Electrical properties of liquid crystal nano-colloids analysed from perspectives of the ionic purity of nano-dopants

The concentration of mobile ions in liquid crystals doped with nano-objects is analysed in the framework of the Langmuir isotherms assuming an ionic contamination of nano-dopants. The level of the ionic purity of nano-dopants is described by means of the dimensionless contamination factor. The applicability of the proposed approach is verified by fitting the broad variety of the existing experimental data. A good agreement between theoretical predictions and experimental data indicates the feasibility of the idea to consider nano-dopants partially contaminated. In addition, it provides the way to deduce a set of important parameters (the surface density of the adsorbing sites, the contamination factor and the ratio of the adsorption constant to the desorption constant) directly from electrical measurements.     

Impact of co-doping concentration in copolymer network liquid crystals

ABSTRACT

The impact of varying the co-doping concentration of a mesogenic and a non-mesogenic monomer in the reactive mixtures used to create a copolymer network LCs was investigated. Use of copolymer has been found to improve the response properties in the obtained liquid crystal composites. The polymer network in the studied copolymer network LCs was examined by scanning electron microscopy and the response times in various samples were investigated. Samples were prepared with various reactive mixtures, each of which had a constant concentration of mesogenic monomer, various concentrations of non-mesogenic monomer, and the same amount of photoinitiator. These reactive mixtures were filled in home assembled test cells with planar alignment and then exposed to UV light. With increasing concentration of the non-mesogenic monomer, the response properties of the resulting copolymer network LC were improved. Usually, if the overall polymer content in a polymer network LC is increased, the threshold voltage is also increased. However, both threshold voltages and response times were lowered and the response properties were thus improved in the studied copolymer network LCs. This unexpected behavior could be traced back to inducing a grainy polymer morphology of the copolymer network by using a non-mesogenic monomer.     

Impact of silica nanoparticles dispersion on the dielectric and electro-optical properties and absorption spectra of host ferroelectric liquid crystal

The present work concerns with the investigation of the effect of dispersion of Silica (SiO₂) nanoparticles (NPs) in host ferroelectric liquid crystal (FLC) KCFLC10S on the dielectric and electro-optical properties and ultraviolet-visible (UV-VIS) absorption spectra of the pristine and dispersed systems. We have found that the dispersion of SiO₂ NPs in the host FLC strongly influences the various properties of dispersed systems. No evidence of aggregates and clumps in the dispersed system has been observed. Due to SiO₂ NPs dispersion, a rapid decrease in dielectric permittivity ε’, increase in conductivity σ with frequency, increase in spontaneous polarisation P_s and decrease in switching time with bias voltage have been observed. Based on the absorption spectra, we have also made an attempt to link the electro-optical and dielectric response with the mechanism of FLC–NPs interactions.     

Ion transport in polymerized lyotropic liquid crystals containing ionic liquid

In this work, we investigate the effect of morphology and segmental dynamics on ion transport in polymerized lyotropic liquid crystals (polyLLCs) containing 1-butyl-3-methylimidazolium tetrafluoroborate as ionic liquid (IL). We demonstrate that two important factors, which affect ion conduction in polyLLCs, are grain size and chain density at the interface. The polyLLC with large grain size (70 nm) shows significant reduction in ion conductivity (one order of magnitude) compared to its homopolymer/IL mixture. However, the polyLLC with small grain size (20 nm) has little difference in ion conductivity compared to its homopolymer/IL mixture. It is observed that decreasing the chain density enhances the interaction of IL with polymer chains and consequently slows the relaxation of polymer chains. In addition, comparing the dynamics of polymer chains in mixtures of homopolymer/IL and templated LLC mesophases shows that the confinement in LLC structure prolongs the relaxation of polymer chains.     

Electrooptic properties of liquid crystals filled with silica nanoparticles of different sorts

In this work we investigate electrooptic properties of nematic liquid crystal (LC) E7 from Merck filled with two types of silica nanoparticles (NPs). The particles of these types are of similar size and shape, however, they are made by different methods. The NPs of the first type, aerosil (A), are prepared by a high-temperature hydrolysis of chlorosilanes. The second type of NPs, based on hydrolysis and controlled precipitation of tetraethylorthosilicate in alcohol, yields monodispersed NP (MNPs) of silica. Transmittance versus applied voltage curves of the suspension layers are measured and analyzed. Our results show a strong dependence of the electrooptic properties on the particle preparation method. The contrast ratio (CR) 61:1 of LC-A suspension is achieved at relatively low A content (17 wt %). Unlike it, the value of the CR of LC-MNP suspensions is low (about 2:1) even at 30 wt % of MNPs in the mixture. Both types of suspensions show electrooptic memory. The maximum of the memory efficiency of LC-A suspensions is detected at 4 wt % of A, while for LC-MNP suspensions the maximum is achieved at 15 wt % of MNPs. The difference in the results for the LC-A and LC-MNP series of composites is caused by much stronger aggregation of MNPs compared with A in the LC matrix. Moreover, reactive particle fusion and formation of silica microcrystallites substantially enhances the effect caused by MNP aggregation. These processes deteriorating electrooptic performance may be stabilized by introduction of a polymer network in LC-MNP suspensions.     

