Defects in a TGBA phase: A theoretical approach

Following our experimental observations of disclination lines in freely suspended droplets and free-standing films (Yu.A. Nastishin et al., Eur. Phys. J. E 5 353 (2001)), topological defects of the twist grain boundary (TGBA) phase are considered according to two aspects: topological and energetical. There are two classes of line defects, disclinations (as in the cholesteric (N*) phase and the liquid vortices phase (NL*), relating to the directors tripod symmetries) and dispirations (relating to the translation-rotation symmetries); there are no topological point defects. Differences between N*, NL* and TGBA disclinations are physical, not topological. The absence of focal conic domains in the TGBA phase is an immediate consequence of the materialization of the helical axis (along the χ-director); the same feature, coupled to the trend to parallelism of the smectic layers, accounts for the predominance of λ-lines. Finally, the presence of defects akin to developable domains is explained in the frame of the leastcurvaturemodel, that requires the introduction of a third type of defects: the densitiesofedgedislocations of the smectic layers. Received 20 February 2002     

Pinning-depinning of the contact line on nanorough surfaces

We study the pinning-depinning phenomenon of a contact line on a solid surface decorated by a random array of nanometric structures. For this purpose, we have investigated the contact angle hysteresis behaviour of six different wetting and non-wetting fluids with surface tensions varying from 25 to 72mN m^-1. For low values of the areal density of defects φ_d, the hysteresis H increases linearly with φ_d indicating that “individual” defects pin the contact line. Then, from a given value of φ_d, the hysteresis H becomes to decrease with increasing φ_d, indicating a new kind of collective depinning. These two regimes were observed for all fluids used. In both cases, our experimental results are compared with the theoretical predictions for contact angle hysteresis induced by single or multiple topographical defects. We ascribe the decrease of H to the formation of cavities along the wetting front.     

Identification of a TGBA liquid crystal phase via its defects

We have shown that cholesteryl nonanoate, a thermotropic compound which is well known to exhibit pretransitional effects at the smectic A (SmA) cholesteric (N*) transition (W.L. McMillan, Phys. Rev. A 4, 1238 (1971); 6, 936 (1972)), has in fact a TGBA phase in between. Our arguments rely on the observation of new TGBA defects, either in Robinson spherulites cooled from the N* phase or in free-standing films. The same new defects can be obtained in a well-documented TGBA phase of a tolane compound. We analyze qualitatively the TGBA defects in both geometries, in particular their relation to the disclination radius of the N* Robinson spherulites. Received 12 February 2001     

Universal non-monotonic smectic fluctuations of liquid crystal films in a magnetic field

Free-standing liquid crystal films with positive diamagnetic susceptibility can have the smectic ordering enhanced by an external field applied perpendicular to the plane layers. Within a quadratic functional integral approach, we investigate the interplay between the smectic order induced by an external field H and that due to the surface tension γ between the film and the surrounding gas. We find that the average smectic fluctuation is a non-monotonic function of film thickness, with a characteristic thickness scale ξ _H delimiting the predominance of surface tension and magnetic field effects. This characteristic thickness obeys simple asymptotic power-law relations as a function of the ordering terms which allows us to represent the average smectic fluctuations in a universal scaling form. Received 7 January 2003 Published online 1st April 2003 RID="a" ID="a"e-mail: marcelo@ising.fis.ufal.br     

The roughening transition of vicinal surfaces

Facetting of a vicinal surface is due to an arrangement of parallel primary steps which is commensurate with the substrate in plane periodicity (for instance one step every pth atomic row). It was shown by [#!Grempel!#] that such a locking requires an interaction between steps together with a finite step stiffness. But this early approach only reveals part of the story, as it is limited to sharp solid-vacuum interfaces in which thermal excitation of energetically expensive kinks controls all fluctuations. In this paper the problem is taken afresh in a language which applies equally well to “soft” interfaces, with important changes in the conclusions. Received 26 June 2001     

Energetics of 2D colloids in free-standing smectic-C films

The formation of regular colloid patterns in free-standing smectic films at the transition from the smectic-C to the isotropic or nematic phase is well known experimentally. The self-organization of isotropic or nematic droplets is caused by their mutual interaction, mediated by elastic distortions of the local director in the surrounding liquid crystal. These distortions are related to the anchoring conditions of the director at the droplet border. We describe analytically the energetics of the liquid crystal environment of a single droplet in one-constant approximation. A method of complex analysis, Conformal Mapping, is employed. Following a suggestion of Dolganov et al. (Phys. Rev. E. 73, 041706 (2006)), energetics of chain and grid patterns built from the colloids are investigated numerically in order to explain experimentally observed formations and their director fields.     

