The effect of spontaneous polarization on two-dimensional elasticity of smectic liquid crystals

The influence of polarity on orientational elasticity and on structures formed in the director field is studied in free-standing smectic films. Periodic stripe patterns and 2π-walls in a magnetic field are investigated. Measurements are performed on a nonpolar racemic mixture, on an optically pure ferroelectric compound, and in mixtures with different concentrations of the chiral isomers of opposite signs. The structure of periodic stripes changes drastically with the polarity of the film. The ratio of the bend K _B and splay K _S elastic constants for smectic films is determined as a function of polarization from the structure of periodic stripe patterns and 2π-walls. We find that the elastic anisotropy K _B /K _S increases essentially with increasing the polarity of the film. Changes of the elasticity and the structure of periodic stripes are explained by polarization charge effects.     

Corona patterns around inclusions in freely suspended smectic films

We discuss the structure and physical origin of corona patterns observed around solid or liquid spherical inclusions in freely suspended smectic films. Such patterns are observed when droplets or solid beads of micrometer size are sprayed onto the films. They are found in the smectic C phase and in the smectic A phase above such a smectic C phase, but disappear, for example, at the transition into a lower-temperature smectic B phase. We show that these structures are equivalent to splay domains found in the meniscus of freely suspended films, originating from surface-induced spontaneous splay.     

Tilted smectic layers of a liquid crystal between homeotropically treated plates

We investigated SmC^* films sandwiched between silane coated glass plates and observed formation of textures exhibiting a uniform tilt of the smectic layers with respect to the boundary plates. The layer tilt angle increases from zero to as the sample is cooled from the smectic A phase to room temperature. These films show linear electro-optical effects because the permanent polarization can be aligned so that it has a component parallel to the applied field without changing the layer structure. Our analysis indicates that mainly two effects determine the layer tilt. On the one hand, the surface tension tends to minimise the layer tilt. On the other hand, the surface energy promotes the director to be normal to the boundary plates. Received 17 July 1998     

Stripe instability in thin films of smectic liquid-crystal polymers

Two-dimensional nanostripes are formed in thin films of side-chain liquid-crystalline polymer films when the material enters the smectic phase. The structure is investigated using transmission electron microscopy. Electron diffraction patterns show that the chain molecules are mostly aligned in the film plane and the average molecular director is parallel to the direction of the stripes. We discuss factors affecting the stripe amplitude and periodicity, such as the film thickness and the temperature of annealing in the nematic phase, and suggest a possible mechanism for their formation. We propose that an equilibrium instability occurs due to a competition between the layer-aligning effect of the substrate and the planar director alignment, forcing smectic layers perpendicular to the film surface. The stripes decorate the overall patterns of nematic director in the polymer film and provide a means of high-resolution imaging for observation of textures and disclinations.Received: 10 June 2003, Published online: 19 August 2003PACS: 68.37.Lp Transmission electron microscopy (TEM) (including STEM, HRTEM, etc.) - 61.30.Vx Polymer liquid crystals - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 68.55.Nq Composition and phase identification     

Spectral investigations of surface ordering in ultrathin molecular films

Surface molecular ordering in ultrathin molecular films is investigated. The optical transmission spectra of molecular films ranging in thickness from 2 to 13 smectic layers (6.7–43 nm) in the region of the electronic absorption bands in the smectic A phase of cyanobiphenyl CB9 are measured. The thickness and temperature dependences of the permittivity are determined. It is found that the orientational ordering of the molecules depends on the film thickness. The penetration depth of the surface molecular orientational order does not exceed two smectic layers (<7 nm). Zh. éksp. Teor. Fiz. 115, 1833–1842 (May 1999)     

Elastic model of the primary stripe texture in free-standing chiral smectic C films

In paper E. Górecka et al.: Phys. Rev. Lett. 75 (1995) 4047 the modulations of the director inside smectic layers of chiral smectic C free-standing film were identified as a periodic system of domain walls on which the director orientation changes by . Domain walls were terminated in the film bulk. An improved model, in which domain walls are terminated by (±)-disclinations, is proposed. The model is an extension of the model of Meyer and Pershan [Solid State Commun. 13 (1973) 989] for the case of chiral smectic C films. The experimental dependence of the periodicity of the system on the film thickness is used to estimate the model parameters.     

