Textures in polygonal arrangements of square nanoparticles in nematic liquid crystal matrices

A systematic analysis of defect textures in faceted nanoparticles with polygonal configurations embedded in a nematic matrix is performed using the Landau-de Gennes model, homeotropic strong anchoring in a square domain with uniform alignment in the outer boundaries. Defect and textures are analyzed as functions of temperature T, polygon size R, and polygon number N. For nematic nanocomposites, the texture satisfies a defect charge balance equation between bulk and surface (particle corner) charges. Upon decreasing the temperature, the central bulk defects split and together with other -1/2 bulk defects are absorbed by the nanoparticle's corners. Increasing the lattice size decreases confinement and eliminates bulk defects. Increasing the polygon number increases the central defect charge at high temperature and the number of surface defects at lower temperatures. The excess energy per particle is lower in even than in odd polygons, and it is minimized for a square particle arrangement. These discrete modeling results show for first time that, even under strong anchoring, defects are attached to particles as corner defects, leaving behind a low energy homogeneous orientation field that favors nanoparticle ordering in nematic matrices. These new insights are consistent with recent thermodynamic approaches to nematic nanocomposites that predict the existence of novel nematic/crystal phases and can be used to design nanocomposites with orientational and positional order.     

Ringlike cores of cylindrically confined nematic point defects

Nematic liquid crystals confined in a cylindrical capillary and subjected to strong homeotropic anchoring conditions is a long-studied fundamental problem that uniquely incorporates nonlinearity, topological stability, defects, and texture physics. The observed and predicted textures that continue to be investigated include escape radial, radial with a line defect, planar polar with two line defects, and periodic array of point defects. This paper presents theory and multiscale simulations of global and fine scale textures of nematic point defects, based on the Landau-de Gennes tensor order parameter equations. The aim of this paper is to further investigate the ringlike nature of point defect cores and its importance on texture transformation mechanisms and stability. The paper shows that the ringlike cores can be oriented either along the cylinder axis or along the radial direction. Axial rings can partially expand but are constrained by the capillary sidewalls. Radial rings can deform into elliptical structures whose major axis is along the capillary axis. The transformation between several families of textures under capillary confinement as well as their stability is discussed in terms of defect ring distortions. A unified view of nematic textures found in the cylindrical cavities is provided.     

A vector grouping algorithm for liquid crystal tensor field visualization

Tensor fields are at the heart of many science and engineering disciplines. Many tensor visualization methods separate the tensor into component eigenvectors and visualize those instead. Eigenvectors are normally ordered according to their eigenvalues: the eigenvectors corresponding to the smallest, median, or largest eigenvalues are in their corresponding groups. We show that this ordering strategy is undesirable for liquid crystal systems and propose a new approach, where the vectors are grouped to minimize some local energy. The grouping process is reminiscent of the epitaxial expansion in the anchoring of liquid crystals on a surface. The new algorithm is successfully applied to a liquid crystal system to study the biaxiality structure near a defect.     

Electrically induced anchoring transition in cholesteric liquid crystal cells with different confinement ratios

Reorientation of cholesteric liquid crystal induced by the electrically controlled ionic modification of surface anchoring within the cell with confinement ratio exceeding 1 has been studied. The change of homeotropic surface anchoring to the planar one on the electrode-anode substrate under the action of DC voltage causes the formation of the modulated hybrid-aligned cholesteric layer in the cell. Optical texture of the liquid crystal layer with such an orientation structure is the linear periodic stripes. Homogeneity of emerging optical texture depending on the confinement ratio as well as on the prehistory of voltage application has been considered. It has been found that the ionic modification of surface anchoring results in total transformation of the diffraction pattern observed after the laser beam passing through the sample.     

Point and ring defects in nematics under capillary confinement

The textures exhibited by nematic liquid crystals confined to cylindrical capillaries under homeotropic anchoring have been studied for nearly thirty years. One of the reasons behind this maintained interest is that the processing of many high-performance fibers including carbon fibers and spider silks involves these textures. Three of these textures, the planar radial with line defect, the planar polar with two line defects (PPLD), and the escape radial (ER), are relatively well understood. A third one, the escape radial with point defects presents, however, some unresolved issues and recent studies have questioned the real nature and dimensionality of the defects involved in this texture. It seems that the defects are not in the form of points but rather in the form of closed lines or rings. This paper presents a detailed study on the connection between point and ring defects in a cylindrical cavity using three-dimensional simulations based on the continuum Landau-de Gennes theory. The results show that true point defects cannot exist in cylindrical cavities and that the merging of two ringlike defects may lead to two qualitatively different stable textures, namely, the ER and PPLD textures. The various results are in qualitative agreement with recent molecular dynamic studies and with theoretical predictions based on experimental observations. The predictions provide new insights on the structural connections between synthetic and biological superfibers.     

