Cybotactic nematic phases of photoisomerisable hockey-stick liquid crystals

New five-ring hockey-stick liquid crystalline materials with 4-bromoresorcinol as the central core unit and an azobenzene-based side arm were synthesised and their mesophase behaviour was investigated by polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and under a triangular wave electric field. Additional structural modification was done by introducing a lateral fluorine atom in the terminal ring of one of the side arms. It is found that regardless of the alkyl chain length or the lateral fluorine substitution, all of the prepared materials are liquid crystalline exhibiting nematic phases composed of cybotactic clusters of the SmC-type (N_CybC) in addition to a monotropic SmC phase for the longest homologue.     

H-shaped liquid crystals inducing nematic order in the isotropic liquid

ABSTRACT

We prepared a homologous series of H-shaped liquid crystals I-n and investigated their phase transition properties using optical microscopy and differential scanning calorimetry. All the compounds exhibited a nematic phase at room temperature. The phase transition behaviour is explained in terms of molecular shape anisotropy. Furthermore, those compounds were found to exhibit electro-optical switching in the isotropic liquid in the vicinity of the nematic–isotropic liquid transition, indicating that the microscopic nematic order with a certain coherence length of the molecules exists in the optically isotropic temperature range.     

Colloidal particles as elastic triads in nematic liquid crystals

ABSTRACT

In this short review we summarise already published results to manifest very important role of high order elastic terms in the formation of colloidal structures in nematic liquid crystals (NLC). We reveal that every colloidal particle in nematics can be effectively represented as a triad of nonzero elastic moments. Usually colloidal particles in NLCs are treated with their elastic dipole and/or quadrupole moments only. But we demonstrate that octupole, hexadecapole and even 64-pole moments play an important role as well and determine parameters of different 1D, 2D and even 3D colloidal crystals in NLCs. In general the triad of the first three nonzero elastic moments can describe almost all colloidal structures observed so far. Dipole particles should be considered as hard spheroids with a triad of the dipole, quadrupole and octupole moments. Quadrupole particles should be treated as hard spheres with a triad of quadrupole, hexadecapole and 64-pole elastic moments

PACS numbers: 61.30.Dk, 82.70.Dd, 64.70.M?     

Effect of liquid oils on the properties of multiple emulsions containing liquid crystals

Recently, many cosmetic researchers have been focused on multiple emulsions due to better performance. Limited application of multiple emulsions has been attributed to their instability, which can be resolved by the presence of liquid crystals. Multiple emulsions containing liquid crystals are affected by various formulation parameters, such as liquid oils. In this paper, the influence of liquid oils on the formation mechanism was studied. Besides, stability, small-angle x-ray scattering (SAXS) spectra analysis, and rheological analysis of the emulsions were investigated as well. The results showed that when the gap of the polarity between inner oils and external liquid oils is greater, the multiple structures were more easily formed. Multiple emulsions containing liquid crystals were superior in stability to multiple emulsions prepared in the same way with liquid oils that did not form liquid crystals. SAXS indicated that the liquid crystal orientation was lamellar. Rheological analysis indicated that the different structure emulsions showed shear-thinning behavior. The presence of liquid crystal decreased the viscosity and resulted in pseudoplastic enhancement. Both the storage modulus (G′) and the loss modulus (G″) of multiple emulsions were slightly higher than those of O/W-type emulsions, implying the existence of multiple structures.     

Highly birefringent nematic and chiral nematic liquid crystals

We report a simple interference method to determine the dispersion of the extraordinary refractive index and birefringence of highly conjugated and coloured nematic liquid crystals used as light‐emitting materials in organic electroluminescent devices. The measurements are made in the nematic glass phase at room temperature. The birefringence is highly dispersive and values up to 1.1 are obtained. Chiral groups are incorporated into the end chains giving a chiral nematic liquid crystal with a very wide stopband in the visible region. The Berreman matrix method is used to simulate transmission through the chiral nematic liquid crystal cell using the refractive index parameters obtained experimentally. Excellent agreement between theory and experiment is found.     

On the determination of order parameters for homogeneous and twisted nematic liquid crystals from Raman spectroscopy

Traditional approaches to the use of Raman spectroscopy as an aid to the determination of local order parameters in liquid crystalline materials have employed polarizations of the excitation source and/or the analyser which are orthogonal to the liquid crystalline director. The present paper describes a Raman study, which seeks to take advantage of the additional information available from examining the complete range of orientations of the director in relation to these polarization directions. A theory is developed which shows how it is possible to use this additional information to derive more reliable values of the P₂ and P₄ local order parameters in homogeneous and twisted nematic liquid crystal cells.     

