The NTB phase in an achiral asymmetrical bent-core liquid crystal terminated with symmetric alkyl chains

ABSTRACT

The characteristics of the twist-bend nematic (N_TB) phase of an achiral asymmetrical rigid bent-core liquid crystal (LC), the ends of which are terminated by symmetric alkyl chains, are reported. The nematic–nematic phase transition and its properties are studied by differential scanning calorimetry (DSC), polarising microscopy and the electro-optic techniques. Large domains of opposite handedness are observed in the absence of the external field in the N_TB phase. Another set of periodic striped pattern consisting of domains with sharp boundaries is formed when a high-frequency electric field with a magnitude above its threshold is applied across a planarly aligned cell. The neighbouring domains are of opposite chirality. The temperature dependence of the heliconical angle θ₀ is determined from the birefringence measurements using Haller’s extrapolation technique. This material shows lower values of the heliconical angle (~9.3° at a temperature of 155°C within the N_TB phase) when compared with the previously reported dimer-based twist-bend nematic LCs (31°±3°).     

Synthesis of new wide nematic diaryl-diacetylenes containing thiophene-based heteromonocyclic and heterobicyclic structures,and their birefringence properties

New monocyclic and bicyclic thiophene-based diaryl-diacetylene liquid crystal (LC) materials were synthesised and demonstrated to exhibit wide enantiotropic nematic phases. One thiophenyl-benzene derivative, in particular, displayed a stable nematic phase across a temperature range of over 100°C. The birefringence properties of the compounds were measured using a multiple-beam interference (MBI) method, with the highest value found to be for the same thiophenyl-benzene molecule (Δn = 0.57, 550 nm) at 10°C above the crystal-to-nematic transition temperature. Furthermore, the effects of the cyclic structure on the mesomorphic behaviours, transition temperatures, and birefringence properties were investigated in detail from both experimental and theoretical viewpoints.     

Fracture toughness and fracture mechanism of liquid‐crystalline epoxy resins with different polydomain structures

Liquid‐crystalline (LC) epoxy resins were cured at different temperatures to obtain polydomain LC phase–cured resins. The cured resins had polydomain structures with a nematic LC phase and their domain diameters differed depending on the curing temperatures. The relationship between the domain diameter and fracture toughness of the diglycidyl ether of terephthalylidene‐bis‐(4‐amino‐3‐methylphenol) (DGETAM)/m‐phenylenediamine (m‐PDA) systems with the nematic phase and the previously reported smectic LC phase structures was investigated. It was clarified that the highly ordered LC structure (smectic phase) in each domain could improve the fracture toughness. In addition, the changes in the network orientation of the DGETAM/m‐PDA systems were evaluated by a mapping of the microscopic infrared dichroism in the fracture process and their toughening mechanism was suggested. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Synthesis,characterisation and phase transition studies in N-(-4-ethyloxybenzylydene)-4’-alkoxyanilines

Synthesis and characterisation are carried out in N-(-4-ethyloxybenzylidene)-4?-alkoxyanilines, 2O.Om liquid crystalline (LC) compounds with m = 3, 4 and 6–10. All the compounds exhibit monovariant nematic phase except with m = 10; the LC material shows bivariant nematic-smectic-C in addition to the nematic phase. Further, the variation in density with temperature in all these seven compounds is studied. The density and thermal expansion coefficient results reveal that the phase transitions, namely isotropic to nematic and nematic to SmC, present in these compounds show first-order nature as expected and that all the parameters show characteristic change in the vicinity of the phase transformation. The results are discussed in the light of the data available on other nO.Om compounds.     