Isotropic-to-nematic phase transition in a liquid-crystal droplet

In this paper, we focus on the isotropic-to-nematic phase transition in a liquid-crystal droplet. We present the results of an experiment to measure the growth of the nematic phase within an isotropic phase liquid-crystal droplet. Experimentally, we observe two primary phase transition regimes. At short time scales, our experimental results (R(t) approximately t0.51) show good agreement with a Stefan-type model of the evolution of the nematic phase within the isotropic phase of a liquid crystal. As time progresses, the growth of the nematic phase is restricted by increased confinement of the droplet boundary. During this stage of growth, the nematic phase grows at a slower rate of R(t) approximately t0.31. The slower growth at later stages might be due to a variety of factors such as confinement-induced latent heat reduction; a change of defect strength during its evolution; or interactions between the defect and the interface between the liquid crystal and oil or between adjacent defects. The presence of two growth regimes is also consistent with the molecular simulations of Bradac et al. (Bradac, Z.; Kralj, S.; Zumer, S. Phys. Rev. E 2002, 65, 021705) who identify an early stage domain regime and a late stage confinement regime. For the domain and confinement regimes, Bradac et al. (Bradac, Z.; Kralj, S.; Zumer, S. Phys. Rev. E 2002, 65, 021705) obtained growth exponents of 0.49 +/- 0.05 and 0.25 +/- 0.05. These are remarkably close to the values 0.51 and 0.31 observed in our experiments.     

Influence of surfactant tail branching and organization on the orientation of liquid crystals at aqueous-liquid crystal interfaces

We have examined the influence of two aspects of surfactant structure--tail branching and tail organization--on the orientational ordering (so-called anchoring) of water-immiscible, thermotropic liquid crystals in contact with aqueous surfactant solutions. First, we evaluated the influence of branches in surfactant tails on the anchoring of nematic liquid crystals at water-liquid crystal interfaces. We compared interfaces that were laden with one of three linear surfactants (sodium dodecyl sulfate, sodium dodecanesulfonate, and isomerically pure linear sodium dodecylbenzenesulfonate) to interfaces laden with branched sodium dodecylbenzenesulfonate. We carried out these experiments at 60 degrees C, above the Krafft temperatures of all the surfactants studied, and used the liquid crystal TL205 (a mixture of cyclohexane-fluorinated biphenyls and fluorinated terphenyls), which forms a nematic phase at 60 degrees C. Linear surfactants caused TL205 to assume a perpendicular orientation (homeotropic anchoring) above a threshold concentration of surfactant and parallel orientation (planar anchoring) at lower concentrations. In contrast, branched sodium dodecylbenzenesulfonate caused planar anchoring of TL205 at all concentrations up to the critical micelle concentration of the surfactant. Second, we used sodium dodecanesulfonate and a commercial linear sodium dodecylbenzenesulfonate to probe the influence of surfactant tail organization on the orientations of liquid crystals at water-liquid crystal interfaces. Commercial linear sodium dodecylbenzenesulfonate, which comprises a mixture of ortho and para isomers, has been previously characterized to form less ordered monolayers than sodium dodecanesulfonate at oil-water interfaces at room temperature. We found sodium dodecanesulfonate to cause homeotropic anchoring of both TL205 and 4'-pentyl-4-cyanobiphenyl (5CB, nematic at room temperature), whereas commercial linear sodium dodecylbenzenesulfonate caused predominantly planar and tilted orientations of both TL205 and 5CB. These results, when combined, lead us to conclude that (1) interactions between the aliphatic tails of surfactants and liquid crystals largely dictate the orientations of liquid crystals at aqueous-liquid crystal interfaces, (2) the interactions that orient the liquid crystals at these interfaces are sensitive to the branching and degree of disorder in the surfactant tails, and (3) differences in the chemical composition of TL205 and 5CB, most notably fluorination of TL205, lead to subtle differences in the orientations of these two nematic liquid crystals.     

Texture formation under phase ordering and phase separation in polymer-liquid crystal mixtures

Computational modeling of texture formation in coupled phase separation-phase ordering processes in polymer/liquid crystal mixtures is performed using a unified model based on the nematic tensor order parameter and gradient orientation elasticity. The computational methods are able to resolve defect nucleation, defect-defect interactions, and defect-particle interactions, as well as global and local morphological features in the concentration and order parameter spatiotemporal behavior. Biphasic structures corresponding to polymer dispersed liquid crystals (PDLCs), crystalline filled nematic (CFNs), and random filled nematics (RFNs) are captured and analyzed using liquid crystal defect physics and structure factors. Under spinodal decomposition due to concentration fluctuations, the PDLC structure emerges, and the nucleation and repulsive interaction of defects within nematic droplets leads to bipolar nematic droplets. Under spinodal decomposition due to ordering fluctuations, the CFNs structure emerges, and the stable polymer droplet crystal is pinned by a lattice of topological defects. For intermediate cases, where the mixture is unstable to both concentration and nematic order fluctuations, the RFN structure emerges, and polymer droplets and fibrils are pinned by a defect network, whose density increases with the curvature of the polymer-liquid crystal interface. The simulations provide an information of the role of topological defects on phase separation-phase ordering processes in polymer-liquid crystal mixtures.     

