Dielectric properties of two high birefringence liquid crystal mixtures in the Sub-THz band

ABSTRACT

In order to produce liquid crystal (LC) with high birefringence (Δn) in the THz band, eight LC monomers were designed and synthesized. We formulate two mixtures (LC S200-2 and E7-2) by adding eight LC monomers to two commercial LCs (S200 and E7), respectively. The dielectric constants of the mixture LCs were measured using the frequency selective surface (FSS) in the region from 90 to 140 GHz. We compare the simulated results with the experimental measurements and determine the dielectric constants of the LCs. The dielectric anisotropy (Δε) of the nematic S200-2 and E7-2 LC mixtures are 16.4% and 16.3% higher than that of the commercial S200 and E7 LCs, respectively. The results show the frequency tunability of the two LC mixtures is greater than that of the commercial LCs.     

Anomalous optical properties of photoactive cholesteric liquid crystal doped with single-walled carbon nanotubes

Optical transmission and selective reflection data are reported for suspensions of single-walled carbon nanotubes (CNTs) in photoactive nematic material ZhK-440 with a mesogenic chiral dopant M5. At small concentrations of CNTs (C ≈ 0.01–0.05%), the preferential localisation of CNTs at oily sticks (cholesteric topological defects) and suppression of the network of oily streaks by CNTs were observed. At the same time, the optical density D was shown to be essentially non-linear and a minimum at certain concentration of CNTs, C ≈ 0.05–0.08%, was observed. This anomalous behaviour was explained by the presence of the structural transition from the loose (ramified) aggregates with highly anisotropic shape (oriented along the anchoring direction on rubbed polyvinyl alcohol) to the compact aggregates with denser packing. The location of this minimum, as well as the selective reflection maximum (helical pitch), was sensitive to partially reversible UV-induced trans–cis–trans isomerisation effects. The UV-controlled helical pitch variation was shown to be only slightly affected by introduction of CNTs.     

Thermal and dielectric properties of oriented liquid crystalline polysiloxane doped with azo‐dye

Investigations of dielectric relaxation and thermal properties of mixtures composed of liquid crystalline side‐chain polysiloxane and low molecular mass azo‐dye have been carried out. The dyes have been chosen to solublize well in the polymer matrix at concentrations up to 0.08 mol fraction. The dielectric relaxation experiments have shown the presence of separate processes attributed to reorientational motions of mesogenic side groups and dye molecules. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 369–377, 1999     

Electro-optic and dielectric properties of new binary ferroelectric and antiferroelectric liquid crystalline mixtures

Several new binary liquid crystalline mixtures have been designed and their properties were studied by complementary methods. It has been shown that even both pure components used for the mixture design possess the ferroelectric behaviour; the induced antiferroelectric smectic phase has been detected for one of the prepared mixtures. The phase diagram has been constructed and the existence of the antiferroelectric phase was confirmed by switching time and dielectric spectroscopy measurements. Some of the resulted mixtures possess very high values of the tilt angle that reaches close below 45° degrees at saturation. Values of spontaneous polarisation were found within 50–200 nC/cm² in dependence of the mixture’s composition. Due to specific properties, the obtained mixtures might be interesting for further design of multicomponent mixtures and formulation of the advanced nanocomposite systems.     

Dielectric relaxation in two liquid crystalline polyacrylates under high hydrostatic pressure

For two polyacrylates with p-cyano-phenyl benzoate side groups and different spacer lengths the dielectric relaxation was measured in the nematic and isotropic phase at pressures up to 5000 bar. The relaxation of the cyano groups was observed as a separate relaxation process; it seems to be closely correlated with the glass relaxation. The pressure dependence of the glass temperature and of the clearing temperature could be derived from the experiments.     

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.     

Synthesis and liquid crystalline properties of a disc-shaped molecule with azobenzene at the periphery

A triphenylene-based novel liquid crystal was synthesised whose peripheral cores are six rod-like azobenzene moieties linked through alkyl chains. A disc-shaped molecule 2,3,6,7,10,11-hexakis-[{4-(4-nitrophenylazo)phenoxy}hexyloxy]triphenylene was prepared by using a ferric chloride oxidative trimerisation of 1,2-bis-[{4-(4-nitrophenylazo)phenoxy}hexyloxy]benzene. Differential scanning calorimetry and polarising optical microscopy analysis revealed the existence of a nematic mesophase.     