Poling of liquid crystals in thin films

We examine the effect of a strong DC electric field on the molecular orientational order and the nonlinear optical response of liquid crystals in thin films. We compare the results of second-harmonic generation measurements with the predictions of two models, one assuming that the dipoles carried by the molecules have no interactions (the isotropic model), and the other assuming that the dipoles evolve in a Maier-Saupe orienting field responsible for the liquid-crystalline order (the Maier-Saupe model). In both cases, we take into account the effect of surfaces and confinement on the behavior of the molecules. We find that the molecular dipoles behave as predicted by the isotropic model, but that their reorientation is correlated in such a way that the apparent dipole moment of the reorienting units is one order of magnitude larger than the molecular dipole moment. Received: 13 December 2002 / Accepted: 22 April 2003 / Published online: 21 May 2003 RID="a" ID="a"Also at FOM-Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands. RID="a" ID="a"Also at FOM-Institute for Atomic and Molecular Physics, Kruislaan 407, 1098 SJ Amsterdam, The Netherlands. RID="b" ID="b"e-mail: jerome@science.uva.nl     

Colloidal inclusions in smectic films with spontaneous bend

Inclusions in free-standing smectic films are simple model systems for two-dimensional anisotropic dispersions. From theory and experiment, different topologies of elastic distortions of the embedding liquid crystal are known. Quadrupolar and different dipolar defect configurations in the vicinity of the inclusion are possible, and these configurations determine the type of interactions between the inclusions. The quadrupolar configuration is often energetically preferred. We show, however, that dipolar director configurations around inclusions can be energetically favourable over quadrupolar arrangements in chiral smectics, as a consequence of a spontaneous-bend term in the elastic-energy formulation. As the inclusion size influences the selection of the deformation types, the corresponding spontaneous-bend constant can be estimated for the strong anchoring limit if the c -director fields around inclusions of different diameters are taken into account.     

Distortion and unwinding of the helical structure in polymer-stabilized short-pitch ferroelectric liquid crystal

We report the effect of an anisotropic polymer network formed from an achiral photoreactive monomer in a short-pitch chiral SmC* phase on the distortion and the unwinding of the helical structure of the ferroelectric phase. The electro-optical behaviour and ferroelectric properties were experimentally determined for films containing various polymer concentrations. The critical field, E_u, for the transition from the distorted structure to the homogeneous state was measured as a function of polymer concentration. A linear increase of E_u versus polymer concentration was observed, showing that the helical structure of the short-pitch SmC* phase was stabilized by the polymer network. This behaviour was expected to be a consequence of the increase of the apparent elastic constants of the ferroelectric liquid crystal stabilized by the anisotropic polymer network films. The polymer network morphology was investigated using atomic-force microscopy, revealing a twisted structure of the polymer fibers. This twisted structure was transferred onto a polymer network during the polymerization process within a short-pitch SmC* phase. The increase of the apparent elasticity can then be interpreted by a strong interaction between polymer network and the liquid-crystal molecules. From our experimental data, the coupling coefficient, W_p, characterizing this interaction was evaluated for all studied polymer concentrations.     

X-ray scattering study of the electric-field-induced layer deformations of an antiferroelectric Liquid Crystal

The effect of an external electric field on the local layer structure is investigated in the SmC^* _A, SmC^* _FI and SmC^* phases using X-ray diffraction. X-ray scattering and spontaneous polarization measurements are performed under several increasing (and decreasing) steps of AC applied voltage. The effects of the electric field differ significantly from one phase to the other. The chevron-to-bookshelf transition occurs abruptly at a high field value in the SmC^* _A phase whereas layer deformations are more progressive and occur at lower field values in the other phases. Comparison of the different behaviours suggests that the destruction of the chevron structure is mainly affected by the local molecular order. Received 16 July 2001 and Received in final form 7 December 2001     

