Investigations of dual-frequency nematic liquid crystals doped with dichroic dye

In this work, we studied and analysed a particular variety of liquid crystals, the so-called dual-frequency nematic liquid crystals (DFNLCs). The interest was to perform dielectric spectroscopy and optical characterisation with two pure and doped mixtures of DFNLCs. By means the dielectric spectroscopy we observed a low value of crossover frequency at room temperature for one dye doped mixture. Additionally, in the spectra studies, a scattering of light at cross-frequency, and a stable and unstable focal conical state was observed, respectively, for the investigated mixtures.     

Dielectric behaviour of binary dual-frequency nematics with low crossover frequencies

Binary dual-frequency nematic liquid crystals synthesised at the Military University of Technology were measured by dielectric means. All the investigated materials exhibit low crossover frequency. They were composed of only two molecules with longitudinal and transverse dipole moments. The main difference is the molecular weight of the molecules. Results of relaxation parameters of detected mode and crossover frequency are shown. The influence of structure on ion conductivity is discussed. The broad phase transition from an isotropic phase to a nematic one was observed.     

Ultrafast switchable wide angle negative refraction in novel dual-frequency liquid crystal mixture

Ultrafast switchable wide angle negative refraction in a novel dual-frequency liquid crystal mixture is demonstrated experimentally. Laterally fluorinated isothiocyanato phenyl-tolane liquid crystal compound is doped into Merck MLC-2048 to acquire the high birefringence dual-frequency liquid crystal. The maximum negative refraction angle achieved is about 12° and the switching time is only 25 ms for a 40-μm cell which is two orders faster than switchable negative refraction achieved before in nematic liquid crystals. Such properties provide a feasible approach to design negative refraction devices based on liquid crystals.     

Ethylenedioxythiophene as a novel central unit for bent-core liquid crystals

We have discovered that ethylenedioxythiophene (EDOT) can be used as a central unit for the synthesis of bent-core liquid crystals (BC LCs). Two series of EDOT-based BC LCs are prepared via Sonogashira coupling reaction. The mesophase behaviour of all the compounds was characterised using a combination of polarising optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. EDOT-based three-ring compounds were found to be nonliquid crystalline, while all the four derivatives of five-ring series, including a branched alkoxy chain derivative, display enantiotropic nematic phase over wide temperature range. The bent angle of these compounds is about 153°, which falls in between typical rod-like and banana liquid crystals. The transition temperature of branched alkoxy chain compound is lower than straight alkoxy chain compounds. The detailed XRD investigations of all the mesogens corroborate the presence of nematic phase.     

A direct assessment of refractive indices of nematic liquid crystals at broad VIS - MWIR range

We developed an interference method for determination refractive indices of nematic liquid crystals in a broad electromagnetic spectrum. Values of ordinary and extraordinary refractive indices were measured in VIS (from 0.4 to 0.8 μm), NIR (from 0.8 to 1.4 μm), SWIR (from 1.4 to 3.0 μm) and at an edge of MWIR (from 3.0 to 4.2 μm) regions. The main task of this work was to develop the efficient and accurate interference method. The absolute error of these measurements is not higher than 0.02. The method was tested on two newly designed mixtures. The first one was a high birefringence liquid crystal mixture for the laser rangefinder, while the second one is intentionally prepared for breathalyser application. The mixture does not possess high absorption bands at 3.4 μm. To measure a dispersion of the refractive indices cells with various thicknesses and dielectric mirrors were prepared. The paper presents a theoretical discussion and experimental results.     

Highly fluorinated liquid crystals with wide nematic phase interval and good solubility

A series of new liquid crystal compounds with both ethylene and difluoromethyleneoxy linking groups have been synthesised and their physical properties were measured. The compounds exhibit lower melting points and broader nematic mesophase temperature range than that of corresponding four-rings compound. Their anisotropic properties are Δε of about 25 and Δn of 0.135. The investigation shows that their solubilities are much better than that of reference compound. A mixture made by equivalent mass ratio of the compounds with side chain of ethyl, propyl and pentyl is found to keep nematic phase from 12°C°C to 109°C, which is rarely observed in highly fluorinated liquid crystals.     