Simulation of texture evolution for nematic liquid crystalline polymers under shear flow

The development of microstructure in nematic liquid crystalline polymers under shear flow is investigated through computational simulation. By using a tensorial expression for the elastic torque, the nemato-dynamic equation is numerically resolved. The simulation shows that elastic anisotropy has a strong influence on the evolution of the director and that the ‘log-rolling’ orientation of the directors emerges for tumbling nematics if the twist constant is smaller than the splay and the bend constants, even though one starts from a structure in which the directors are aligned within the velocity and velocity gradient plane. The interaction of wedge disclination pairs subject to a shear flow field is also simulated. The generation, multiplication and interaction of inversion wall defects during shearing have been revealed. In general the wall moves to the boundaries and is absorbed by the boundaries. When two walls of opposite orientation meet, a loop may form, then shrink, and finally collapse. Correspondingly, if they have the same orientation, commutation will occur.     

Free residual DC voltage for nematic liquid crystals on solution-derived lanthanum tin oxide film

We present the liquid crystal (LC) alignment properties of solution-derived lanthanum tin oxide (LaSnO) films cured at various temperatures and exposed to ion-beam (IB) irradiation. Using a solution process, LaSnO films were deposited on the indium-tin-oxide glass substrates and IB irradiation was used as an alignment method. Homogeneous and uniform LC alignment was achieved and observed by cross-polarised optical microscopy. Pre-tilt angle results with low standard deviation supported the notion of uniform LC alignment. The LaSnO film cured at 300°C showed nearly zero capacitance–voltage hysteresis. The change of the surface morphology of the LaSnO film due to IB irradiation was observed by atomic force microscopy. The effects of IB irradiation on the LC alignment layer were further demonstrated by X-ray photoelectron spectroscopy. The strong IB irradiation broke the metal–oxide bonds present, which in turn induced an increased number of oxygen vacancies on the whole surface. Uniform LC alignment was attributed to surface reformation and van der Waals forces.     

Variety of mesophases in compounds with an increasing number of lactate units in the chiral chain

Liquid-crystalline compounds with different numbers of lactate units, n, in the chiral part were synthesised and mesomorphic properties studied. Physical properties were compared with respect to n. In the compound with one lactate unit in the chiral part the TGBA–TGBC–SmC* phase sequence was detected. For two lactate units the antiferroelectric SmC*_A phase occurs. Finally, three-lactate material exhibits the tilted hexatic SmI*(F*) phase below the ferroelectric SmC* phase. Dielectric spectroscopy and spontaneous tilt and polarisation were measured. For the three-lactate compound the temperature dependences were analysed in the vicinity of the SmC*–hexatic phase transition, and these properties compared with the theoretically predicted behaviour.     

Curvature and defects in nematic liquid crystals

ABSTRACT

The use of nematic liquid crystals for directed assembly of particles and for the creation of multistable systems depends on the ability to control the topological defects and the distortions of the director field. These are not only driven by topological constraints and by anchoring energies but also by the curvature field created by the bounding surfaces. This review explores the interaction between defects, topology, inclusions and curvature in nematics. I will introduce the relationship between curvature and the Frank elastic energy in nematics, and then I will give an overview of specific examples that show how this coupling can create unexpected behaviours, such as lock-and-key interactions, anchoring transitions on curved surfaces and memory effects.     

Light-induced hydrodynamic reorientation of hybrid aligned nematic liquid crystals caused by direct volume expansion

The dynamics of the direct volume expansion mechanism of light-induced hydrodynamic motions in hybrid-oriented nematic liquid crystal (NLC) have been studied experimentally. It was shown that heating caused by the absorption of a laser beam results in expansion of a NLC volume and induces hydrodynamic flow in a planar capillary. The hydrodynamic flow reorients the NLC molecules and thus the optical properties of the NLC layer are changing. A change of the tilt direction of the NLC director is demonstrated experimentally, and it is shown that hybrid-oriented NLC could be considered as ‘flexible ribbon’. Velocity gradient brings about an increase of curvature when hydrodynamic flow velocity is directed out of the ‘flexible ribbon’s’ curvature. The ‘flexible ribbon’ reverses its curvature when velocity is directed into ‘flexible ribbon’s’ curvature.     

Synthesis of novel nematic liquid crystals containing 3,3'-dimethyl-2,2'-bipyridyl

Liquid-crystalline 3,3′-dimethyl-2,2′-bipyridyl derivatives with long 4-(alkoxyphenyl)ethynyl (-C≡C-C₆H₄-OR) groups in the 5,5′-positions were synthesized by palladium-catalysed crosscoupling reactions. The compounds exhibit exclusively nematic behaviour; for example, the hexyl derivative showed a nematic phase over the temperature range 145.2–205.0°C. On increasing the length of the terminal chain, the transition temperatures were lowered; for example, the hexadecyl derivative was nematic in the range 117.0–126.8°C.     