Smectic-A edge dislocations in a very thin cell

We study stable “bookshelf” smectic-A structures within a very thin plane-parallel cell of thickness L in which the mismatch between surface preferred (d _s) and intrinsic (d₀) smectic layer thicknesses occurs. The Landau-Ginzburg approach based on a complex smectic order parameter is used. For a weak enough smectic positional anchoring strength W smectic layers adopt the modified bookshelf profile. In a thick enough cell with increasing W a lattice of edge dislocations is continuously formed at the confining surfaces and then depinned from them. The structure with dislocations is formed when the condition d ₀/( d ₀/d _s - 1) ∼ 2 is fulfilled, where is the positional surface anchoring extrapolation length. If the cell is thin enough the dislocations formed at opposite cell plates annihilate and consequently the smectic layers adopt a locked bookshelf structure. This transition is discontinuous and takes place when d ₀/(L d ₀/d _s - 1) ∼ 5 is realized. To observe these transitions in a cell of thickness L∼ 1μm the conditions W∼ 10^-6 J/m ² and d ₀/d _s - 1∼ 5 ^. 10^-4 have to be fulfilled. All the three qualitatively different structures coexist at the triple point. Received 21 February 2002     

A molecular theory of smectic C liquid crystals made of rod-like molecules

Organic compounds exhibiting the smectic C phase are made of rod-like molecules that have dipolar groups with lateral components. We argue that the off-axis character of the lateral dipolar groups can account for tilt in layered smectics (SmC, SmC*, SmI etc.). We develop a mean-field theory of the smectic C phase based on a single-particle potential of the form U _C ∝ sin(2θ)cosφ, consistent with the biaxial nature of the phase, where θ and φ are the polar and azimuthal angles, respectively. The hard-rod interactions that favour the smectic A phase with zero tilt angle are also included. The theoretical phase diagrams compare favourably with experimental trends. Our theory also leads to the following results: i) a first-order smectic C to smectic A transition above some value of the McMillan parameter α, leading to a tricritical point on the smectic C to smectic A transition line and ii) a first-order smectic C to smectic C transition over a very small range of values of the model parameters. We have also extended the theory to include the next higher-order term in the tilting potential and to include the effect of different tilt angles for the molecular core and the chain in the SmC phase. Received 3 August 2002 RID="a" ID="a"Present address: Department of Physics, Vijaya College, R. V. Road, Bangalore - 560 004, India. RID="b" ID="b"e-mail: nvmadhu@rri.res.in     

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.     

Influence of surface ordering on the wetting of structured liquids

The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition (ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent field calculations of the free energy of the system for different situations, depending on the relative tendency for the different block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization of a film that would otherwise dewet. Received 3 August 2001 and Received in final form 1 November 2001     

Temperature effects on capillary instabilities in a thin nematic liquid crystalline fiber embedded in a viscous matrix

Linear stability analysis of capillary instabilities in a thin nematic liquid crystalline cylindrical fiber embedded in an immiscible viscous matrix is performed by formulating and solving the governing nemato-capillary equations, that include the effect of temperature on the nematic ordering as well as the effect of the nematic orientation. A representative axial nematic orientation texture with the planar easy axis at the fiber surface is studied. The surface disturbance is expressed in normal modes, which include the azimuthal wave number m to take into account non-axisymmetric modes. Capillary instabilities in nematic fibers reflect the anisotropic nature of liquid crystals, such as the ordering and orientation contributions to the surface elasticity and surface normal and bending stresses. Surface gradients of normal and bending stresses provide additional anisotropic contributions to the capillary pressure that may renormalize the classical displacement and curvature forces that exist in any fluid fiber. The exact nature (stabilizing and destabilizing) and magnitude of the renormalization of the displacement and curvature forces depend on the nematic ordering and orientation, i.e. the anisotropic contribution to the surface energy, and accordingly capillary instabilities may be axisymmetric or non-axisymmetric. In addition, when the interface curvature effects are accounted for as contributions of the work of interfacial bending and torsion to the total energy of the system, the higher-order bending moment contribution to the surface stress tensor is critical in stabilizing the fiber instabilities. For the planar easy axis, the nematic ordering contribution to the surface energy, which renormalizes the effect of the fiber shape, plays a crucial role to determine the instability mechanisms. Moreover, the unstable modes, which are most likely observed, can be driven by the dependence of surface energy on the surface area. Low-ordering fibers display the classical axisymmetric mode, since the surface energy decreases by decreasing the surface area. Decreasing temperature gives rise to the encounter with a local maximum or to monotonic increase of the characteristic length of the axisymmetric mode. Meanwhile, in the presence of high surface ordering, non-axisymmetric finite wavelength instabilities emerge, with higher modes growing faster since the surface energy decreases by increasing the surface area. As temperature decreases, the pitches of the chiral microstructures become smaller. However, this non-axisymmetric instability mechanism can be regulated by taking account of the surface bending moment, which contains higher order variations in the interface curvatures. More and more non-axisymmetric modes emerge as temperature decreases, but, at constant temperature, only a finite number of non-axisymmetric modes are unstable and a single fastest growing mode emerges with lower and higher unstable modes growing slower. For nematic fibers, the classical fiber-to-droplet transformation is one of several possible instability pathways, while others include chiral microstructures. The capillary instabilities' growth rate of a thin nematic fiber in a viscous matrix is suppressed by increasing either the fiber or matrix viscosity, but the estimated droplet sizes after fiber breakup in axisymmetric instabilities decrease with increasing the matrix viscosity. Received 15 April 2002 and Received in final form 3 October 2002 RID="a" ID="a"e-mail: alejandro.rey@mcgill.ca     

