Crystallisation of nematic liquid crystal mixtures

In this paper, we propose a method to accelerate the crystallisation of nematic liquid crystal mixtures based on crystallisation theory. This method is to hold a nematic liquid crystal sample at a temperature suitable for crystal growth after aging it at a temperature suitable for nucleation. After we specified these temperatures of a nematic liquid crystal mixture using differential scanning calorimetry, we demonstrate that the two-temperature aging method is effective for the crystallisation of other nematic liquid crystal mixtures in which the crystal-liquid crystal transition temperature has so far been undetectable.     

Optical reorientation in cholesteric nematic mixtures

Abstract

The optical Fréedericksz transition for linearly polarized light at normal incidence is studied in mixtures of nematic E7 and cholesteric C15 in cells coated for homeotropic alignment. The reorientation process is found to be dramatically different from the case of pure nematic samples showing the phenomenon of optical phase locking and large hysteresis. These effects are ascribed to the occurrence of self-induced stimulated light scattering, which does not occur in pure nematics.     

Rod-shaped dopants for flexoelectric nematic mixtures

We report the synthesis and liquid crystalline behaviour of two series of para-substituted terphenyls as dopants with a rigid rod-like shape, rather than a wedge-, pear- or banana-shape, for guest–host nematic mixtures with flexoelectric properties. One series of liquid crystalline dopants is of low-to-strongly negative dielectric anisotropy and the other is of low-to-strongly positive dielectric anisotropy. The usefulness of apolar and polar rod-like dopants as components of flexoelectric nematic mixtures of positive dielectric anisotropy for use in LCDs is investigated in general and the dependence of the flexoelectric properties of the doped nematic mixtures on the polarity of the dopants is studied in particular. The correlation between the concentration of the dopant and the magnitude of the flexoelastic ratio of several guest–host nematic mixtures is investigated.     

Creation of nematic and reentrant nematic phases in bi- and multi-component smectic mixtures

Abstract

Experimental results referring to the transformation of smectic phases, mainly smectic A, into nematic and reentrant nematic phases are reviewed. A new explanation of some experimental results is proposed. Factors which are responsible for the depression of smectic phases in mixtures of polar mesogens are discussed and the possibility of forming mixtures with a broad temperature range of nematic phase from smectic compounds, which can be useful for liquid crystal displays (LCDs), is shown. A nematic gap observed in some cases between monolayer (S_A1) or monolayer and partially bilayer (S_Ad) smectics results from the differences in the organization of the molecules in the smectic layers. It is concluded that polar phase from smectic A₁ phases can be divided into two groups: (a) the first one is characteristic for compounds with the -NCS, -F, -CI, -I or ?COC _m H_{2m + 1} terminal group. The spacing of the smectic layer slowly expands with the increase in alkyl chain length and the structure of the smectic A₁ phase slowly changes to be more like the smectic A_d phase (d/1 > 1). It is proposed that such a smectic is called an enhanced monolayer smectic (S_A1e (b) the second one is typical for compounds with the -CN terminal group. This kind of smectic A₁ phase is rapidly transformed into the smectic A_d phase with increasing alkyl chain length. These latter monolayer mesogens easily form the reentrant nematic phase when they are mixed with other polar smectic mesogens.     

Study of the nematic electroclinic effect in mixtures

The temperature dependence of the nematic electroclinic effect has been studied in binary mixtures prepared from two chiral compounds with nematic-smectic A-smectic C and nematic-smectic C phase sequences. The data obtained show a substantial difference in the magnitude of the effect, not only with the type of phase sequence, but also with the temperature range of the subsequent smectic A phase. These results suggest that short-range smectic fluctuations can play an important role in the nematic electroclinic effect at least when a smectic C phase is close to the nematic. In addition, the dynamic behaviour of the electroclinic effect has been investigated in the compound with the nematic-smectic A transition. As in previous work, an anomaly in the electroclinic response time has been found around the nematic-smectic A transition. This fact is analysed qualitatively assuming two different mechanisms contributing to the electroclinic effect.     

Visco-elastic properties of reentrant nematic liquid crystalline mixtures

The visco-elastic properties for binary mixtures of 4-n -hexyloxy-4′-cyanobiphenyl (6OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0–29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems.     