Dielectric analysis of the interaction of nematic liquid crystals with carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) have been shown to self-organise, and when added as a guest to form a nanocomposite, their director couples with an organic liquid crystal (LC) host. Here, effects of MWCNTs on the low-frequency dielectric properties and Fréedericksz transition of the LC 4-cyano-4?-pentylbiphenyl (5CB) are studied. Anti-parallel electro-optic cells were filled with nanocomposites at weight percent concentrations of MWCNT to 5CB of: 0 (neat), 0.01, 0.10, 0.20, and 0.50. Low concentration was chosen to minimise Van der Waals attraction normally responsible for aggregation of MWCNTs. Dielectric relaxation spectroscopy was used to study interactions between MWCNTs and 5CB at frequencies from 20 Hz to 1 MHz. We propose a mechanism based upon measurements of the complex dielectric function which suggests that MWCNTs act as a slow-moving boundary within the sample cell at low frequencies and low applied electric fields, where the MWCNTs reorient along with the 5CB LC molecules. At higher frequencies and larger applied electric fields, the 5CB molecules rotate about their long axes while motion of the MWCNTs is frozen out.     

Terahertz properties of liquid crystals doped with ferroelectric BaTiO3 nanoparticles

In this paper, we present the results of the terahertz measurements of liquid crystal (LC) ferroelectric BaTiO₃ nanoparticles (nps) suspensions in the range of frequency from 0.3 up to 3.0 THz. Two different sol-gel methods and the harvesting technique were used to fabricate the nanoparticles. Five LC materials served as hosts for the suspensions: two single compounds: 6CHBT and 2,3′,5′-trifluoro-4-(4-pentylcyclohexyl)-4′-(trifluoromethoxy)-1,1′-biphenyl, and three mixtures: 1867, 2037 and 2020. We characterise, for the first time, the refractive indices and absorption parameters of suspensions with harvested nps in the terahertz range and show how the process of the nps’ preparation affects their response. We observed the increase of birefringence for few LC suspensions in comparison with the pure LCs. The highest increase of birefringence was for 2020 suspension with one kind of ferroelectric nps. On the other hand in most cases the addition of ferroelectric nps to LC causes the increase of its absorption in the THz range. The measurements of LCs terahertz properties by using time-pulsed spectrometer were performed.     

Enhanced electrical and mechanical properties of multiwall carbon nanotube rubber composites

Multiwall carbon nanotube‐filled elastomers are prepared by solution blending using a sonication process. It is shown that the processing conditions have a strong effect on the composite properties especially on electrical properties, which are very sensitive to nanotube dispersion within the elastomeric matrix. The percolation threshold is seen to be shifted to a lower nanotube content than that previously reported. With regard to the unfilled elastomer, large increases in the elastic and tensile moduli are obtained with the nanotube loading, thus highlighting the potential of this type of particles as reinforcing fillers for elastomeric matrices. Raman spectroscopy under strain has been used to evaluate the strength of the polymer–filler interface. Weak interfacial interactions are deduced, but the debundling of the nanotubes and the orientational effects of the polymeric chains are observed when the composite is submitted to a uniaxial deformation. Copyright © 2012 John Wiley & Sons, Ltd.     

Sulfonated liquid crystalline polyesters as resin matrix for single wall carbon nanotube and nanodiamond composites