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     

Induced ferrielectricity in antiferroelectric liquid crystals

The behaviour of the antiferroelectric SmC_A liquid crystal phase under applied electric field is discussed theoretically. The phase diagram involving the SmA, SmC_A and SmC _A ^* phases is worked out and shown to exhibit a Lifshitz critical point. The deformation of the bilayer structures induced by the field transforms the SmC_A phases into a ferrielectric phase whose specific configuration is described. Received: 23 October 1997 / Revised: 8 April 1998 / Accepted: 14 July 1998     

Faceting and stability of smectic A droplets on a solid substrate

It is shown that a smectic A droplet deposited on a solid substrate treated for strong homeotropic anchoring is faceted at the top in spite of the fact that there are no steps at the free surface, but instead edge dislocations in the bulk. The radius of the facet and the full profile of the curved part of the droplet are determined as a function of the temperature in the vicinity of a nematic-smectic A phase transition. It is shown that the observed profiles do not correspond to the actual equilibrium shape, but to metastable configurations close to their point of marginal stability. In addition, we predict that the profiles must be different for a given temperature depending on whether the droplet has been heated or cooled down to reach this temperature. Finally, we discuss the problem of the formation of giant dislocations in big droplets (Grandjean terraces).     

Temperature dependence of the effective anchoring energy for a nematic-ferroelectric interface

Specific features of the anisotropic interaction between a nematic mixture and a polar surface of a ferroelectric triglycine sulfate crystal have been studied over a wide temperature range including the substrate's Curie point T_c. The mixture was composed of two nematic liquid crystals, 60% of p-methoxybenzylidene-p-n-butylaniline (MBBA) and 40% of p-ethoxybenzylidene-p-n-butylaniline (EBBA), and doped with a small amount of a dichroic dye. The temperature dependence of the polarized components of optical density D_j of the dye absorption band for the nematic and isotropic phases of the MBBA+EBBA mixture has been obtained using polarization optic techniques. The temperature-induced structural changes in the nematic layer near T_c were found to be related to the changes in the orientational part of the tensor order parameter Q_ik. The experimental data have been interpreted using the model, in which the dispersive van der Waals forces of the substrate stabilize the planar orientation of the nematic in the bulk competing with the short-range anchoring forces in the vicinity of T_c. At the same time, the anisotropic part of the surface energy has two terms with the orthogonal easy axes. The nature of the surface electric field and its effect on the director alignment at the interface have been clarified. Taking into account the known relation between anchoring strength and the nematic order parameter, the effective anchoring energy w_eff for the studied system has been determined as a function of temperature.     

Theoretical investigations of rotational phenomena and dielectric properties in a nematic liquid crystal

The molecular dynamics (MD) simulation, based on a realistic atom-atom interaction potential, was performed on 4-n-pentyl-4'-cyanobiphenyl (5CB) in the nematic phase. The rotational viscosity coefficients (RVCs) γ _i, (i = 1, 2) and the ratio of the RVCs λ = - γ ₂/γ ₁ were investigated. Furthermore, static and frequency-dependent dielectric constants and ε were calculated using parameters obtained from the MD simulation. Time correlation functions were computed and used to determine the rotational diffusion coefficient, D _⊥. The RVCs and λ were evaluated using the existing statistical-mechanical approach (SMA), based on a rotational diffusion model. The SMA rests on a model in which it is assumed that the reorientation of an individual molecule is a stochastic Brownian motion in a certain potential of mean torque. According to the SMA, γ _i are dependent on the orientational order and rotational diffusion coefficients. The former was characterized using: i) orientational distribution function (ODF), and ii) a set of order parameters, both derived from analyses of the MD trajectory. A reasonable agreement between the calculated and experimental values of γ _i and λ was obtained. Received 22 March 2000 and Received in final form 8 October 2000