Spontaneous periodic deformations in nonchiral planar-aligned bimesogens with a nematic-nematic transition and a negative elastic constant

Hydrocarbon linked mesogenic dimers are found to exhibit an additional nematic phase below the conventional uniaxial nematic phase as confirmed by x-ray diffraction. The phase produces unusual periodic stripe domains in planar cells. The stripes are found to be parallel to the rubbing direction (in rubbed cells) with a well-defined period equal to double the cell gap. The stripes appear without external electromagnetic field, temperature or thickness gradients, rubbing or hybrid alignment treatments. Simple modeling proposes a negative sign for at least one of the two elastic constants: splay and twist, as a necessary condition for the observed pattern.     

Phase transition to anticlinic texture in free-standing smectic c films

Experimental data on the optical reflectance of free-standing smectic C films were analyzed within the framework of a phenomenological Landau approach. At a certain temperature T _0N (determined from experimental data), which exceeds the known temperature T _c of the volume phase transition from smectic A to smectic C state, a surface phase transition takes place whereby molecules in the surface layer become sloped relative to the normal of the smectic layers. The transition temperatures T _0N ^s,a for N-layer films possessing synclinic (symmetric) and anticlinic (antisymmetric) textures of the order parameter (tilt angle θ) were determined. A comparison of the theoretical and experimental data allowed all parameters of the model to be determined (including critical indices of the correlation length and the surface order parameter). Three possible models of the transition from the state with transverse polarization (perpendicular to the molecular tilt plane) to the state with longitudinal polarization (parallel to this plane) are analyzed. The transition takes place at low (°–°) values of the order parameter θ in the middle layer of the film.     

The synthesis of the chiral non-mesogenic d-seco estrone derivatives and their influence on the phase transitions of cholesteric liquid crystals

The synthesis of new chiral seco-estrone derivatives is presented, as well as their influence on the phase transition of binary mixtures of cholesteryc liquid crystals. The new chiral derivatives do not posses any liquid crystalline phases and were synthesized in several synthetic steps, starting from estrone. We have studied the mixtures of cholesteryl non-anoate (40%) with cholesteryl myristate (40%) and addition of new chiral derivatives 3 4, or 5 (20%). It was concluded that the addition of chiral derivative 3 to the binary mixture stabilizes smectic A and cholesteric phase and shifts the phase transition temperature with respect to pure binary mixture for about 5°C towards lower temperatures. The extension of the temperature range of the cholesteric phase from 5°C to 15°C was established in the case when the derivatives 3 and 4 are added to the binary mixture of cholesteryl nonanoate with cholesteryl myristate. The phase diagrams of investigated compounds are formed on the basis of data obtained by the optical microscopy. Using X-ray diffraction on the crystalline powder of unoriented samples we have determined the molecular parameters: the thickness of smectic and cholesteric layers and average distance between the long axes of neighboring molecules.     

Nonlinearities in tilt and layer displacements of planar lipid bilayers

A novel continuum model is proposed to describe the deformations of a planar lipid bilayer suspended across a circular pore. The model is derived within a new theoretical framework for smectic A liquid crystals in which the usual director n , which defines the average orientation of the molecules, is not constrained to be normal to the layers. The free energy is defined by considering the elastic splay of the director, the bending and compression of the lipid bilayer, the cost of tilting the director with respect to the layer normal, the surface tension, and the weak anchoring of the director. Variational methods are used to derive the equilibrium equations and boundary conditions. The resulting boundary value problem is then solved numerically to compute the fully nonlinear displacement of the layers and tilt of the lipid molecules. A parametric study shows that an increase in surface tension produces a decrease in the deformation of the lipid bilayers while an opposite effect is obtained when increasing the anchoring strength.     