The focus of this study is on incorporating pendant sulfonate groups along the backbone of a liquid crystalline polyester (LCPE) with the aim to improve the dispersion of single wall carbon nanotubes (SWNTs) and nanodiamonds (NDs). Two LCPE matrices, one sulfonated (LCPE‐S) and one nonsulfonated reference polymer (LCPE‐R), were successfully synthesized via a melt condensation method using aromatic and aliphatic AB, AA, and BB‐type monomers. Upon the introduction of SWNT and ND particles, the glass transition temperature (T_g) of the sulfonated LCPE increased from 21.5 °C to 41.0 °C and 41.9 °C, for SWNTs and NDs, respectively. When sulfonate groups were absent, a decrease in T_g was observed. The storage modulus (E′) followed a similar trend, i.e., E′ increased from 1.3 GPa to 5.2 GPa and 3.4 GPa, upon the addition of NDs and SWNTs. The LCPE‐S showed a lower thermal stability due to the loss of sulfonate groups, i.e. the 5% weight loss temperature (T) is ～280 °C for LCPE‐S vs. 333 °C for LCPE‐R. The decomposition temperature increased somewhat upon addition of the nanoparticles. The ability of dispersing carbon‐based nanostructures combined with an accessible melt processing window makes sulfonated LCPs attractive matrices towards preparing nanocomposites with improved thermal and mechanical properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Dielectric and electro-optical properties of a nematic liquid crystalline material with gold nanoparticles

ABSTRACT

We have prepared the composites of a room temperature nematic liquid crystalline material namely 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzoate (6CHBT) and gold nanoparticles (GNPs). Thermodynamic, electro-optical and dielectric properties have been investigated. Effect of dispersion of GNPs on various electro-optical and display parameters of host liquid crystalline material have been studied. Physical parameters such as threshold voltage, dielectric anisotropy and splay elastic constant have altered for composite systems. Due to the dispersion of GNPs, nematic to isotropic transition temperature is significantly increased. Relaxation frequency corresponding to flip-flop motion of the 6CHBT molecules about their short axes has increased due to the presence of GNPs.     

Dielectric properties of a strongly polar nematic liquid crystal compound doped with gold nanoparticles

This study focuses on the electrical characteristics of a strongly polar nematic liquid crystal, Hexyloxy-cyanobiphenyl (6OCB), doped with a low concentration (2% by weight) of citrate buffer stabilised gold nanoparticles (GNPs) at low frequencies between 20 Hz and 35 MHz. The doped samples have lower values of nematic–isotropic transition temperature, permittivity (both parallel and perpendicular to the field direction) and dielectric anisotropy; however, relaxation time and activation energy were increased. The observed results could be explained on the basis of weakly anisotropic nature of GNPs and a local rearrangement of liquid crystal molecules surrounding the nanoparticles. Moreover, a complimentary suggestion on a possible change in the dipole–dipole correlation is made to explain the difference in changes (qualitative and quantitative) observed for permittivity of the host nematic liquid crystal doped with GNP. Temperature dependent dielectric relaxation studies indicate an increase in viscosity and potential barrier; and hence a change in strength of inter-molecular and intra-molecular interactions is suggested.     

Enhancement of the properties and mesophases stability after the electron beam irradiation on a racemic anti-ferroelectric liquid crystalline mixture

The display parameters and the stability of the various mesophases of a newly synthesised racemic mixture of anti-ferroelectric liquid crystals (AFLCs) have been boosted with the help of the electron beam irradiation. The mixture has phase sequence of isotropic–smectic C–smectic C_A crystal. The effective macroscopic polarisation and transition temperatures of the various mesophases of the irradiated mixture have increased as compared with the pure mixture. The macroscopic polarisation of the mixture has increased from 21 to 27 nC/cm² due to the irradiation. From various studies, we have observed that the temperature range of the smectic C_A phase has increased by 20.6°C with marginal decrease in the temperature range of the smectic C phase.     

Synthesis of rod-like bis-ester liquid crystals and their influence on photoelectric properties of liquid crystalline materials

Six novel rod-like magnetic liquid crystals have been prepared,in which trans-bicyclohexyl or trans-cyclohexylphenyl and biphenylcarboxylic acid phenyl ester mesogenic cores with n-propyl and n-pentyl substituents were terminated by 4-hydroxyl-TEMPO (TEMPO=2,2,6,6-tetramethylpiperidine-1-oxy).Their structures were confirmed by elemental analysis,IR and MS. Determined by SQUID,EPR,DSC and HS-POM(heat stage polarizing optical microscope),the six compounds all have both magnetic and liquid crystalline prope...     

Model studies towards liquid crystalline dendrimers with mesogenic repeat units throughout the structure

Model studies towards liquid crystal dendrimers in which the mesogenic units are based on alkoxyalkylbiphenyls and repeat through the structure are described; the parent monomers show smectic mesophases demonstrating the suitability of the motifs.     

