Elastic constants of a nematic liquid crystal: Quadrupole-quadrupole interaction in the ellipsoidal approximation

The elastic constants of a nematic liquid crystal are calculated by means of a pseudo-molecular method that considers the quadrupolar intermolecular interaction with a screening length governing the range of the forces. The bulk as well as the surface-like elastic constants are determined as functions of the eccentricity of the interaction volume of ellipsoidal shape. It is shown that the elastic constants become negative for some values of the eccentricity, and, therefore, that the screened quadrupolar interaction could be the source of instabilities in the nematic phase and should be taken into account to interpret threshold phenomena in these systems.     

Langmuir-Blodgett film and nematic interface

The orientation induced by a Langmuir-Blodgett film on a Nematic Liquid Crystal (NLC) is theoretically analyzed. We show that the effective surface energy is due to different contributions connected with steric and van der Waals interactions between the nematic and the solid substrate. The analysis shows that the Langmuir-Blodgett film orientation depends on the surface density of the molecules. The initial homeotropic orientation may become unstable giving rise to a tilted film. The average orientation of the nematic molecules is also analyzed. We show that, in the event in which the steric interaction Nematic-Langmuir-Blodgett film is very large with respect to the dispersion interaction Nematic-Substrate, the nematic orientation coincides with the one of the film. On the contrary, when the two interactions are comparable, the orientation of the two media may differ. In particular, we analyze how the stable orientation depends on the surface molecular density of the film.     

Geometry of nematic liquid crystals under shearing flow

In this work, an extended version of the Hess-Baalss conformal approach is used to propose a relation connecting the viscosity coefficients of the nematic liquid crystals. Starting from the well-known fact that, in its usual form, the conformal transformation leads to results which are not observed experimentally, it is shown that, when the director field of an ordered nematic phase under sheared motion is taken as a three-dimensional surface with torsion, the resulting theory describes the observed experimental data efficiently. Moreover, this model predicts that the five viscosity coefficients of the Leslie ah hoc model are not independent, but connected. A comparison of the deduced relationship with experimental data is performed and an excellent agreement is obtained.     

The effect of photoisomerization on the nonlinearity of an azo dye-doped nematic mixture

We used the pump-probe method to study of nonlinear behavior of an azo dye-doped nematic mixture. We demonstrated that the light-induced nonlinearity can be reversed via both of the ordinary and extraordinary components of the pump beam. It is also showed that the light-induced torque can be changed as the angle between the wave vector of the extraordinary component of the pump beam and the director is varied; a high fraction of the isomers are in the trans case for small angles, and for above a critical angle the cis isomer concentration is overcome. In addition, it was shown that the nonlinearity of the sample could be changed by an ordinary component of pump beam. Consequently, an ordinary ray can control the nonlinear behavior of the sample.     

Phase transitions in lyotropic nematic gels

In this paper, we discuss the equilibrium phases and collapse transitions of a lyotropic nematic gel immersed in an isotropic solvent. A nematic gel consists of a cross-linked polymer network with rod-like molecules embedded in it. Upon decreasing the quality of the solvent, we find that a lyotropic nematic gel undergoes a discontinuous volume change accompanied by an isotropic-nematic transition. We also present phase diagrams that these systems may exhibit. In particular, we show that coexistence of two isotropic phases, of two nematic phases, or of an isotropic and a nematic phase can occur. Received 15 February 2002 and Received in final form 14 June 2002     

The structural transitions in ferronematics and ferronematic droplets

The paper presents an overview of the observations of structural transitions in ferronematic based on thermotropic nematic 6CHBT (4-trans-4′-n-hexyl-cyclohexyl-isothiocyanato-benzene) and in ferronematic droplets. The type of anchoring was determined using the results of the capacitance measurements. The ferronematic droplets were observed in solutions of nematogenic 6CHBT with fine magnetic particles and phenyl isocyanate. The phase diagram of the transitions between isotropic and nematic phases was found. The magneto-dielectric measurements of various structural transitions in this new system enabled to estimate the type of anchoring of nematic molecules on magnetic particles surfaces in droplets.     

Critical exponents for Fréedericskz transition in nematics between concentric cylinders

The equilibrium tilt angle profile in a cell limited by two concentric cylinders filled with nematic liquid crystals is determined for strong homeotropic anchoring at the surfaces. The anchoring condition is such that the nematic director is perpendicular to the cylinder axes and a radial nonuniform electric field is applied to investigate a Fréedericksz transition. The distortions induced by the field remain in the plane perpendicular to the cylinder axes, and a threshold field is analytically determined indicating a transition from a pure splay to a splay-bend conformation of the director. It is shown that this transition can be induced by the thickness of the region between the two cylinders, and can be detected even in the absence of an external field. If the maximum value of the tilt angle is assumed as an order parameter, its behavior near to the transition can be used to obtain the critical exponent, which is the same as the one obtained in the mean field approximation. These results are indications that nontrivial consequences may occur when complex fluids are subject to non-planar geometries.     

