Effect of YBa2Cu3O7-x thin films on the textures and orientational properties of liquid crystals

In the present work, the effect of thin films of YBa₂Cu₃O_7-x complex compound on the mesomorphic and orientational properties of thermotropic nematic liquid crystals has been studied. Homogeneous, stable and reproducible homeotropic and tilted oriented textures of nematic liquid crystals were obtained. The effect of YBa₂Cu₃O_7-x thin films on the morphologic, orientational and optical properties of thermotropic nematic liquid crystals are discussed.     

Symmetry rules and temperature-induced anchoring transitions

A sandwich cell made of two flat glass substrates covered with obliquely evaporated SiO_x and filled with a common thermotropic nematic liquid crystal is considered. The two glasses are assembled with their evaporation directions antiparallel to each other in order to provide a uniformly pretilted nematic layer, without any local distortion. By means of a Landau-de Gennes approach, based on the general symmetry properties of the flat glass surface, including the anisotropy induced by the SiO_x, and of the nematic tensor order parameter, a temperature variation of the director azimuthal and tilt angle in the nematic phase is predicted. Observations via polarizing microscopy were performed and the fits, made according to the proposed model, compare well with the experimental data presented here.     

Pulsed-Field-Gradient NMR Study of Anisotropic Molecular Translational Diffusion in nOCB Liquid Crystals

Pulsed-field-gradient nuclear magnetic resonance (NMR) combined with magic echo decoupling is applied to study anisotropic diffusion in samples with strong static dipolar spin interactions. The approach, due to its moderate demands on the NMR hardware, can be implemented on standard commercial equipment for routine diffusion studies of liquid crystals. Using a microimaging probe, measurement of diffusion in arbitrary spatial direction is possible. Hence, the principal components of the diffusion tensor are directly obtained. Anisotropic diffusion is investigated in the thermotropic mesophases of a homologous series of nOCB liquid crystals and an analogous compound with hydroxyl groups. The geometric average diffusion coefficient changes continuously at the isotropic–nematic phase transition. Experimental data are described in terms of the molecular translation models in the nematic phase and for the second-order nematic–smectic A phase transition. The diffusion anisotropy is higher for the sample with terminal hydroxyl groups suggesting significant molecular association via hydrogen bonding.     

Changes of thermo-morphologic and thermotropic properties of liquid crystals at direct and reverse nematic mesophase ↔ isotropic liquid phase transitions: surface-induced effect

In this work, the effect of thin films on the thermo-morphologic and thermotropic properties of the phase transitions between the nematic mesophase and isotropic liquid has been investigated. Investigations have been carried out for both the heating and cooling processes. The temperature and linear widths of the biphasic regions of the direct and reverse phase transitions in nematic liquid crystals versus thickness of the thin films have been calculated with a high accuracy. The shift of the nematic mesophase–isotropic liquid and the isotropic liquid–nematic mesophase phase transition temperatures to higher temperatures and the enlargement of the temperature and linear widths of the biphasic regions as the effect of surfaces have been found.     

Polarizabilities and susceptibilities of nematic azoxybenzenes

The mean polarizabilities of homologous series of nematic liquid crystals of p,p' -di-n-alkyl azoxybenzenes are evaluated by using a modified Lippincott-δ-function potential model.¹ From these polarizabilities, the diamagnetic susceptibilities of the liquid crystals are calculated by using the method of Rao and Murthy.² The merits and limitations of the method are discussed.     

Effect of the rotational depolarization in flourescent measurements of the nematic order parameters

The effect of the rotational depolarization of the values of the order parameters <p₂ > … <p₄ > of nematic liquid crystals, determined by polarization flourescence measurements has been considered using the theory recently developed by Zannoni. For this purpose an approximate solution of the equation for the rotational diffusion in a nematic phase has been obtained in an analytical form. The order parameters of the nematic p-ethoxy-benzylidene-p-n-butylaniline have been determined experimentally and the neglect of the rotational molecular motion was found to lead to incorrect values of the order parameters.     