Studies on relation between columnar order and electrical conductivity in HAT6 discotic liquid crystals using temperature-dependent Raman spectroscopy and DFT calculations

The vibrational property of 2,3,6,7,10,11-hexakis(hexyloxy)triphenylene (HAT6) discotic liquid crystal (DLC) material is investigated in this research by using temperature-dependent Raman spectroscopy technique. One-dimensional (1D) charge transport mechanism in the DLC molecules is enabled in the columnar liquid crystalline (D_h) phase. The result indicates a high core-to-core correlation in the liquid crystal columnar phase, which has a ‘memory’ like effect that extends into isotropic phase at femtosecond timescale. This correlation is also confirmed through electrical conductivity measurement of DLCs, in which the electrical conductivity is enhanced in the DLC phase. DFT simulation was also carried out in order to elucidate the basic properties of HAT6 such as the band gap in the light of Raman spectra. An interesting outcome is that a freely unspecified boundary model produces in a more flexible molecule, resulting in a reduced band gap. Thus, this work provides an understanding of relationship between columnar order and electrical conductivity of HAT6 molecule, and potential strategy for design of DLCs in electronics application.     

Synthesis and mesomorphic properties of fluoro and isothiocyanato biphenyl tolane liquid crystals

Four series of high birefringence biphenyl tolane liquid crystals having a terminal isothiocyanato or fluoro group were synthesized; their mesomorphic properties were studied by optical polarizing microscopy and DSC. These biphenyl tolane compounds exhibit reasonably low melting points and high birefringence of 0.37–0.49. By using these compounds a eutectic mixture was formulated exhibiting a wide nematic range, high figure‐of‐merit and low viscosity.     

Enhancement of the nematic order of polar liquid crystals in thin cells

Experimental observations show that the nematic order parameter (S) is significantly enhanced as the thickness of the cell is reduced. However, calculations based on earlier theories are not in good agreement with the experimental data. We earlier developed a molecular mean field model that assumes that the medium with polar molecules consists of inter-converting anti-parallel and parallel pairs, to explain the molecular origin of the ‘two lengths’ model. The model has been used to explain effects such as double re-entrance and the effect of electric field on the nematic–isotropic transition temperature, T _NI. We have recently extended the Maier–Saupe (M–S) theory using an empirical variation of surface potential, to account for the enhancement in which a molecule near the surface is assumed to feel the mean field potential (M–S type) and also the surface-induced potential. Variation in the density of the medium due to variation of S has been ignored. In the present paper, the change in the relative proportion of the parallel pairs due to changes in the density of the medium is included in the M–S theory with the surface potential. This results in improved agreement with the experimental data.     

Computer simulation of the homeotropic to planar transition in cholesteric liquid crystals

The transition from the homeotropic to the planar state in cholesteric liquid crystal displays is investigated through computer simulation. The simulation reproduces the observed relaxation from the homeotropic state to the long pitch transient planar state. The simulation also agrees with the suggestion that the transition from the transient planar state to the planar state proceeds through a bulk modulation resulting in folding and buckling of cholesteric layers without introduction of defect cores. The model obtained agrees well with earlier experimental observations showing that the process includes a tilting of cholesteric helices, and that the surface plays only a minor role in the relaxation process.     

The birefringence and extinction coefficient of positive and negative liquid crystals in the terahertz range

Birefringence and extinction coefficients of positive nematic liquid crystal (NLC) MLC-2142 and negative NLC BHR28000-400 are measured by terahertz time-domain spectroscopy system (THz-TDS). Frequency ranging from 0.1 to 0.6 THz, the birefringence of positive NLC MLC-2142 increases with the increase of frequency, and keeps larger than 0.23, which exhibits application potential in tunable broadband LC THz device where a large birefringence is required. In contrast, the birefringence of BHR28000-400 decreases with the increased frequency, which shows a completely different optical property from the positive NLC. The extinction coefficient of the above two kinds of liquid crystals are also investigated.     

