk liquid–gas coexistence in a presence of a sinusoidally corrugated substrate exhibits not only the wetting transition, but additionally a first-order, thin–thick transition. The mean-field analysis of this transition based on a simple effective Hamiltonian is valid only in long wavelength limit. In this case the filling transition occurs so close to the wetting temperature, that the behavior of the interface is dominated by fluctuations, therefore the mean-field approach breaks down. We analyze the filling transition with the help of Hamiltonian evaluated from Landau theory. The applicability of our Hamiltonian is not restricted only to the vicinity of the wetting point. We obtain the phase diagram valid beyond the temperature range corresponding to the strong fluctuations regime. It displays more complex dependence on different length scales of the system and includes the old one as a particular case.     

基于Wenzel模型的粗糙界面异质形核分析

异质形核是形核发生的主要形式. 经典形核理论对基底界面作了理想化平面假设,然而实际异质形核体系中理想平直的固体界面是不存在的,这导致了异质形核描述与实际情况的偏差. 考察了固相晶胚在非平整界面上的异质形核过程,基于Wenzel润湿模型,分析了非理想界面的粗糙度因子对固相晶胚形核功的影响规律. 结果表明:当基底与晶核之间的本征润湿角小于90°时,基底界面越粗糙越有利于形核;本征润湿角大于90°时,基底界面越粗糙越不利于形核. 同时,游离晶胚在基底上润湿是球冠晶胚形成的重要途径,粗糙界面润湿过程中界面自由能的 关键词： 异质形核 粗糙界面 Wenzel模型 润湿过程     

Kinetic pathways for the isotropic-nematic phase transition in a system of colloidal hard rods: a simulation study

We study the kinetic pathways for the isotropic-to-nematic transition in a fluid of colloidal hard rods. In order to follow the formation of the nematic phase, we develop a new cluster criterion that distinguishes nematic clusters from the isotropic phase. Applying this criterion in Monte Carlo simulations, we find spinodal decomposition as well as nucleation and growth depending on the supersaturation. We determine the height of the nucleation barrier and we study the shape and structure of the cluster. More specifically, we find ellipsoidal nematic clusters with an aspect ratio of about 1.7 and a homogeneous nematic director field. Our results are consistent with theoretical predictions on the shape and director field of nematic tactoids. Classical nucleation theory gives reasonable predictions for the height of the nucleation barrier and the critical nucleus size.     

Wetting behaviour of a model symmetric binary mixture with partially miscible components from a density functional approach

We investigate wetting transitions in a binary fluid at a solid surface by means of a density functional approach. For this purpose we use the symmetric binary mixture model, which exhibits a demixing in a bulk phase. We concentrate on the evaluation of the phase diagrams in the case of adsorption from a gas phase at a fixed composition. Our calculations have revealed different scenarios, leading to the change of wettability of the surface. In the case of adsorption from an equimolar bulk gas the wetting transition may be of the first or of the second order. In the case of non-equimolar bulk composition we observe either a transition from partial to complete wetting, or a first-order transition between two partial wetting states.     

Hyperthermal molecular beam deposition of highly ordered organic thin films

We use a seeded supersonic molecular beam to control the kinetic energy of pentacene (C22H14) during deposition and growth on Ag(111). Highly ordered thin films are grown at low substrate temperatures (approximately 200 K) at kinetic energies of a few electron volts, as shown by low energy He diffraction and x-ray reflectivity spectra. In contrast, deposition of thermal molecules yields only amorphous films. Growth at room or higher temperature substrates yields films of poorer quality irrespective of the depositing beam energy. We find that after the first wetting layer is completed, a new ordered phase is formed, whose in-plane lattice spacings match one of the bulk crystal planes. The high quality of the films can be interpreted as the result of local annealing induced by the impact of the impinging high-energy molecules.     

Simple model for active nematics: quasi-long-range order and giant fluctuations

We propose a simple microscopic model for active nematic particles similar in spirit to the Vicsek model for self-propelled polar particles. In two dimensions, we show that this model exhibits a Kosterlitz-Thouless-like transition to quasi-long-range orientational order and that in this nonequilibrium context, the ordered phase is characterized by giant density fluctuations, in agreement with the predictions of Ramaswamy et al.     

The hard ellipsoid-of-revolution fluid I. Monte Carlo simulations

We present the results of Monte Carlo simulations on a system of hard ellipsoids of revolution with length-to-breadth ratios a/b = 3, 2.75, 2, 1.25 and b/a = 3, 2.75, 2, 1.25. We identify four distinct phases, viz. isotropic fluid, nematic fluid, ordered solid and plastic solid. The coexistence points of all first order phase transitions are located by performing absolute free energy computations for all coexisting phases. We find nematic phases only for a/b ≥ 2.75 and a/b ≤ 1/2.75. A plastic solid is only observed for 1.25 ≥ a/b ≥ 0.8. It is found that the phase diagram is surprisingly symmetric under interchange of the major and minor axes of the ellipsoids.