Liquid crystal composites with a high percentage of gold nanoparticles

We have reported in our previous work that doping low concentrations (up to 10% by weight) of gold nanoparticles (GNP) in a polar nematic 4’-hexyl-4-biphenylcarbonitrile (HBPCN) increases the dielectric anisotropy, while the switching voltage and times, and the nematic–isotropic liquid (IL) transition point of the mixtures are not affected by doped nanoparticles. In the current work we extend our study of the behaviour of HBPCN doped with higher than 10% GNP. We show that at certain gold concentrations – 35% and 45% – the nematic–IL phase transition point increases by 15°C in comparison with the pure nematic value. At the same concentrations the dielectric anisotropy increases from its value for the pure nematic by about 2.2 times for 35% and twice for 45%. Also, the threshold voltage increases by 0.2 V for 35% and decreases by 0.15 V for 45%. However, the switching-off times decrease for both concentrations: 7 ms for 35% and 12 ms for 45%. We propose that the described effects of doped GNP on the properties of the nematic are due to the formation of different kinds of aggregations between two components of the mixtures.     

Nematic nanocomposites with enhanced optical birefringence

The proper performance of electro-optical devices utilising liquid crystals (LCs) requires materials with high diffraction efficiency, i.e. with high optical/dielectric anisotropy, low threshold voltage and fast switching. One can achieve increase of dielectric anisotropy by using chemical synthesis or mixing LC materials. However, in most cases, this causes an increase in the threshold voltage and switching times. Therefore obtaining materials with high dielectric anisotropy and keeping threshold voltage and switching times low is a challenging task. We achieved promising results by making binary mixtures of a polar nematic LC 4'-hexyl-4-biphenylcarbonitrile (HBPCN) with low percentage (1–10% by weight) gold nanoparticles. We report that for the mixtures with 1% and 2% gold the dielectric anisotropy increases by 100% and the birefringence by about 50% of their values for pure nematic. We also report that the increase of the dielectric anisotropy in the mixtures only slightly affects threshold voltage and switching times. We propose that this increase is caused by cluster formation in the mixtures.     

Synthesis,mesogenic and dielectric properties of fluorosubstituted isothiocyanatoterphenyls

The synthesis, mesomorphic and physical properties of 14 homologous series of laterally fluorinated 4?-alkyl-4-isothiocyanatoterphenyls were described. Influence of the number of fluorine atoms and their position in the terphenyl core on the phase transition temperatures, nematic range, dielectric and optic anisotropy as well as bulk viscosity were discussed. The compounds with the most optimal properties for formulation of nematic mixtures were selected, and mixture examples with low viscosity and medium or high birefringence were presented.     

Synthesis and properties of new non-symmetric 2,5-bis(4-alkylphenylethynyl)thiophenes

The synthesis and characterisation of new non-symmetric 2,5-bis(4-alkylphenylethynyl)thiophenes are described. Phase transition properties of these non-symmetric homologues are compared to those of the corresponding symmetric analogues. Furthermore, optical, dielectric and elastic data of investigated compounds and nematic mixture are provided. Compounds are characterised by ¹H NMR spectroscopy and mass spectrometry (electron ionization) analysis. They show an enantiotropic nematic behaviour in broad temperature ranges, confirmed by a polarising thermomicroscopy and differential scanning calorimetry. Detailed synthetic procedures are attached, showing a great synthetic versatility of the thiophene ring substitution. Synthesised compounds stand as promising components of highly birefringent liquid crystalline mixtures.     