The even–odd effect in the dependence of optical anisotropy on the number of protons in complexing agent ions of liquid-crystal coordination compounds of lanthanides

The values of optical anisotropy of two series of thermotropic nematic liquid crystalline complexes based on the ions Eu⁺³, Gd⁺³, Tb⁺³, and Dy⁺³ have been determined. Even–odd alternation of optical anisotropy with an increasing number of protons in ions of lanthanides has been observed. It is established that, in the considered series of lanthanidomesogens, optical anisotropy is more sensitive to changes in the ligand structure of complexes than to the variation of the complexing agent.     

Diffusion in thermotropic liquid crystals

Diffusion coefficients in mesophases of thermotropic liquid crystals have been measured to a considerable extent only during the last twelve years. Some theories on diffusion in mesophases have been developed too. Measurements in nematic, smectic A, smectic B, and smectic C mesophases have been carried out by mass transport techniques, detected by radio-tracers or optically, by NMR spin-echo techniques, and by quasi-elastic neutron scattering. The diffusion is anisotropic in most of the cases. In nematics self-diffusion parallel to the molecular director (D₆) is somewhat faster than perpendicular (D_⊥). Both diffusion coefficients show about the same activation energy. Impurity diffusion (small molecules dissolved in mesophases) demonstrates the same behaviour with less anisotropy. In smectics A and C the diffusion coefficients D₆ and D_⊥ can be nearly equal. The anisotropy is now shown in their respective activation energies with E₆>E_⊥. This effect is more pronounced in impurity than in self-diffusion. In addition impurity diffusion shows a strong anisotropy of the diffusion coefficients (D_⊥?D₆). In smectics B the activation energies E₆ and E_⊥ of self-diffusion seem again to be equal and the diffusion coefficients show a small anisotropy (D_⊥≥D₆).     

The rα structure,chemical shift anisotropy,and the abnormal orientation of methyldichlorophosphine from the NMR spectrum

NMR studies of methyldichlorophosphine have been undertaken in the nematic phase of mixed liquid crystals of opposite diamagnetic anisotropies. The r_α structure is derived. The proton chemical-shift anisotropy has been determined from the studies without the use of a reference compound and without a change of experimental conditions. It is shown that the molecule orients in the liquid crystal with positive diamagnetic anisotropy in such a way that the C₃ symmetry axis of the CH₃P moiety is preferentially aligned perpendicular to the direction of the magnetic field, unlike other similar systems. This is interpreted in terms of the formation of a weak solvent-solute molecular complex. The heteronuclear indirect spin-spin coupling constants are determined. The sign of the two-bond J_PH is found to be positive.     

New optical methods to study director orientation in liquid crystals

Summary We report new optical methods useful to investigate the orientational order of nematic liquid crystals. The first one uses a linear optical technique and a variable-thickness cell to get a precise measurement of the anchoring energies at the boundaries. The second one exploits the nonlinear self-phase modulation to evaluate the elastic anisotropy of a nematic liquid crystal. Examples are reported of measurements performed on hybrid aligned liquid crystals. Also with GNSM and CISM, Unità di Cosenza.     

The formation of biaxial nematic phases in binary mixtures of thermotropic liquid-crystals composed of uniaxial molecules

ABSTRACT

Monte Carlo simulations in the isothermal-isobaric ensemble are used to investigate the formation of an ordered, biaxial nematic phase in a binary mixture of thermotropic liquid crystals. The orientational dependence of the interaction between molecules of each pure component is the same as in the well-known Maier-Saupe model; each pure component of the mixture is therefore capable of forming a uniaxial nematic phase. For the interaction between molecules of different components, we use the same Maier-Saupe model but change the sign of the coupling constant. As a consequence a T-shaped arrangement of these molecules is energetically favoured. The formation of the biaxial phase occurs in two steps. At higher temperatures T, one of the components forms a uniaxial nematic phase whereas the other is in a quasi two-dimensional restricted isotropic liquid state. We develop a simple theoretical model to understand the high degree of (ostensible) nematic order in the latter. At lower T, the second component becomes nematic and then the entire mixture of the two compounds has biaxial symmetry. The biaxial nematic phase does not demix into domains rich in molecules of one or the other species.     

