Anchoring transitions with polar and non-polar nematic liquid crystals on incompletely oxidized silane substrates

The active oxygen gas arising from a plasma reactor is used to realize progressive chemical modifications onto silane coatings that could be particularly interesting as alignment layers for liquid crystal display applications. Depending on the oxygen density grafted onto the substrate, these alignment layers provide different zenithal anchoring angles, or pretilt angles, with anchoring transitions, for polar and non-polar nematic liquid crystals as 5CB and MBBA, respectively. The anchoring transitions are found to be smoother with the polar nematics. Such a behavior is discussed in terms of the differential wetting model by adding a cosine term to the interaction energy between the nematic and the substrate. A local justification is proposed for this symmetry breaking term. Received: 18 May 1998     

Helically modulated electroclinical effects in twist grain boundary liquid crystals

We report the first observation of an electroclinical effect at the TGB-TGB transition induced by an external DC electric field applied perpendicular to the pitch direction. Upon increasing the field, the smectic layers rather than the director field tilt over relative to the helical axis, allowing to detect the effect by X-ray scattering from well aligned samples. The observations are qualitatively interpreted in the frame of a mean field phenomenological model of a helically modulated electroclinical effect. Received: 24 April 1998 / Revised: 22 June 1998 / Accepted: 31 July 1998     

Azimuthal anchoring of nematic on undulated substrate: Elasticity memory

We measure the azimuthal anchoring energy of the nematic 5CB on sinusoidal holographic unidimensional and bidimensional gratings. We find that the anchoring strength is almost the same for all of the gratings and up to one order of magnitude stronger than expected by the topographic mechanism proposed by Berreman. We observe strong memory effects which dominate both the elastic anchoring and the easy axis gliding. We show that these memory effects limit from below the anchoring energy and are the main obstacle in the realization of substrates with weak anchoring conditions. Received: 29 April 1998 / Accepted: 23 June 1998     

Competition between ferroelectric and flexoelectric polarization in freely suspended smectic films

We report a detailed ellipsometric study of freely suspended films of chiral liquid-crystal compounds possessing smectic-A and smectic-C phases. In the temperature region between the smectic-A - smectic-C bulk and surface transitions, a discontinuous reconstruction of the tilt profile across the film is observed in the presence of a constant d.c. electric field. Comparison of the measured ellipsometric quantities with values calculated from model tilt profiles reveals a competition between a structure possessing a homogeneous tilt direction and large ferroelectric polarization and a structure with opposite tilt direction in the two film halfs and large flexoelectric polarization. Received 21 October 1998     

Optical reflectivity study of synclinic and anticlinic structures in thin freely suspended smectic films

Optical reflectivity studies have been conducted on freely suspended films with synclinic and anticlinic structures. For the first time quantitative data were obtained on orientational ordering in films with anticlinic structure. In the same wide temperature range of more than 30 K we observed both transverse and longitudinal ferroelectricity in the films of the same thickness. Equilibrium transition temperatures between structures with transverse and longitudinal polarization were above the bulk transition temperature to the SmC phase. The molecule tilt was determined in superthin films with synclinic and anticlinic ordering. Received 29 October 1999 and Received in final form 17 February 2000     

Highly anisotropic elasticity of a dendrimeric liquid crystal

Magnetic and electrical Freedericksz measurements were performed on the second generation monodendritic liquid crystal G₂(OH). The deduced elastic constants were found to be exceptionally anisotropic: the splay elastic constant K₁₁ is more than an order of magnitude larger than the bend elastic constant K₃₃, and the twist constant K₂₂ is approximately twice K₃₃. The results are discussed in terms of molecular conformations. Received: 23 February 1998 / Revised and Accepted: 26 May 1998     