Viscosity of nematic mixtures: A free-volume approach

Abstract

The five Leslie viscosities for a mixture of two nematic materials are computed as functions of the temperature, composition and order parameter. It is shown that, for a nematic mixture of A and B, the equations describing the composition and temperature behaviour of the Leslie viscosities have the same form as those for the pure components, provided that composition-averaged values of the parameters are used. For the case where the free volume is additive, the relaxation times for the mixtures can be directly expressed as functions of the parameters for the pure components. These results are compared with the experimental data on λ₁ for MBBA/EBBA mixtures, and fairly good agreement is found.     

Visco-elastic properties of reentrant nematic liquid crystalline mixtures

The visco-elastic properties for binary mixtures of 4- n -hexyloxy-4'-cyanobiphenyl (6OCB) and 4- n -octyloxy-4'-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0-29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems.     

Banana‐shaped dopants for flexoelectric nematic mixtures

The synthesis is reported of new meta‐substituted quaterphenyls and several related dimers as dopants for nematic mixtures with flexoelectric properties. The number and nature of the terminal substituents is varied from apolar with a small dipole moment to polar with a strong dipole moment. The number of methylene units in the flexible aliphatic spacer between the polyfluorinated aromatic groups of the dimers is also varied. Dimers capable of banana‐shaped conformers induce an increase in the flexoelectric coefficients of mixtures containing them and reduce the clearing point to a small extent.     

Orientational order and refractive indices in binary nematic mixtures

Mean field theory is used to calculate the temperature-composition phase diagram and component order parameters of binary nematic mixtures. Experimental values for the mixture order parameter of a binary nematic mixture close to the nematic/isotropic transition have been obtained from refractive index measurements. The experimental results qualitatively confirm the predictions of the theory.     

Dielectric studies of smectogenic dioxane mixtures revealing a nematic gap

The results of dielectric studies of two bi-component mixtures of well separated members (fourth and twelfth) of the series of 5-n-alkyl-2-(4-isothiocyanatophenyl)-1,3-dioxanes (nDBTs) are presented. Pure nDBTs exhibit the smectic A phase only, whereas the mixtures of well separated members of the series create a nematic gap. It was found that molecular rotations around the short axes are hindered by a lower activation barrier in the smectic A than in the nematic phase of the mixture, similarly to the situation for many pure substances with the same phase sequence. In the case of the large concentration of the longer component, a crystalline phase is created in which the short component performs uniaxial rotations in cages formed by the long molecules of the second component.     

Photochemical behavior of lanthanide-containing polymer materials

Light-transforming polymer materials activated by compositions based on the mixed-ligand europium carboxylates and anthranilic acid exhibiting an intense luminescence in the spectral region 400–700 nm are prepared. The photolysis of the polymer materials is investigated. For the obtained compositions the flaring of intensity of luminescence of europium ion and anthranilic acid was detected.     

High birefringence and high resistivity isothiocyanate-based nematic liquid crystal mixtures

The molecular structures and physical properties of several single- and double-fluorinated isothiocyanatotolane, isothiocyanatocyclohexyltolane, and isothiocyanatoterphenyl compounds are reported. Two eutectic mixtures comprising these compounds are formulated and their properties evaluated. These mixtures exhibit a high birefringence, relatively low viscosity, high resistivity, and good photo and thermal stabilities. Potential applications of these mixtures for spatial light modulators, optical phased arrays, and high speed photonics are discussed.     

Electro-optic behaviour of a non-polar nematic liquid crystal and its mixtures

In this work we report preliminary results on the properties of a non-polar bicyclohexane nematic liquid crystal. Moreover, its binary mixtures both with a low viscosity phenylcyclohexane and with a normal polar nematic liquid have been investigated. The elastic, viscous and electro-optical properties of these compounds are presented. The non-polar compound, and its mixture with a low percentage of the well known liquid crystal MBBA, exhibit an electrohydrodynamic behaviour in which the conducting regime is absent, while the dielectric regime spreads to low frequencies. Additionally, at higher frequencies of the applied electric field, a regime whose thresholds are linear in frequency is observed. On the other hand, the mixture formed by 50 wt % of the non-polar compound with MBBA exhibits at low frequencies the usual behaviour, followed at higher frequencies by the linear regime.     