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     

c-director relaxation around a vortex of strength +1 in free-standing smectic-C films

The relaxation of director fields in freely suspended smectic films is studied experimentally by means of polarizing microscopy, and analyzed by solving the torque balance equation under appropriate initial and boundary conditions. We consider in particular the role of anchoring conditions of the c-director at particles and defects in the film. The structure of regular relaxation patterns allows to determine the elastic anisotropy of smectic materials. The splay elastic constant can exceed the bend constant by a factor of two and more. A remarkable consequence of this anisotropy is the stick-slip-like relaxation around a central defect of topological strength s = + 1.     

X-ray studies of the smectic B phase of the 4-bromobenzylidene-4′-alkoxyanilines

The results of X-ray studies of the nine members (4?÷?12) of the 4-bromobenzylidene-4′-alkyloxyaniline homologous series (nBBAA) in smectic B (SmB) and smectic A (SmA) phases are presented. Interestingly, no SmC phase was identified. The thickness of smectic layers in the SmA and SmB phases was estimated showing unexpectedly that in SmA it is bigger than in the SmB. For the SmB phase, orthorhombic unit cell parameters were determined as a function of temperature. The obtained data are discussed in relation to rotational dynamics.     

Texture transitions in the liquid crystalline alkyloxybenzoic acid 6OBAC

The 4,n-alkyloxybenzoic acid 6OBAC has a very rich variety of crystalline structures and two nematic sub-phases, characterised by different textures. It is a material belonging to a family of liquid crystals formed by hydrogen bonded molecules, the 4,n-alkyloxybenzoic acids (n indicates the homologue number). The homologues with 7?≤?n?≤?13 display both smectic C and N phases. In spite of the absence of a smectic phase, 6OBAC exhibits two sub-phases with different textures, as it happens in other materials of the homologue series which possess the smectic phase. This is the first material that exhibits a texture transition in a nematic phase directly originating from a crystal phase. Here we present the results of an image processing assisted optical investigation to characterise the textures and the transitions between textures. This processing is necessary to discriminate between crystal modifications and nematic sub-phases.     

Curvature walls and focal conic domains in a lyotropic lamellar phase

In the quasi-ternary CPCl/brine/hexanol lyotropic system, the interface of the lamellar and L₃ sponge phases displays a phenomenon of epitaxy: the layers of the lamellar phase tend to make a constant non-trivial angle with the interface. Thin samples of lamellar phase embedded in the sponge phase are thus submitted to oblique anchoring conditions and defects are created in the lamellar phase in order to satisfy the bulk lamellar ordering and the boundary conditions. We have studied small droplets of lamellar phase in the sponge phase. They do not exhibit the classic defects (focal conic domains) but wall defects, which appear in order to satisfy the smectic elasticity and the boundary conditions. Moreover we show through experiments in controlled geometry that, even in the presence of focal conic domains, wall defects control the size and periodicity of the textures which are observed at the interface. Received 4 November 1998     

Comparative Investigations of Light Transmission in Aligned and Non-aligned Textures of Homogeneous Mixtures of 4-n-alkyl-4′-Cyanibiphenyl Mesogens at Direct and Reverse <Emphasis Type="Italic">smectic A</Emphasis> ↔ <Emphasis Type="Italic">isotropic liquid</Emphasis> Phase Transitions

The thermo-optical properties of various types of textures (the homeotropic, planar, and tilted aligned and non-aligned textures) in liquid crystalline materials with smectic A mesophase have been investigated. Investigations have been carried out for large temperature interval and at the direct smectic A mesophase–isotropic liquid (SmA–I) and isotropic liquid–smectic A mesophase (I–SmA) phase transitions that have been carried out. Homogeneous mixtures of 4-n-octyl-4′-cyanobiphenyl with 4-n-decyl-4′-cyanobiphenyl were the objects of the investigations. Temperature dependences of the optical transmission for aligned and non-aligned textures have been measured. Temperature widths of the heterophase regions for the SmA–I and I–SmA phase transitions have been determined. The temperature shift in the optical transmission dependences to low temperatures for the reverse I–SmA phase transition temperatures and the thermal hysteresis has been found for the aligned and non-aligned textures.     