Thermal tuning band gap in cholesteric liquid crystals

The phase of a liquid crystal (LC) changing from a nematic phase to a cholesteric (Ch) mesophase is achieved by adding different ratios of chiral dopants S811. By studying the transmission spectrum, we are able to measure the helical pitch in cholesteric phase. The pitch in the mixtures of nematic E7 and chiral dopants S811 as a function of the concentration of the dopant and temperature is investigated. The sensitivity of the selective reflection notch of the cholesteric phase to the thermal tuning depends strongly on the ratios of the chiral dopants. It reveals that the influence of temperature is more profound for those cholesteric liquid crystals (CLCs) which exhibit smectic A (SmA) at lower temperatures. When fitted using Keating's formula, the helical pitch calculated from our experimental results lies on the predicted curve. Optimised ratios of the mixture CLCs for the optimised reflection band with the specified wavelength ranging from 467 nm to 2123 nm are suggested.     

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.     

Dielectric Spectroscopy Analysis of Liquid Crystals Recovered from End-of-Life Liquid Crystal Displays

In the present work, the dielectric properties of recycled liquid crystals (LCs) (non-purified, purified, and doped with diamond nanoparticles at 0.05, 0.1, and 0.2 wt%) were investigated. The studied LC mixtures were obtained from industrial recycling of end-of-life LC displays presenting mainly nematic phases. Dielectric measurements were carried out at room temperature on a frequency range from 0.1 to 10⁶ Hz using an impedance analyzer. The amplitude of the oscillating voltage was fixed at 1 V using cells with homogeneous and homeotropic alignments. Results show that the dielectric anisotropy of all purified samples presents positive values and decreases after the addition of diamond nanoparticles to the LC mixtures. DC conductivity values were obtained by applying the universal law of dielectric response proposed by Jonscher. In addition, conductivity of the doped LC mixtures is lower than that of the undoped and non-purified LC.     

Nematic mesophase enhanced via lateral monofluorine substitution on benzoxazole-liquid crystals

Fluorine is widely used as a lateral substituent to modify the physical properties of liquid crystals. Here, laterally monofluorinated compounds, 2-(4?-alkoxy-2-fluorobiphenyl-4-yl)-benzoxazole derivatives (nPPF(2)Bx) bearing different substituents (H, CH₃, NO₂, coded as nPPF(2)BH, nPPF(2)BM and nPPF(2)BN, respectively) at 5-position, were synthesised and characterised. It is interesting to note that these only display enantiotropic nematic mesophases with mesophase ranges of 12–28°C and 13–45°C on heating and cooling for nPPF(2)BH, 46–97°C and 62–120°C for nPPF(2)BM and 82–108°C and 87–113°C for nPPF(2)BN, which are very different from the corresponding monofluorine-substituted analogue (compounds I) with enantiotropic smectic or smectic/nematic mesophases. The enhanced nematic mesophase is attributed to the reduced π–π interaction/conjugation resulting from the twisted structure of the molecule caused by the introduction of a fluorine atom into the inter-ring of the biphenyl unit. These results suggest that modification of the monofluorine substituent position is an effective method to improve the nematic mesophase in benzoxazole-liquid crystals.     

Physical properties of chlorinated liquid crystals

Dielectric, optical and electro-optical properties of four chlorinated nematic liquid crystal compounds and a eutectic mixture were characterized. Some chlorinated liquid crystals are found to exhibit a wide nematic range, modest dielectric and optical anisotropies, low viscosity and small UV absorption. Potential application of mixtures containing chlorinated liquid crystals for information displays in the visible spectral region is foreseeable.     

Dielectric relaxation study of a H shaped liquid crystal dimer

The present article reports dielectric relaxation study of an unusual shaped liquid crystal dimer (H shape) in the temperature range 40–85°C. The study of this liquid crystal dimer is important due to the presence of azo central linkage, which is photosensitive. The dielectric relaxation study indicates coupling between the electric field and the liquid crystal molecule of H shaped dimer. Various dielectric properties for this liquid crystal dimer are quite different from the conventional liquid crystals. The dielectric relaxation observed in the smectic phase is due to the reorientation of molecule along the director in the presence of an applied electric field. The temperature dependence of the dielectric parameters, such as relaxation frequency, relaxation strength and distribution parameter have been evaluated for this liquid crystal dimer for both planar as well as homeotropically aligned cell and then compared. The Cole–Cole equation has been used to evaluate the aforementioned parameters.     