Influence of transitional metal ions on lyotropic liquid crystals of hydroxyethyl cellulose acetate in N,N-dimethylformamide

The influence of inorganic salts on the formation of lyotropic liquid crystals of hydroxyethyl cellulose acetate (HECA) in N,N′dimethylformamide (DMF) was studied. In the presence of CaCl₂, an inorganic salt of a principal group metal, the solution of HECA/DMF/CaCl₂ was a biphasic system. The temperature of the transformation from the liquid crystalline phase to the isotropic one increased with adding CaCl₂ because local HECA concentration increases in the HECA/DMF phase. When CuCl₂ or CoCl₂, inorganic salts of transitional metals, was added, the solutions were monophasic systems and the complexes of HECA with Cu²⁺ or Co²⁺ were formed in solutions, which results in the increase of the temperature of the transfomation from the liquid crystalline phase to the isotropic one.     

Enhanced electro-optical properties of a nematic liquid crystals in presence of BaTiO3 nanoparticles

Composites of nematic liquid crystals (NLCs) and ferroelectric barium titanate (BaTiO₃) nanoparticles (NPs) have been prepared. The alignments of NPs in the host medium have been demonstrated. Effect of NPs doping on various display parameters of NLCs, namely, threshold voltage, dielectric anisotropy and splay elastic constant has been studied using electro-optical and dielectric studies. The nematic ordering of host supports alignment of NPs parallel to the director which consequently improves electro-optical parameters in the composite system. The dielectric and electro-optic properties of LC–NPs composites have been discussed in frame of conventional theories of NLCs.     

离子色谱法同时测定离子液体中的三氟乙酸根、氟硼酸根及卤素离子

采用离子色谱-直接电导检测法同时测定了离子液体中的三氟乙酸根(CF3COO~)、氟硼酸根(BF4~)及卤素离子(F~、Cl~、Br~)。实验采用Shim-pack IC-A3阴离子交换色谱柱,分别选用邻苯二甲酸氢钾、邻苯二甲酸+三(羟甲基)氨基甲烷、对羟基苯甲酸+三(羟甲基)氨基甲烷+硼酸为淋洗液,考察了淋洗液种类和浓度、乙腈浓度、色谱柱温度对分离测定三氟乙酸根、氟硼酸根及卤素离子的影响。确定的最佳色谱条件为: 以1.2 mmol/L邻苯二甲酸氢钾为淋洗液,柱温45 ℃,流速1.0 mL/min。在此条件下,可同时分离上述5种阴离子,且色谱峰形对称。所测阴离子的检出限(以信噪比为3计)为0.01～0.50 mg/L,保留时间和峰面积的相对标准偏差(n=5)分别不大于0.2%和1.2%。将方法应用于测定离子液体中的三氟乙酸根、氟硼酸根及卤素离子,加标回收率为98.0%～103.2%。该方法简单、准确、可靠,具有较好的实用性。     

Anomalies in the twist elastic behaviour of mixtures of calamitic and bent-core liquid crystals

ABSTRACT

The splay, twist and bend elastic constants (K₁₁, K₂₂ and K₃₃) have been measured as a function of temperature in bent-core/calamitic mixtures based on three different calamitic materials (5CB, 8CB and ZLI1132) and two bent-core dopants. The behaviour of the splay and bend constants are as expected; a reduction in K₃₃ of ~20%, in line with predictions from mixing rules and other observations. Interestingly, no change is seen in the splay constant, K₁₁ of the calamitic hosts. Surprisingly though, the twist elastic constant exhibits a reduction of 30 – 40% in all mixtures across the nematic range, an effect not previously reported and much larger than mixing rules can explain. The elastic behaviour is universal in our mixtures. We explain part of the reduction in the twist deformation by considering the influence of the chiral conformer fluctuations of the bent-core molecules on the twist elastic constants of the mixtures. However, the dramatic reduction can only be fully explained by also including contributions from chiral conformer fluctuations of the calamitic host, a form of chiral amplification.     

Magnetic anisotropy of liquid crystals based on lanthanide mesogenic complexes

The values of magnetic anisotropy of smectic A-phases for a number of lanthanide complexes (LH)₂LM(NO₃)₂, where M=Nd, Eu, Gd, Tb, Dy, Ho, and Er, and LH is a Schiff's base), were measured. These values are two orders of magnitude larger than those normally found for diamagnetic liquid crystals and are well correlated with magnetic birefringence constants and molecular mangetic anisotropy of nomesogenic lanthanide diketonates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 694–697, April, 1999.