Structures and orientational transitions in thin smectic films of tilted hexatic

We present detailed systematic studies of structural transformations in thin liquid crystal films with the transition from the smectic-C (SmC) to hexatic (HSmB) phase. For the first time, all possible structures reported in the literature are observed for one material (5O.6) with varying temperature and thickness. In unusual modulated structures, the equilibrium period of stripes is twice the domain size. We interpret these patterns in the framework of a phenomenological Landau-type theory, as equilibrium phenomena produced by a natural geometric frustration in a system having spontaneous splay distortion. The text was submitted by the authors in English.     

Discrete thinning of free-standing smectic films in the de Gennes “pre-smectic liquid” model

It is shown that the successive discrete thinning of free-standing smectic films (FSSFs), which is observed when the films are heated above the temperature of the smectic A-nematic bulk phase transition, has a natural explanation in terms of the de Gennes “pre-smectic liquid” model, provided that a sufficiently large external compressive force is applied to the free surfaces of the FSSF. In a real situation this force stems from the curvature of the surrounding miniscus, which plays the role of a volume reservoir. In this model a superheated FSSF is stabilized by balancing the external compressive and elastic forces. When heating takes place the bulk modulus of the pre-smectic lattice decreases, and when the superheating reaches a critical value, the FSSF is subject to a long-wavelength instability in thickness beause the external compressive and elastic forces can no longer be balanced for a fixed number of smectic layers. If a superheated FSSF possesses adequate stability against disruption, the balance of forces, which was disrupted, and hence the stability of the FSSF can be restored as a result of spontaneous thinning of the film to a thickness corresponding to a smaller number of smectic layers. In general, heating of a superheated FSSF is accompanied by a series of such thinning transitions. Near the critical points where the balance of the forces breaks down, the dislocation mechanism of spontaneous thinning, which could be responsible for the stratified nature of the progressive discrete thinning of real FSSFs, can become dangerous. Zh. éksp. Teor. Fiz. 115, 61–69 (January 1999)     

Theoretical description of fluctuations in free-standing smectic-A films including spatial non-uniformity of their elastic characteristics

A theoretical study is reported of fluctuations in smectic layer displacements and of the correlations between them in free-standing smectic-A films formed of liquid-crystal compounds with smectic-A-isotropic liquid (Sm-A-I) and Sm-A-nematic (Sm-A-N) bulk phase transitions. The study took into account the dependence of the elastic constants for bending, K, and tension (compression), B, of smectic layers on distance to the free film surfaces. The calculations are compared with the results obtained within Hołyst’s model for spatially uniform, free-standing smectic-A films. It has been established that, below the temperature at which smectic order in the bulk of a liquid crystal disappears, taking into account the profiles of the elastic moduli K and B does not produce noticeable differences from this model. However, at temperatures considerably above the Sm-A-I and Sm-A-N phase transitions, their inclusion results in considerable discrepancies from the predictions of Hołyst’s model. Fiz. Tverd. Tela (St. Petersburg) 41, 1882–1889 (October 1999)     

Optical characterization of a nanoscale incommensurate pitch in a new liquid-crystal phase

As a remarkable orientationally ordered soft-condensed matter system, the smectic-C*(alpha) phase exhibits an incommensurate nanoscale helical pitch of more than four smectic layers. Recent theoretical advances predict the existence of a new phase showing a helical pitch of less than four smectic layers (<16 nm). By applying a novel optical technique to the study of freestanding films with increments in thickness of one smectic layer, we have measured the size of this pitch using 633 nm HeNe laser light. Our results confirm the existence of the newly predicted phase in one unique compound.