Mean-Field Limit and Phase Transitions for Nematic Liquid Crystals in the Continuum

We discuss thermotropic nematic liquid crystals in the mean-field regime. In the first part of this article, we rigorously carry out the mean-field limit of a system of N rod-like particles as \(N\rightarrow \infty \), which yields an effective ‘one-body’ free energy functional. In the second part, we focus on spatially homogeneous systems, for which we study the associated Euler–Lagrange equation, with a focus on phase transitions for general axisymmetric potentials. We prove that the system is isotropic at high temperature, while anisotropic distributions appear through a transcritical bifurcation as the temperature is lowered. Finally, as the temperature goes to zero we also prove, in the concrete case of the Maier–Saupe potential, that the system converges to perfect nematic order.     

Solution-grown single crystals of random terpolymer liquid crystal polymers: Chain folding,morphology, and effect of annealing

Thin (100–150 Å thick) single crystals of large lateral dimensions have been grown from dilute solution in xylene of random terpolymer, thermotropic, liquid crystal polymers containing approximately equimolar amounts of C₆ or C₇ flexible segments, oxybenzoate, and dioxyphenyl. With both polymers having molecular lengths of 800 Å or longer, electron diffraction patterns indicate chain folding. The crystal structure, hexagonal, is less perfect than found previously for thin films of the C₇ (and C₅) polymer crystallized from the nematic state by slow cooling (orthorhombic). Annealing of the crystals below the crystal-liquid crystal transition results in merging of overgrowths and rough crystal edges into the main crystal and a surface roughening, followed, at longer times and/or higher temperatures, by lamella thickening. Annealing in the nematic state results in the development of rosettes of lamellae. Implications of the results for crystallization mechanisms and morphology of the nematic state are discussed.     

Anisotropic diffusion in a nematic liquid crystal- An electric field PFG NMR approach

The access to self-diffusion coefficients in anisotropic systems such as thermotropic liquid crystals by means of PFG NMR is complicated by strong dipolar interactions. Additionally, problems arise due to the immediate orientation of low-molar-mass nematic liquid crystals in an external field. The director orientation can be changed by the application of an additional electric field. This can be exploited in order to reduce the dipolar interaction to such an extent that the NMR linewidths change from a solid-state to a liquid-like situation enabling PFG NMR experiments.     

Numerical study of deformations induced by ac electric field in insulating flexoelectric nematic layers

The influence of the frequency f of applied ac electric field on the time dependence of electric field induced deformations of homeotropic nematic layers is studied numerically. Three kinds of nematic liquid crystals were considered:

Elastic energy-driven phase separation of phospholipid monolayers at the nematic liquid-crystal-aqueous interface

Experimental measurements and a thermodynamic model reveal that nematic elasticity can induce lateral phase separation of amphiphilic molecules assembled at interfaces between thermotropic liquid crystals (LCs) and immiscible aqueous phases. The morphologies of the phase-separated domains of amphiphiles induced by nematic elasticity are shown to be strongly dependent on the nature of the deformation of the LC. This study provides important insight into the physics that controls the ordering of molecules at interfaces of soft anisotropic materials, and identifies a new mechanism of phase separation at these interfaces.     

Localized electromagnetic modes and the transmission spectrum of a one-dimensional photonic crystal with lattice defects

The properties of localized electromagnetic modes in a one-dimensional photonic crystal with a structural defect layer were studied. The role of the defect was played by an anisotropic nematic liquid crystal layer. The frequency and the damping factor of defect modes were shown to substantially depend on the defect layer thickness and the orientation of the optical axis of the nematic. The transmission spectra of photonic crystals with one and two lattice defects were studied. Taking into account the special feature of nematic liquid crystals distinguishing them from usual crystals, namely, large permittivity anisotropy, it was shown that the transmission spectrum of the photonic crystal could be controlled by varying the orientation of the optical axis of the nematic, for instance, under the action of an external electric field.     

Dynamic light scattering study of biaxial ordering in a thermotropic liquid crystal

Dynamic light scattering from orientational order fluctuations in a liquid crystalline tetrapode reveals successive, weakly first-order isotropic to uniaxial and uniaxial to biaxial nematic phase transitions. The order parameter relaxation rates exhibit temperature dependences consistent with Landau-de Gennes mean field theory. Combined with previous evidence of a second-order uniaxial-biaxial transition in a closely related tetrapode, the present study supports the existence of a nematic-nematic tricritical point in thermotropic liquid crystals.