Nonlinear molecular deformations and solitons in a nematic liquid crystal

We studied nonlinear molecular deformations in a nematic liquid crystal with homeotropically aligned molecules and hard boundaries. As the basic dynamical equation for the director axis of the liquid crystal resembles the Landau-Lifshitz equation representing spin dynamics in a one dimensional classical continuum isotropic Heisenberg ferromagnetic spin chain, we invoke here the space curve formalism and the stereographic projection technique used in the case of the Heisenberg spin chain. Under space curve mapping, the director dynamics with elastic deformation is found to be governed by a perturbed nonlinear Schrödinger equation. A multiple-scale perturbation analysis brings out perturbed solitons to represent molecular deformations in the nematic liquid crystal. However, when a constant electric field is applied, the director dynamics is expressed under stereographic projection and the molecular deformations are found to be governed by periodic and localized static planar director configurations. A linear stability analysis on the static planar configurations shows that the system exhibits stable deformations.     

Probing liquid crystals nonlinearly

Optical second-harmonic generation has been used to study the anisotropic orientation behavior of liquid-erystal siloxane molecules embedded in a nematic and/or ferroelectric host matrix. All of the studied guest-host systems show an exceedingly high degree of in-plane anisotropy along the direction of the rubbed interior polyimide layer of the surface-stabilized liquid-crystal sample cell. Alongitudinally applied electrical field leads to susceptibility components exceeding 1 pm/V for a poled sample cell of 5 m thickness containing 10% by weight of the siloxane guest in a nematic matrix.Paper presented at the 129th WE-Heraeus-Seminar on Surface Studies by Nonlinear Laser Spectroscopies, Kassel, Germany, May 30 to June 1, 1994     

Azimuthal anchoring energy at the interface between a nematic liquid crystal and a PTFE substrate

The azimuthal anchoring energy of the nematic liquid crystal 4-pentyl-4'-cyanobiphenil (5CB) on a poly(tetrafluoroethylene) (teflon, PTFE) film is measured for the first time. The PTFE film is deposed using the Wittmann and Smith technique which consists on rubbing a bar of this polymer against a glass substrate at a controlled temperature and pressure. Measurements of the azimuthal anchoring energy are made with a reflectometric technique which provides high accuracy and sensitivity. The dependence of the azimuthal anchoring energy on temperature and on the rubbing pressure is investigated. The extrapolation length remains virtually constant in the whole temperature range of the nematic phase except for an increase of 25% close to the clearing temperature. The azimuthal anchoring energy is somewhat strong and increases with increasing the deposition pressure of PTFE. The observation of a relevant pre-transitional anisotropy of the reflection coefficients in the isotropic phase proves that the surface interactions favor an excess of orientational order. Ageing of the anchoring energy and gliding of the easy axis are experimentally observed. Both these phenomena suggest the presence of an anisotropic adsorbed layer of nematic molecules on the PTFE film.     

Theory of microphase separation on side-chain liquid-crystalline polymers with flexible spacers

We model a melt of monodisperse side-chain liquid-crystalline polymers as a melt of comb copolymers in which the side groups are rod-coil diblock copolymers. We consider both excluded-volume and Maier-Saupe interactions. The first acts among any pair of segments while the latter acts only between rods. Using a free-energy functional calculated from this microscopic model, we study the spinodal stability of the isotropic phase against density and orientational fluctuations. The phase diagram obtained in this way predicts nematic and smectic instabilities as well as the existence of microphases or phases with modulated wave vector but without nematic ordering. Such microphases are the result of the competition between the incompatibility among the blocks and the connectivity constraints imposed by the spacer and the backbone. Also the effects of the polymerization degree and structural conformation of the monomeric units on the phase behavior of the side-chain liquid-crystalline polymers are studied.     

Splay-bend textures involving tetrahedratic order

We show that defect-free splay-bend textures are less energetic compared to uniform states in liquid-crystalline phases that possess both quadrupolar (nematic) and octupolar (tetrahedratic) order. This is because, in such systems, there is a symmetry-allowed linear gradient term in the energy. Another unusual feature of these splay-bend textures is the fact that they have a non-homogeneous, space-dependent free-energy density. These results may help clarify some mysterious features noted for the B7 liquid-crystal phase formed by achiral banana-shaped molecules.     

Corresponding states of nematic birefringence: an order parameter universality

In this work, experimental birefringence data of several nematic liquid crystals, which share the presence of a nematic–isotropic and a nematic–crystalline phase transition, are used to show that the birefringence presents a universal behaviour which encompasses the entire range of the nematic phase. The meaning and consequences of such behaviour are discussed; as the order parameter is proportional to the birefringence, this result implies that the order parameter has an extended universal profile, similar to a corresponding state law, which is independent of the liquid crystal compound and becomes determined once the temperature interval of the existence of the nematic compounds is obtained.     