Switching of banana liquid crystal mesophases under field

Taking advantage of the great number of bent-core or “banana" compounds synthesized and studied in the laboratory, we describe their behaviour under the application of an external electric field. If the field were a static one, we would work within the frame of an equilibrium phase diagram in a (field E, temperature T) space where some phases would be simple dielectrics and others ferroelectric ones with a macroscopic polarization, either spontaneous or induced by the field. In this paper, we deal with the basic responses of “banana” liquid crystals under the application of a low frequency (1 to 100 Hz) AC field. Firstly square-wave voltages allow us to locate the phase boundary between dielectric (at lower field) and ferroelectric phases (higher field) at a given temperature and field threshold. Then we apply slowly varying AC voltages with shapes like triangle or “triple-plateau” to check out the stability of the induced ferroelectric phase versus field removal. Three behaviours are encountered, the unstable one (short lifetime of the high-field ferroelectric phase) where the macroscopic polarization is destroyed and then rebuilt in the opposite direction during each half period and usually called “antiferroelectric”; the stable one (long lifetime) with a polarization that rotates at constant modulus which is labeled as “ferroelectric” and a new one where the macroscopic polarization is proportional to the applied fied, we named this behaviour as “superparaelectric”. Let us stress that these observations apply to the ferroelectric phases of the (E, T) phase diagram not to the zero field (0,T) phases observed in the usual phase characterization experiments except for an eventual spontaneous ferroelectric phase. Received 18 April 2002 and Received in final form 17 January 2003 Published online: 16 April 2003 RID="a" ID="a"e-mail: marcerou@crpp.u-bordeaux.fr RID="b" ID="b"URL: http://www.crpp-bordeaux.cnrs.fr     

Self-organization of N<Superscript>*</Superscript> inclusions in SmC<Superscript>*</Superscript> free-standing films

The behaviour of freely suspended smectic-C* ( SmC^*) films at the bulk SmC^*-cholesteric ( N^*) phase transition has been investigated using polarized-reflected-light microscopy. Our experimental observations show that above the bulk SmC^*- N^* phase transition the N^* order appears in different ways according to the film thickness. In thin films, the conventional layer-by-layer thinning occurs. In films of intermediate thickness N^* inclusions nucleate inside the SmC^* film. The distortions of the in-plane orientational order of the SmC^* host phase induce elastic interactions between the inclusions and lead to their self-organization in chain-like structures. Both the dynamic of the chaining and the parameters driving the equilibrium distance between the inclusions in the chain are investigated. In thick films, N^* fingers grow inside the film. The influence of the experimental conditions on the various processes is analysed. Received 1 July 2002 / Published online: 15 April 2003 RID="a" ID="a"e-mail: Philippe.cluzeau@univ-lille1.fr     

Effect of surface electric field on the anchoring of nematic liquid crystals

We analyse the influence of adsorbed ions and the resulting surface electric field and its gradient on the anchoring properties of nematics with ionic conductivity. We take into account two physical mechanisms for the coupling of the nematic director with the surface electric field: (i) the dielectric anisotropy and (ii) the coupling of the quadrupolar component of the flexoelectric coefficient with the field gradient. It is shown that for sufficiently large fields near saturated coverage of the adsorbed ions, there can be a spontaneous curvature distortion in the cell even when the anchoring energy is infinitely strong. We also discuss the director distortion when the anchoring energy of the surface is finite. Received: 29 September 1997 / Received in final from: 10 November 1997 / Accepted: 18 November 1997     

Effect of high electric fields on the nematic to isotropic transition in a material exhibiting large negative dielectric anisotropy

We report the experimental high electric field phase diagram of a nematic liquid crystal which exhibits a large negative dielectric anisotropy. We measure simultaneously the birefringence (Δn) and the dielectric constant (epsilon_⊥) at various applied fields as functions of the local temperature of an aligned sample. We also measure the higher harmonics of the electrical response of the medium. The following experimental results are noted: (i) enhancement of orientational order parameter S in the nematic phase due to both the Kerr effect and quenching of director fluctuations; (ii) enhancement in the paranematic to nematic transition temperature (T_PN) with field; (iii) divergence of the order parameter susceptibility beyond the tricritical point as measured by third harmonic electrical signal; (iv) a small second harmonic electrical signal which also diverges near T_PN, indicating the presence of polarised domains. Our measurements show that ΔT_PN(= T_PN(E)-T_NI(0)) varies linearly with |E| whereas the Landau de Gennes theory predicts a dependence on E². It is argued that the quenching of director fluctuations by the field makes the dominant contribution to all the observations, including the thermodynamics of the transition.     