Theory of nematic–smectic phase separation in thin twisted liquid crystal cells

Recently it has been shown experimentally by the authors that a highly twisted thin nematic cell at low temperatures can separate into a smectic A region in the middle of the cell surrounded by twisted nematic layers at the boundaries. In this case the twist is expelled into the nematic layers and the nematic–smectic A transition temperature is strongly depressed. We present a thermodynamic theory of such a phase transition in a twisted nematic cell, taking into account that the smectic A slab inside the nematic cell can be stable only if the decrease of free energy in the smectic region overcomes the increase in distortion energy of the twist deformation in the nematic layers plus the energy of the nematic–smectic A interface. In such a system the equilibrium thickness of the smectic A slab corresponds to the minimum of the total free energy of the whole cell, which includes all the bulk and surface contributions. Existing experimental data are at least qualitatively explained by the results of the present theory. This opens a unique possibility to study the properties of the nematic–smectic interface which is perpendicular to the smectic layers.     

Random lasing in unbounded dye-doped nematic liquid crystals

Random lasing in dye-doped nematic liquid crystals (NLCs) contained in a quartz cuvette was studied. With the pumping energy rising, random lasing with nonresonant feedback and resonant feedback emerge successively with the lasing threshold of 20 and 40 μJ, respectively. The lasing properties including fluctuation of the emission spectrum, divergence angle of emission, independence of the emission on the polarisation of the pump beam and the depolarisation of emission are distinct from those of dye-doped nematics confined in the sandwich structure cell or the capillary tube. The distinctions are associated with the thermal fluctuation of dielectric tensor since there is negligible surface anchoring for the nematics in the pump volume. This indicates that the anchoring state of NLCs is an important factor determining the random lasing properties.     

Columnar and smectic liquid crystals based on crown ethers

Unsymmetrical benzo[15]crown-5 ethers 5 with one lateral ortho-terphenyl unit bearing alkoxy side chains of varying chain lengths (C5-C14) were prepared from 3,4-dialkoxyphenylbromides 2. Complexation with metal salts MX (M = Na, Cs) afforded the corresponding derivatives MX5. The uncomplexed crown ethers 5 h and 5 i, with dodecyloxy and tetradecyloxy side chains, respectively, exhibit liquid crystalline properties. In the series of complexed crown ethers, liquid crystal properties appeared as early as NaI5 f with C9H19 side chains. Whereas the uncomplexed 5 h,i form smectic mesophases, the complexed NaI5 g and NaI5 h exhibit textures typical of columnar mesophases. These results were supported by X-ray diffraction measurements (WAXS, SAXS), which revealed smectic (5 h,i), rectangular columnar (NaI5 g), and hexagonal columnar (NaI5 h) mesophases. As the liquid crystalline phase might retain packing features of the solid-state structure, single-crystal X-ray analyses were also performed for some of the uncomplexed and complexed crown ether derivatives. The complex NaI(3)5 a displays a sandwich-type structure, with the crown ether cores mutually antiperiplanar and maintaining an almost perfect crown conformation. In contrast, non-mesogenic uncomplexed crown ether 5 b displays a layer-type ordering in the solid phase.     

Alignment of a nematic liquid crystal using substituted calixarene Langmuir-Blodgett films

The alignment of a nematic liquid crystal (5CB) induced by several substituted calixarene-based films is reported. Calixarene molecules consisting of four or six moieties and different substituents (acyl and azobenzene groups) were synthesized. Films of such molecules were deposited using a Langmuir-Blodgett technique onto glass plates and were characterized using atomic force microscopy. These treated plates were used to prepare liquid crystal cells, and the overall alignment studied. In the case of photosensitive molecules, photoinduced reorientation experiments were undertaken and are reported. It is shown that it is not important to have a large number of interacting sites on the surface to induce a reorientation of the liquid crystal.     

Orientation and anchoring effects in stretched polymer dispersed nematic liquid crystals

The induction of liquid crystal orientation through mechanical stretching was investigated for polymer dispersed liquid crystals (PDLCs) by means of infrared dichroism. Using a nematic liquid crystal BL006 and polyacrylic acid as the polymer matrix, it was possible to stretch the PDLC films with BL006 in either the isotropic or the nematic phase. After cooling the films under strain to room temperature, the molecular orientation of BL006 was found to be much higher for films that contained isotropic liquid droplets of BL006 at the time of stretching than for films that had nematic droplets. Stretching PDLC films with isotropic droplets results in no molecular orientation, but the orientation is induced during the subsequent cooling when BL006 goes through the isotropic-to-nematic phase transition. Interestingly for PAA/BL006, the nematic director orients along the long axes of the elongated droplets despite liquid crystal anchoring perpendicular to the polymer interface.