Helical twisting power and compatibility in twisted nematic phase of new chiral liquid crystalline dopants with various liquid crystalline matrices

ABSTRACT

Four chiral dopants exhibiting smectic LC phases themselves were prepared and their helical twisting power (HTP) and thermal phase behaviour in mixtures with four various LC hosts were studied. The influence of host liquid crystal on HTP was evaluated and generally higher values were found for hosts with high birefringence. Unexpectedly, high enhancement was found for an LC-chiral dopant pair, both having a similar aromatic core – biphenyl ring substituted with polar group. All studied chiral dopants exhibited limited compatibility with the LC hosts in twisted nematic phase at room temperature. For one of the studied mixtures, it was able to obtain single twisted nematic phase with selective light reflection band with maximum at wavelength about 1.0 µm. Carboxylic acid-type dopants exhibited total compatibility with the studied host in single twisted nematic phase at elevated temperatures, allowing preparation of mixtures with reflection band in the visible range. In case of the carboxylic acid dopants, blue phases for optimised compositions were observed. Intermolecular hydrogen bonding between carboxylic acid proton and pyridine nitrogen of chiral dopants was found. Doping the LC host with these dopants led to slight enhancement of HTP value and higher solubility in the LC host.     

Electrooptical properties of new type fluorinated phenyl-tolane isothiocyanate liquid crystal compounds

A series of 4?-(4-alkyl-phenyl)-2?,6?-difluorotolane isothiocyanate liquid crystal (LC) compounds were synthesised, and their phase transitions and electrooptical properties were investigated. These compounds exhibit high birefringence, about 0.47–0.52. As the number of carbon atoms in the alkyl chains increases, these LC compounds can exhibit smectic phases. When these LCs were mixed into the commercial LCs, the birefringence values of LC mixtures become higher than pure commercial LCs, and the visco-elastic coefficients of five LC mixtures are very close to each other at every test temperature. The results of response properties indicate that the compounds with a tri-fluorine substitution and n-propyl end group possess better response performance than the others. These LC compounds are particularly attractive for achieving fast response times in LC optic devices.     

New isothiocyanato liquid crystals containing thieno[3,2-b]thiophene central core

New isothiocyanato liquid crystal (LC) materials based on thieno[3,2-b]thiophene core have been synthesised and characterised. Their mesomorphic and physical properties were evaluated. The results indicate that most of the new compounds exhibit only enantiotropic smectic A phases with high clearing points, and the difluorinated compounds (A3 and A6), in particular, also display a stable nematic phase with low melting points. Compared with the corresponding biphenyl and thiophene-phenyl analogues, these thieno[3,2-b]thiophene-based compounds possess increased birefringence (the highest value found to be 0.40) and mesogenic phase intervals. These new thieno[3,2-b]thiophene-based LCs exhibit a high birefringence and a high clearing point and are of potential use as components of high birefringence mixtures.     

Theory of a helicoidal cholesteric phase induced by an external field

We present a mean field theory to describe a helicoidal cholesteric phase for mixtures of a chiral nematic liquid crystal (LC) and a polymer chain as well as for pure chiral nematic LC molecules in the presence of a longitudinal external field parallel to the pitch axis of a cholesteric (Ch) phase. The free energy of the helicoidal Ch phase (Ch_H) is derived as a function of a usual orientational order parameter and an order parameter of the Ch_H phase. On increasing the strength of the external field, we find that the Ch phase changes to the nematic (N) phase through the Ch_H phase. Depending on the temperature and the strength of the external field, we find the second-order N–Ch_H and Ch_H–Ch phase transitions and the first-order paranematic (pN)–N, pN–Ch_H and pN–Ch phase transitions. We also predict phase diagrams in mixtures of a flexible polymer and a Ch LC molecule under the external field.     

Influence of the anisometry of magnetic particles on the isotropic–nematic phase transition

The influence of the shape anisotropy of magnetic particles on the isotropic–nematic phase transition was studied in ferronematics based on the nematic liquid crystal (LC) 4-(trans-4-n-hexylcyclohexyl)-isothiocyanato-benzene (6CHBT). The LC was doped with spherical or rod-like magnetic particles of different size and volume concentrations. The phase transition from isotropic to nematic phase was observed by polarising microscope as well as by capacitance measurements. The influence of the concentration and the shape anisotropy of the magnetic particles on the isotropic–nematic phase transition in LC are demonstrated here. The results are in a good agreement with recent theoretical predictions.     