Synthesis and characterization of novel epoxy monomers and liquid crystal thermosets

Four new epoxy monomers have been synthesized and characterized as part of a program to prepare novel liquid crystal thermoset (LCT) materials. Three of the new epoxy monomers contained a biphenyl mesogen and were not liquid crystalline (LC). The remaining epoxy monomer, which contained a 1,4-dibenzoyloxybenzene mesogen, was synthesized in an overall yield of 30% and displayed a broad (83°C) nematic liquid crystalline phase. The new liquid crystalline epoxy monomer was cured at 120°C and postcured at 175°C with a stoichiometric amount of 1,4-phenylenediamine. The thermal transitions of the resulting LCT were studied by differential scanning calorimetry (DSC), polarized light optical microscopy (POM), thermomechanical analysis (TMA), and wide angle x-ray diffraction (WAXD) as a function of cure time and temperature. A process characterization diagram was constructed which shows that LCTs based on this new LC monomer can be processed in the liquid crystalline phase over a broad range of times and temperatures. Qualitative agreement with previous epoxy LCT results was found, as LCT's with smectic phases and without clearing temperatures were observed at long cure times (high crosslink densities), whereas nematic phases with clearing temperatures predominated in networks at short cure times (low crosslink densities). © 1993 John Wiley & Sons, Inc.     

Influence of low concentration silver nanoparticles on the electrical and electro-optical parameters of nematic liquid crystals

Thermodynamical, optical, dielectric and electro-optical characterisation of nematic liquid crystals (LCs) and silver nanoparticle (NP) composites have been carried out. Transition temperatures of pure and composites systems have been measured. Thermodynamical studies suggest increase of clearing temperature of the composite material as compared to the pure material. Threshold voltage for switching from bright to dark state and splay elastic constant of the pure and composite materials have been determined. From frequency dependence of dielectric measurements, permittivity, loss, relaxation frequency and dielectric strength of flip-flop mechanism of LC molecules in the nematic phase have been calculated. Dielectric properties of composites have been explained in reference of Maier and Meier theory. The effects of doping of NPs on dielectric and electro-optic properties of LC-NP composites have been discussed.     

Enhancement of electrical conductivity,director relaxation frequency and slope of electro-optical characteristics in the composites of single-walled carbon nanotubes and a strongly polar nematic liquid crystal

In the present work, single-walled carbon nanotubes (SWCNTs) were dispersed in a room temperature nematic liquid crystal 4-pentyl-4′-cyanobiphenyl at the concentration of 0.02 and 0.05 wt%. Differential scanning calorimetry and temperature-dependent dielectric studies suggest decrease in clearing temperature of the composite materials as compared to the pure material. Ionic conductivity increases by two orders of magnitude due to the dispersion of such a low concentration (0.05 wt%) of SWCNTs. Dielectric studies also show that the presence of the SWCNTs decreases the effective longitudinal as well as transverse components of the dielectric permittivity. For homeotropic aligned samples, a relaxation mechanism has been detected in the lower MHz region both for the pure as well as dispersed samples. Presence of SWCNTs increases the relaxation frequency corresponding to flip-flop motion of molecules around their short axes. From frequency-dependent dielectric studies, important dielectric parameters such as relaxation frequency, dielectric strength and distribution parameters have been determined. Electro-optical experiments show that the threshold voltage decreases and the steepness of the transmission voltage curve improves due to the dispersion of SWCNTs.     

Design of new super-high birefringent isothiocyanato bistolanes – synthesis and properties

We report the synthesis of new laterally ethyl-substituted high birefringent phenylethynyltolane liquid crystals with alkylsulphanyl chain and isothiocyanate terminal group. The thermal and optical properties such as birefringence are measured and discussed based on their molecular structures. The compounds exhibit birefringence (Δn) in the range of 0.63–0.75 and are expected to be excellent components of high birefringent nematic mixtures for various applications.