Flow properties of the optically isotropic tetrahedratic phase

We discuss the coupling between flow and other hydrodynamic variables that can occur in the optically isotropic tetrahedratic phase (T_d) characterized by a third rank tensor order parameter T_ijk. We point out that an applied electric field or an applied temperature gradient will lead to flow. Reciprocally we predict that, for example, a shear flow applied to a tetrahedratic phase leads to an induced electric field and a temperature gradient. Similarities to recent experimental observations in the vicinity of the isotropic-B7 phase transitions in materials formed by banana-shaped molecules are discussed. Received 31 July 2001     

Using the full Raman depolarisation in the determination of the order parameters in liquid crystal systems

The depolarisation ratio for the Raman-active phenyl stretching mode has been measured over the whole of the mesophase range, and the orientational order parameters deduced, in the uniaxial nematic liquid crystal octylcyanobiphenyl (8CB). Linearly polarised light was incident normally on a homogeneously aligned sample and a χ² minimisation routine performed on the 360^° depolarisation ratio profile. The order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 , together with the differential polarisability ratio, r , are used as fitting parameters and measured as a function of temperature. Interestingly, we show that the value for r , conventionally measured in the isotropic phase and assumed to remain constant, has a clear temperature dependence, ranging from -0.032±0.008 in the isotropic phase through to -0.245±0.015 at the nematic-to-smectic A phase transition. The measured order parameters 〈P ₂₀₀〉 and 〈P ₄₀₀〉 varied from 0.35- 0.55±0.02 and 0.180- 0.245±0.02 , respectively, across the 8 ^° C wide nematic phase range. The values of both 〈P ₂₀₀〉 and 〈P ₄₀₀〉 are in excellent agreement with theory, but it is noteworthy that 〈P ₄₀₀〉 shows a much better quantitative match than has been reported in previous work. Crucially the temperature dependence of r is shown to be a contributing factor in the low 〈P ₄₀₀〉 values that have been conventionally reported from Raman scattering measurements. The potential for fitting the entire angular depolarisation ratio distribution in liquid crystalline systems that are described by more order parameters, specifically biaxial materials, is discussed.     

Orientational phase transition and the solvation force in a nematic liquid crystal confined between inhomogeneous substrates

A nematic liquid crystal confined between two identical flat solid substrates, with an alternating stripe pattern of planar and homeotropic anchoring, is studied in the framework of the Frank-Oseen theory. By means of numerical minimization of the free energy functional we study the effect of the sample thickness D on the location of the phase transition between a uniform alignment, either planar or homeotropic, and a distorted nematic texture. The solvation force f due to distortions of the nematic director is also studied. It is found that f is always attractive, and for D small compared to the periodicity of the surface structure it exhibits two distinct asymptotic behaviors: f ∼ - D ^-1/2 or f ∼ - D ^-1, depending on the relation between D and the extrapolation lengths. Received 12 November 2002 Published online: 16 April 2003     

Line defect dynamics around a colloidal particle

We study experimentally the dynamics of a topological defect located around a colloidal particle suspended in a thermotropic nematic liquid crystal. The considered defect consists of a disclination loop encircling the particle at the equator. Under specific conditions, it is shown that this disclination continuously shrinks to a hedgehog defect located in the immediate vicinity of the particle. This phenomenon corresponds to a transition between an elastic quadrupolar configuration and an elastic dipolar configuration. We performed a basic numerical calculation to get an estimate of the dissipated energy during the transition; we compare the results with theoretical predictions that describe the elastic energy of particles surrounded by defects. Received 21 December 2001     