Solubility effects of multicomponent liquid crystal blends towards poly (n-butyl-acrylate)

Blends composed of isotropic linear poly (n-butylacrylate) of molecular weight M _w?=?112,000 g mol^?1 and the commercial four-component nematic low molecular weight liquid crystal (LC) mixture E7 exhibit a strong shift of the single nematic–isotropic transition temperature T _NI compared to that of the pure LCs, which was evidenced by using two complementary experimental techniques: differential scanning calorimetry (DSC) and high-performance liquid chromatography. The first one provides direct information about phase behaviour and variation of T _NI of the polymer/LC blends, whereas the second one consists of analysing qualitatively and quantitatively the composition of millimetre-sized segregated LC domains in the two-phase region of the phase diagram.

In order to understand the origin of the unusual phase behaviour, several LC blends were prepared by modifying the concentration of the four single LC components that are present in the eutectic E7 mixture, following the results from the previous chromatographic analysis. These model blends were investigated by DSC measurements, showing that the variation, particularly of the terphenyl LC compound concentration, plays a determining role for the phase behaviour of the LC mixture and the shift of T _NI.     

New isothiocyanatotolane liquid crystals with terminal but-3-enyl substitute

Four kinds of new but-3-enyl-based isothiocyanate liquid crystals composed of tolane core and but-3-enyl terminal group (A1–A4) were synthesised via seven step reactions based on 2-(4-bromophenethyl)-1,3-dioxolane, and four n-butyl analogues B1–B4 as comparison structures were also prepared. The mesomorphic properties and physical properties of the compounds were investigated. Single fluorinated compounds A2 and A3 exhibit monotropic nematic phase, and they have lower melting enthalpy and higher clearing points than those of the comparison compounds B2 and B3. The non-fluoro-substituted compound A1 and difluorinated compound A4 exhibit no nematic phase. Replacement of n-butyl chain by but-3-enyl as terminal group is enabled to increase birefringence (Δn ~ 0.394–0.430) and reduce rotational viscosity. These isothiocyanatotolanes with terminal but-3-enyl substitution have potential application for high birefringence mixtures.     

Photoinduced liquid crystal blue phase by bent-shaped cis isomer of the azobenzene doped in chiral nematic liquid crystal

A photoresponsive azobenzene molecule DCAZO2 with two cholesteryl groups linked to both sides of the azobenzene group is doped in a mixture of nematic liquid crystal E7 and chiral dopant S811 (61.9 wt% E7, 36.1 wt% S811 and 2.0 wt% DCAZO2). Cooled from isotropic phase to 33.0°C, chiral nematic liquid crystal (N*LC) was formed in the sample and then the temperature was kept unchanged at 33.0°C. UV light irradiation induces the trans–cis photoisomerisation and thus an obvious phase transition. When the azobenzene groups isomerise to a cis-saturated state, the UV light was turned off and the white light was turned on at the same time. The bent-shaped cis isomer then turns back to the planar trans isomer gradually. A blue–green platelet texture representing cubic blue phase (BP) was observed and the size of the platelets was increased along with the cis–trans isomerisation. UV–vis absorption spectra indicate that the photoinduced BP exists when the isomerisation degree is between 79% and 18%, and further cis–trans isomerisation change BP back into N*LC. The large geometric structure of the cholesteryl groups and the large bent angle θ of the cis isomer are supposed to be responsible for the interesting result.     

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.     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4′-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1–4; and X = C _n H_2n+1, F, CF₃ or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF₃ when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices. Four of the diacetylenes with m = 1 (A, B = H) were also prepared (X = C₆H₁₃, F, n= 2, 3). When X was C₆H₁₃ (n=2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X=F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X=C₆H₁₃ and n=2 had a melting temperature below room temperature.     

Random nematic structures in the absence of inherent frustrations

We study the impact of anisotropic nanoparticles (NPs) on the nematic liquid crystal (LC) order. Within a mesoscopic Flory–Huggins-type approach we have estimated regimes where LC–NP mixtures are essentially homogenous. Using a lattice Lebwohl–Lasher type approach we have also studied the impact of anisotropic NPs on LC ordering. We analysed the cases where the orientations of NPs are either frozen-in or could be varied, to which we refer as random field mixtures and annealed mixtures, respectively. In the latter case we have demonstrated the existence of qualitatively different regimes. In particular, we determined the concentration regime, where LC configurations resembling a transparent nematic phase could be observed. Such domain patterns are stabilised by NPs hindering the annihilation of topological defects in LC order.     