Dielectric and electro-optic behaviour of nematic-SWCNT nanocomposites under applied bias field

We have prepared the composites of a room temperature Nematic Liquid Crystals and Single-Walled Carbon Nanotubes. Effect of dispersion of nanotubes on various dielectric and electro-optic parameters on host nematic liquid crystals were investigated. The changes in dielectric and electro-optic parameters (viz: relative permittivity, dielectric anisotropy, switching threshold voltage and splay elastic constant) were observed for composite systems. The composites filled in the cells have been probed under applied bias electric field and it enhanced the nematic ordering of the liquid crystal molecules in the composites which results overall improvement of dielectric and electro-optic parameters of the prepared composites.     

Dielectric spectroscopy of polyazomethine with vinylene moieties in the main chain

We have explored the dielectric properties of polyazomethine with vinylene moieties in the main chain (PAZ-PV). The dialdehyde 2,5-bis(hexyloxy)-1,4-bis[(2,5-bis(hexyloxy)-4-formyl-phenylenevinylene]benzene was polymerised in solid-state with the diamine poly(1,4-butanediol)bis(4-aminobenzoate). The polymer obtained exhibited liquid crystal properties. The molecular dynamics and phase transitions including the liquid crystal phase of PAZ-PV were investigated by dielectric spectroscopy. The dielectric constant decreases with a decrease in the temperature, except in the nematic phase region, where a slight increase was observed. The temperatures of the phase transitions were well seen and were compared with differential scanning calorimetry (DSC) and polarised optical microscopy experiments. All values determined from dielectric data were a few degrees higher than those obtained in previous measurements (DSC).     

Preparation and properties of natural rubber composites reinforced with pretreated carbon nanotubes

In order to achieve dramatic improvements in the performance of rubber materials, the development of carbon nanotube (CNT)‐reinforced rubber composites was attempted. The CNT/natural rubber (NR) nanocomposite was prepared through solvent mixing on the basis of pretreatment of CNTs. Thermal properties, vulcanization characteristics, and physical and mechanical properties of the CNT/NR nanocomposites were characterized in contrast to the carbon black (CB)/NR composite. Through the addition of the CNTs treated using acid bath followed by ball milling with HRH (hydrated silica, resorcinol, and hexamethylene tetramine) bonding systems, the crystallization melting peak in differential scanning calorimetry (DSC) curves of NR weakened and the curing rate of NR slightly decreased. Meanwhile, the over‐curing reversion of CNT/NR nanocomposites was alleviated. The dispersion of the treated CNTs in the rubber matrix and interfacial bonding between them were rather good. The mechanical properties of the CNT‐reinforced NR showed a considerable increase compared to the neat NR and traditional CB/NR composite. At the same time, the CNT/NR nanocomposites exhibited better rebound resilience and dynamic compression properties. The storage modulus of the CNT/NR nanocomposites greatly exceeds that of neat NR and CB/NR composites under all temperature regions. The thermal stability of NR was also obviously improved with the addition of the treated CNTs. Copyright © 2008 John Wiley & Sons, Ltd.     

Dielectric properties of four room temperature ferroelectric and antiferroelectric multi-component liquid crystalline mixtures

Dielectric properties of four recently formulated room temperature multi-component liquid crystalline mixtures with paraelectric (SmA*), ferroelectric (SmC*) and antiferroelectric (SmC*_A) phases have been studied as a function of temperature and frequency. Under planer anchoring condition, dielectric spectroscopy revealed all the characteristic modes: low frequency P_L and high frequency P_H mode in SmC*_A phase, Goldstone mode (GM) in SmC* phase and soft mode (SM) in SmA* phase. Dielectric behaviour has also been studied under the application of DC bias electric field. With bias electric field, we have been able to study the soft mode dielectric behaviour in the SmC* phase. An unknown high frequency mode (X-mode) with and without bias is also observed in SmC* phase. Dielectric results are explained in the light of generalised Landau theory. The mixtures show very high soft mode electroclinic coefficient in the SmA* phase in addition to fast switching in SmC*_A and SmC* phases [30].