Surface and flexoelectric polarization in a nematic liquid crystal 5CB

The temperature dependence of the surface polarization has been measured for both the planar and homeotropic orientation of a nematic liquid crystal at a solid substrate. A conventional liquid crystal 5CB, pure and doped with an azo-dye, was used in cells with controlled asymmetry for light absorption. The measurements have been made by a pyroelectric technique using short pulses of a YAG laser to create a temperature increment. The latter, in turn, was measured independently by a novel time-resolved “optical thermometer” technique monitoring temperature-dependent birefringence by a He- Ne laser beam. In accordance with the symmetry of the order parameter, the surface polarization has different sign for the two orientations, its magnitude ranges from -4 to +2pC/m. The same technique has been used for the measurement of the flexoelectric polarization in hybrid cells. The sum of the flexoelectric coefficients is e ₁ + e ₃ = - 13pC/m at 25°C. Received 28 February 2000 and Received in final form 5 September 2000     

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     

Influence of pressure on the electric-field-induced phase transitions in liquid crystals

Within the framework of Landau-de-Gennes formulation, we analyse the effect of pressure on electric-field-induced phase transitions in a liquid crystal which shows spontaneously an isotropic-smectic A transition. Inferring from the experimental pressure dependences on the layer spacing in smectic A phase, as well as the nematic-smectic A metastable temperature T^*_AN, we incorporated the pressure dependence in the free energy through (the surface energy term) and the coupling between the quadrupolar nematic ordering Q_ij and the smectic order parameter ψ. From the S-T phase diagram, we found that the stability of field-induced nematic phase increases with pressure, whereas the discontinuity of the transition decreases. Also, the region where paranematic phase transits directly to smectic A phase increases with pressure.     

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     

A biaxial nematic gel phase in aqueous vanadium pentoxide suspensions

Aqueous suspensions of V₂O₅ ribbons are one of the very few examples of mineral liquid crystals. In the concentrated regime, we show that these ribbons organize in a biaxial nematic gel phase. A Couette shear cell was used to produce a well oriented sample for in situ synchrotron X-ray scattering studies. We observed two perpendicular anisotropic sections of reciprocal space, which proves the biaxial symmetry of the nematic order. The thermodynamic and flow properties of the biaxial nematic are well described by hard-core theories. We suggest the use of a shear geometry to produce and investigate single domains of other biaxial nematics, reported but still questioned in the literature. Received 26 May 1999     

Depletion effects in smectic phases of hard-rod-hard-sphere mixtures

It is known that when hard spheres are added to a pure system of hard rods the stability of the smectic phase may be greatly enhanced, and that this effect can be rationalised in terms of depletion forces. In the present paper we first study the effect of orientational order on depletion forces in this particular binary system, comparing our results with those obtained adopting the usual approximation of considering the rods parallel and their orientations frozen. We consider mixtures with rods of different aspect ratios and spheres of different diameters, and we treat them within Onsager theory. Our results indicate that depletion effects, and consequently smectic stability, decrease significantly as a result of orientational disorder in the smectic phase when compared with corresponding data based on the frozen-orientation approximation. These results are discussed in terms of the τ parameter, which has been proposed as a convenient measure of depletion strength. We present closed expressions for τ, and show that it is intimately connected with the depletion potential. We then analyse the effect of particle geometry by comparing results pertaining to systems of parallel rods of different shapes (spherocylinders, cylinders and parallelepipeds). We finally provide results based on the Zwanzig approximation of a fundamental-measure density-functional theory applied to mixtures of parallelepipeds and cubes of different sizes. In this case, we show that the τ parameter exhibits a linear asymptotic behaviour in the limit of large values of the hard-rod aspect ratio, in conformity with Onsager theory, as well as in the limit of large values of the ratio of rod breadth to cube side length, d, in contrast to Onsager approximation, which predicts τ ∼ d ³. Based on both this result and the Percus-Yevick approximation for the direct correlation function for a hard-sphere binary mixture in the same limit of infinite asymmetry, we speculate that, for spherocylinders and spheres, the τ parameter should be of order unity as d tends to infinity.