Director configurations in nematic droplets with tilted surface anchoring

The polymer dispersed nematic liquid crystal (LC) with the tilted surface anchoring has been studied. The droplet orientational structures with two point surface defects – boojums and the surface ring defect – are formed within the films. The director tilt angle α = 40° ± 4° at the droplet interface and LC surface anchoring strength W_s ~ 10^–6 (J m^?2) have been estimated. The bipolar axes within the studied droplets of oblate ellipsoidal form can be randomly oriented are oriented randomly relatively to the ellipsoid axes as opposed to the droplets with homeotropic and tangential anchoring.     

Nematic to smectic-A phase transition in mixture of liquid crystal and nonmesogenic impurities: existence of tricritical point

Experiments on the mixture of liquid crystals and nonmesogenic impurities showed the significant role of nonmesogenic impurities on the nematic–smectic-A phase transition. Using both Flory–Huggins theory of isotropic mixing and Landau–de Gennes theory, we present a phenomenological theory that discusses the role of such impurities on the nematic–smectic-A phase transition in a mixture of smectic liquid crystal and nonmesogenic impurities. We discuss the impact of nonmesogenic impurities on the order parameters, Frank elastic constants (splay and bend) and transition temperature of the nematic–smectic-A phase transition. Our theoretical results show that there exists a tricritical point for which the second-order nematic–smectic-A phase transition becomes first order at a tricritical point by increasing the concentration of nonmesogenic solute. We find a remarkable agreement between theoretical and experimental results.     

Topological defects in dispersed words and worlds around liquid crystals, or liquid crystal drops

The structure of dispersed liquid crystal droplets elasticity, surface tension, and surface anchoring. For sufficiently large droplets with radius R K / W a, where K is the bulk elastic constant and W a is the anchoring coefficient, the surface terms prevail. As a result, the equilibrium states of large droplets contain topologically stable defects. Application of topological theorems to and hedgehogs is reviewed. is controlled by a balance of the bulk defect structures, e.g. monopoles, boojums     

Fine structures of zeolite-Linde-L (LTL): surface structures, growth unit and defects

High-resolution electron microscopy (HREM) has been used to image the surface structure of nano- and micrometer-sized synthetic crystals of zeolite-Linde-L (LTL). Columnar holes and rotational, nano-sized, wheel-like defects were observed within the crystals, where the hole has a minimum size equal to that of the rotational defect. Predictions of surface structure from atomistic computer simulation concur with the observations from HREM and provide insight into the crystal growth mechanism of perfect and defective LTL. Analysis of the energetics of the formation of rotational defect structures reveals that the driving force for defect creation is thermodynamic and furthermore, the rotational defects could be created in high concentrations. Formation of a columnar hole is found to be slightly energetically unfavourable and therefore we speculate that the incidence of both rotational and nano-sized vacancy defects is strongly dependent on kinetic factors and reaction conditions. The morphology of nano- and microcrystalline LTL is contradistinct and we use insights from simulation to propose an explanation of the disparity in crystal shape.     

Formation of spatially patterned colloidal photonic crystals through the control of capillary forces and template recognition

We report the formation of microscopic patterns of substrate-supported, 3D planar colloidal crystals using physical confinement in conjunction with surfaces displaying predetermined binary patterns of hydropholicity. The formation process involves a primary self-assembly wherein nano- and microscale colloids order into a photonic fcc lattice via capillary interactions followed by a secondary template-induced crystal cleavage step. Following this method, arbitrary arrays of pattern elements, which preserve structural and orientational properties of the parent crystal, can be easily obtained.     

Control of surface anchoring properties of liquid crystal by thermo-transfer printing of siloxane oligomers

We presented the results for the surface anchoring properties of a nematic liquid crystal (LC) in a wide range of the substrate wettability through thermo-transfer printing of siloxane oligomers. For the modification of the surface energy, poly(dimethylsiloxane) (PDMS) oligomers were directly transferred onto a glass substrate from a bulk PDMS plate by contact printing at elevated temperatures. The hydrophobicity of the PDMS-modified surface was found to increase with the temperature of the substrate during transfer printing. The LC alignment on the PDMS-modified substrate exhibited continuous variations of the pretilt angle from nearly 0° to 90° and the polar anchoring strength according to the surface energy.     