Blue phase stability of n-OCB homologue chiral nematic liquid crystal mixtures

Blue phase (BP) stability of a chiral nematic liquid crystal (LC) mixture is dependent upon chemical structure as well as physical properties. In this study, the blue phase temperature range dependent on alkyl chain length was investigated in order to evaluate the relationship between blue phase stability and the molecular structures of four kinds of 4-n-alkyloxy-4'-cyanobiphenyl (n-OCB) homologue chiral nematic LC mixtures composed of rod-like nematic LCs. It was confirmed that the blue phase temperature range was strongly dependent upon the molecular parity, K ₃₃/K ₁₁ and the helical twist power of the n-OCB homologues chiral nematic LC mixtures.     

Electro-optic behaviour of a non-polar nematic liquid crystal and its mixtures

In this work we report preliminary results on the properties of a non-polar bicyclohexane nematic liquid crystal. Moreover, its binary mixtures both with a low viscosity phenylcyclohexane and with a normal polar nematic liquid have been investigated. The elastic, viscous and electro-optical properties of these compounds are presented. The non-polar compound, and its mixture with a low percentage of the well known liquid crystal MBBA, exhibit an electrohydrodynamic behaviour in which the conducting regime is absent, while the dielectric regime spreads to low frequencies. Additionally, at higher frequencies of the applied electric field, a regime whose thresholds are linear in frequency is observed. On the other hand, the mixture formed by 50 wt % of the non-polar compound with MBBA exhibits at low frequencies the usual behaviour, followed at higher frequencies by the linear regime.     

Dielectric studies on binary mixtures of systems exhibiting intermediate nematic phase

Two binary phase diagrams of the liquid crystals (4-n-pentylphenyl-4-n-hexyloxybenzoate (PPHB) with 4-nitrophenyl-4-n-pentylbenzoate (NPPB) and 4-n-hexyloxyphenyl-4-n-decyloxybenzoate (HPDB) with NPPB) have been studied. PPHB shows only a nematic phase where as for HPDB trimorphism, with the SmC, SmA and nematic phases, was observed. Substance NPPB which has a strong polar nitro group is non-mesogenic one. Both the phase diagrams show an induction and stabilization of SmA phase and appearance of the nematic state in the high concentration range of polar component. The dielectric measurements confirm the phase transition temperatures and show changes in the short range interaction at the phase transitions.     

Viscoelastic properties of dilute nematic mixtures containing cyclic and hyperbranched liquid crystal polymers dissolved in a nematic solvent

The twist and bend viscosities of dilute solutions of cyclic and hyperbranched liquid crystal polymers (LCP) dissolved in low molar mass nematic solvents were determined via dynamic light scattering analysis. These results were compared to those of linear chains with similar chemical repeat structures. The nematic solvent used was 4′-pentyloxy-4-cyanobiphenyl (50CB). The cyclic LCP oligomers, Cy TPB10, have a mesogenic group, 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl) butane, separated by flexible decamethylene spacers. The twist viscosity of the cyclic Cy-TPB10 oligomers increases with molecular weight more strongly than the linear, TPB-10, suggesting that the hydrodynamic behavior of Cy-TPB10 is closer to that of a rigid rod than TPB10. Surprisingly, the intrinsic bend viscosity [η_bend] of Cy-TPB10 decreases with molecular weight, in contrast to the positive dependence for linear TPB10. This may reflect the higher strain energy in the smaller ring sizes. The hyperbranched LCP, TPD-b-8, is also based on the mesogen 10-bromo-1-(4-hydroxy-4′-biphenyl)-2(4-hydroxyphenyl) decane but with octyl groups at the chain ends. We compare the viscoelastic behavior of dilute nematic solutions of TPD-b-8 in 50CB against that of a linear main-chain LCP, TPB7, with the same mesogenic group but with heptamethylene spacers. The viscometric properties of TPD-b-8/50CB and TPB7/50CB are quite different. The results suggest that each chain is prolate (i. e., R_∥ > R_⊥) but that TPD-b-8 has a smaller chain anisotropy than that of TPB7. © 1995 John Wiley & Sons, Inc.