Director configurations in nematic droplets with tilted surface anchoring

The polymer dispersed nematic liquid crystal (LC) with the tilted surface anchoring has been studied. The droplet orientational structures with two point surface defects – boojums and the surface ring defect – are formed within the films. The director tilt angle α = 40° ± 4° at the droplet interface and LC surface anchoring strength W_s ~ 10^–6 (J m^?2) have been estimated. The bipolar axes within the studied droplets of oblate ellipsoidal form can be randomly oriented are oriented randomly relatively to the ellipsoid axes as opposed to the droplets with homeotropic and tangential anchoring.     

Helical polyacetylene—Origins and synthesis

We present the origins and synthesis of helical polyacetylene (H‐PA) by focusing on its peculiar spiral morphology. Interfacial polymerization of acetylene was carried out in an asymmetric reaction field consisting of chiral nematic liquid crystal (N*‐LC) and Ziegler–Natta catalyst. As the N*‐LC is composed of nematic liquid crystal and a chiral compound such as a binaphthyl derivative with either the R‐ or S‐configuration, the screw directions of the polyacetylene chain and fibril bundle—and even the spiral morphology—are rigorously controlled by the chirality of the selected compound. Interestingly, the screw directions of the fibril and the bundle in H‐PA were found to be opposite to that of N*‐LC. It is worthwhile to emphasize that the hierarchical spiral morphology involving the primary to higher order structure is generated in a synthetic polymer such as polyacetylene by using N*‐LC as an asymmetric polymerization solvent. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 395–406; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20163     

Electrical conductivity and dielectric constant measurements of liquid crystal–gold nanoparticle composites

The behaviour of the anisotropic electrical conductivity of liquid crystal–gold nanoparticle (LC‐GNP) composites consisting of a commercially available room temperature nematic compound doped with alkylthiol‐capped GNPs has been investigated. The nematic–isotropic transition of the composite decreases nearly linearly with increasing X, the concentration of GNP (in weight %) at a rate of about 1°C /weight %. The inclusion of GNPs increases the electrical conductivity of the system with the value increasing by more than two orders of magnitude for X = 5%. However, the anisotropy in conductivity, defined as the ratio of the conductivity along (σ_∥) and orthogonal (σ_⊥) to the director shows a much smaller but definite decrease as X increases.     

Cholesteric induction power of β-galactose derivatives

Galactose derivatives were explored as chiral dopants, effective for inducing chiral nematic liquid crystal (LC) phases. Galactose bearing O-isopropylidene substituents at the C3 and C4 and butoxybiphenyl substituents at the C2 and C6 positions exhibits a high helical twisting power (HTP) value of ?74.4 μm^?1. Such a high HTP value for the galactose derivative is attributed to (1) linkage of the C3 and C4 carbons with the O-isopropylidene substituent, which places the C2 and C6 substitutes in a skew arrangement at a large angle and (2) enhancement of the affinity with the host nematic LCs by incorporating aromatic substituents at the C2 and C6 positions that are similar to those in the host.     

Effects of chemical structure and composition of the polymer matrix on the morphology and electro-optical performance of polymer-dispersed liquid crystal films

Polymer-dispersed liquid crystal (PDLC) systems on the basis of nematic liquid crystal E7 and amphiphilic binary copolymers of acrylic acid (AA) with such acrylates as 2-ethylhexyl acrylate (EHA), n-butyl acrylate (BA), and methyl acrylate (MA) are investigated. It is shown that the liquid crystal (LC) drops in the copolymer EHA–AA have submicrometre sizes, and their dependence on the composition of the photo-curable monomer mixture is described by a parabolic curve. The highly oriented domain structure in the same system is first revealed when electric field is applied. The threshold voltage for all systems begins to increase with some critical composition of a monomer mixture in which the longer the hydrocarbonic radical in an acrylate molecule, the higher the content of AA. The PDLC system based on the BA–AA copolymer with 30 wt% LC exhibits the least value of the driving voltage, 1 V μm^–1, and the lowest memory effect.