On the effect of an applied magnetic field on the shear-induced pattern formation in nematic polymer liquid crystals

The effect of an applied magnetic field and of the boundaries on the stability of the shear flow of nematic polymer liquid crystals of the tumbling type with respect to the formation of the transient spatially periodic patterns that appears after the start-up of shearing is studied. The unidirectional shear of a nematic director initially uniformly oriented orthogonally to the sample plane and with strong anchoring is considered. The magnetic field is applied orthogonally to the sample plane or in the same direction of the flow. For a given value of the Ericksen number of the flow a critical value of the magnetic-to-viscous energy ratio shows up above which the uniform flow is stable. When the influence of the boundaries may be neglected, an internal Ericksen number that stays constant in a given material is considered such that the wavelength of the periodic pattern is a self-adjusted length. An internal generalized Ericksen number is defined such that it is a universal function of the magnetic-to-viscous energy ratio.To the memory of my mother     

Orientational diffusivities measured by Rayleigh scattering in a lyotropic calamitic nematic () liquid crystal phase: the backflow problem revisited

Using a light-beating technique we have measured the damping time of thermal fluctuations of the nematic director for the so called cylindrical or calamitic nematic (N_C) phase of the lyotropic system K-laurate/decanol/. By varying the scattering angle in suitable geometries, we have been able to estimate the orientational diffusivities associated to the three pure deformations of splay, twist and bend. A former measurement made in the disk-like N_D phase of the same system yielded a large deviation between the splay and twist diffusivities. The effect was then attributed to induced flows, or backflow, which could be responsible for the reduction of the splay viscosity. In fact, this is the analogous effect, for disks, to the one recognized since long time ago arriving for rod-like molecules in a classical nematic, though in this case it is associated with bend deformations. The analogy comes about thanks to the interchange of the role played by disks and cylinders for, respectively, splay and bend fluctuations.The measurements reported here provide a new test on the applicability of the backflow model to a nematic system composed of micelles, that is, aggregates made of amphiphilic (surfactant) molecules, in its cylindrical-like variant, i.e. the N_C phase. In addition, the comparative study made here with the previous results existing in the literature for the N_D phase, allows us to conjecture on structural issues concerning lyotropic nematics. Received: 29 April 1998 / Revised: 19 August 1998 / Accepted: 31 August 1998     

Rectangular to hexagonal columnar phase transition exhibited by a biforked mesogen

We present the structural study of a biforked compound exhibiting a Col_r-Col_h phase transition. This study was performed by means of DSC, optical microscopy, X-ray diffraction, dilatometry and molecular modelling. The molecular packing within the two columnar mesophases of this compound is discussed. For the first time, it is shown that the clusters of adjacent molecules which form the elementary section of a column are tilted with respect to the columnar axis in the rectangular mesophase. From the whole set of experimental data, the number of molecules in a columnar section is found to be about 5 in the rectangular mesophase, and 4 in the hexagonal one. The transition between the two columnar mesophases is discussed with respect to its slow kinetics. Received 1st October 2002 Published online: 16 April 2003 RID="a" ID="a"e-mail: ribeiro@cii.fc.ul.pt RID="b" ID="b"UMR 7504     

Peculiarities of biphasic regions at phase transitions in oriented textures of 4-cyano-4′-n-pentylbiphenyl

Peculiarities of the biphasic regions at the direct and reverse phase transitions between homeotropic oriented nematic mesophase and isotropic liquid have been investigated in detail in this work. The shift of phase transition temperatures to the low temperatures by the reverse phase transitions have been observed for this mesophase. Nonlinearity of thermotropic and thermo-optical properties at the phase transitions between nematic mesophase and isotropic liquid have been found.     

Critical voltages and blocking stresses in nematic gels

We present a model of the dynamics of director rotation in nematic gels under combined electro-mechanical loading. Focusing on a model specimen, we describe the critical voltages that must be exceeded to achieve director reorientation, and the blocking stresses that prevent alignment of the nematic director with the applied electric field. The corresponding phase diagram shows that the dynamic thresholds defined above are different from those predicted on the sole basis of energetics. Multistep loading programs are used to explore the energy landscape of our model specimen, showing the existence of multiple local minima under the same voltage and applied stress. This leads us to conclude that hysteresis should be expected in the electro-mechanical response of nematic gels.     

An anchoring transition at surfaces with grafted liquid-crystalline chain molecules

The anchoring of nematic liquid crystals on surfaces with grafted liquid-crystalline chain molecules is studied by computer simulations and within a mean-field approach. The computer simulations show that a swollen layer of collectively tilted chains may induce untilted homeotropic (perpendicular) alignment in the nematic fluid. The results can be understood within a simple theoretical model. The anchoring on a layer of mutually attractive chains is determined by the structure of the interface between the layer of chain molecules and the solvent. It is controlled by an interplay between the attractive chain interactions, the translational entropy of the solvent and its elasticity. A second-order anchoring transition driven by the grafting density from tilted-to-homeotropic alignment is predicted. Received 5 July 2001 and Received in final form 16 November 2001