Nematodynamics and structures in junctions of cylindrical micropores

ABSTRACT

We explore equilibrium structures and flow-driven deformations of nematic liquid crystals confined to 3D junctions of cylindrical micropores with homeotropic surface anchoring. The topological state of the nematic ordering field in such basic unit of porous networks is controlled by nematic orientation profiles in individual pores, anchoring frustration along the edges of joining pores and coupling to the material flow field. We numerically investigate formation of the flow-aligned configurations in single cylindrical pores and pore junctions. Depending on the arrangement of inlet and outlet flows in the junction, we demonstrate existence of numerous stationary nematic configurations, characterised by specific bulk defects and surface disclinations along joining edges. Observed bulk defects are nonsingular escaped structures, disclinations in the form of loops or disclination lines pinned to the joining edges of the pores. Furthermore, we show examples of defect dynamics during the flow-induced topological transformations.     

Large-amplitude motion in polymer crystals and mesophases

Large-amplitude motion of macromolecules involves mainly rotation about bonds (conformational motion). In the liquid phases, the large-amplitude motion is coupled with disorder and accounts for the flow and viscoelastic behavior. Perfectly ordered crystals, in contrast, permit only little large-amplitude motion. The mesophases are intermediate in order and mobility. In crystals, large-amplitude motion leads initially to gauche defects and kinks (conformational defects), and ultimately may produce conformationally disordered crystals (condis crystals). Molecular dynamics simulations of crystals with up to 30 000 atoms have been carried out. They show the mechanism of defect formation, permit the study of the distribution of defects, and lead to a visualization of the hexagonal crystal phase. The main-chain liquid-crystalline macromolecules and condis crystals, the two mesophases of polymers, can be distinguished on the basis of an analysis of the phase separation (partial crystallinity), present in condis crystals and not in liquid crystals. Solid state NMR is the tool of choice for the detection of mobile and rigid phases. In highly drawn fibers one can find four different states of order and mobility. Besides the (defect) crystalline phase and the isotropic amorphous phase, an intermediate oriented phase and a rigid amorphous phase exist.     

Surface engineering of microchannel walls for protein separation and directed microfluidic flow

The preparation of surfaces in microfluidic devices that selectively retain proteins may be difficult to implement due to the incompatibility of derivatization methods with microdevice fabrication techniques. This review describes recently reported developments in simple and rapid methods for engineering the surface chemistries of microchannels based on construction of press-fit microdevices. These devices are fabricated by placing a glass fiber on a PDMS film and pressing the film on a silicon wafer or a microscope slide that has been derivatized with octadecyltrichlorosilane (ODS). The film adheres to the slide and forms an elliptically shaped channel around the fiber. The combination of surface wettability of a hydrophilic glass microfiber and the surrounding hydrophobic microchannel surfaces directs a narrow boundary layer of liquid next to the fiber in order to bring the sample in contact with the separation media and results in selective retention of proteins. This phenomenon may be exploited to enable microscale separation applications since there are a wide variety of fibers available with different chemistries. These may be used to rapidly fabricate microchannels that serve as stationary phases for separation at a microscale. The fundamental properties of such devices are discussed.     

Nematic liquid crystal in contact with periodically patterned surfaces

Nematic liquid crystals confined between two different substrates, possessing alternating stripe patterns of planar and homeotropic anchoring, are studied within the Frank–Oseen theory, in which the anchoring energy function is given by the Rapini–Papoular expression. By numerical minimization of the free energy we determine phase transitions between uniform and distorted nematic textures. The calculations reveal that these phase transitions can be triggered by changing the shift of the stripe patterns with respect to each other. A hybrid nematic cell model together with an effective anchoring strength can be used to describe the phase behaviour for sample thicknesses larger than the periodicity of the stripe pattern. Rich phase behaviour is predicted for the case of a generalized expression for the surface free energy.     

Nematic liquid crystal in contact with periodically patterned surfaces

Nematic liquid crystals confined between two different substrates, possessing alternating stripe patterns of planar and homeotropic anchoring, are studied within the Frank-Oseen theory, in which the anchoring energy function is given by the Rapini-Papoular expression. By numerical minimization of the free energy we determine phase transitions between uniform and distorted nematic textures. The calculations reveal that these phase transitions can be triggered by changing the shift of the stripe patterns with respect to each other. A hybrid nematic cell model together with an effective anchoring strength can be used to describe the phase behaviour for sample thicknesses larger than the periodicity of the stripe pattern. Rich phase behaviour is predicted for the case of a generalized expression for the surface free energy.