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.     

Textural,thermal, optical and electrical properties of Iron nanoparticles dispersed 4′-(Hexyloxy)-4-biphenylcarbonitrile liquid crystal mixture

In this work, the effect of Iron nanoparticles (Fe NPs) dispersion in 4′-(Hexyloxy)-4-biphenylcarbonitrile (6OCB) nematic liquid crystal properties has been studied. Inclusion of Fe NPs (0.25 wt. %) in 6OCB liquid crystal (LC) on textures, isotropic–nematic transition temperature (T_I–N), electro-optical and dielectric properties have been investigated in planar aligned cell. The threshold voltage (V_th) and T_I–N decrease after dispersion of Fe NPs. Dielectric spectroscopy in nematic phase show that relaxation frequency (f_r) also decreases after dispersion of Fe NPs in 6OCB. The observed relaxation mode is due to the flip-flop motion of LC molecules about their short axis. The band gap and AC conductivity in case of 6OCB-Fe sample increase over pure 6OCB sample. A decrease in activation energy is also noticed.     

Graphene and liquid crystal mediated interactions

ABSTRACT

The two-dimensional graphene-honeycomb structure can interact with the liquid crystal’s (LC) benzene rings through π–π electron stacking. This LC–graphene interaction gives rise to a number of interesting physical and optical phenomena in the LC. In this paper, we present a combination of a review and original research of the exploration of novel themes of LC ordering at the nanoscale graphene surface and its macroscopic effects on the LC’s nematic and smectic phases. We show that monolayer graphene films impose planar alignment on the LC, creating pseudo-nematic domains (PNDs) at the surface of graphene. In a graphene-nematic suspension, these PNDs enhance the orientational order parameter, exhibiting a giant enhancement in the dielectric anisotropy of the LC. These anisotropic domains interact with the external electric field, resulting in a non-zero dielectric anisotropy in the isotropic phase as well. We also show that graphene flakes in an LC reduce the free ion concentration in the nematic media by an ion-trapping process. The reduction of mobile ions in the LC is found to have subsequent impacts on the LC’s rotational viscosity, allowing the nematic director to respond quicker on switching the electric field on and off. In a ferroelectric LC (smectic-C* phase), suspended graphene flakes enhance the spontaneous polarisation by improving the tilted smectic-C* ordering resulting from the π–π electron stacking. This effect accelerates the ferroelectric-switching phenomenon. Graphene can possess strain chirality due to a soft shear mode. This surface chirality of graphene can be transmitted into LC molecules exhibiting two types of chiral signatures in the LCs: an electroclinic effect (a polar tilt of the LC director perpendicular to, and linear in, an applied electric field) in the smectic-A phase, and a macroscopic helical twist of the LC director in the nematic phase. Finally, we show that a graphene-based LC cell can be fabricated without using any aligning layers and ITO electrodes. Graphene itself can be used as the electrodes as well as the aligning layers, obtaining an electro-optic effect of the LC inside the cell.     

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.     

Synthesis and evaluation of dinaphthylacetylene nematic liquid crystals for high-birefringence materials

We synthesised 1,2-bis(6-alkoxy-2-naphthyl)acetylene as a new dinaphthylacetylene liquid crystal (LC) compound with alkoxy tails of length m (DNA–OCm) and characterised their phase behaviour by polarising optical microscopy and differential scanning calorimetry, where all compounds exhibited a nematic phase. Also, we measured the actual, and not extrapolated, Δn values of this target compound, and our results show the birefringence potential of the pure LC compound. They have high birefringence values, with the highest value of approximately 0.5 obtained for DNA–OC2 at 550 nm at 10°C above the nematic?crystal transition temperature.     

Alignment of liquid crystals using Langmuir‒Blodgett films of unsymmetrical bent-core liquid crystals

ABSTRACT

The properties of the thin films of liquid crystal (LC) molecules can be governed easily by external fields. The anisotropic structure of the LC molecules has a large impact on the electrical and optical properties of the film. The Langmuir monolayer (LM) of LC molecules at the air–water interface is known to exhibit a variety of surface phases which can be transferred onto a solid substrate using the Langmuir?Blodgett (LB) technique. Here, we have studied the LM and LB films of asymmetrically substituted bent-core LC molecules. The morphology of LB film of the molecules is found to be a controlling parameter for aligning bulk LC in the nematic phase. It was found that the LB films of the bent-core molecules possessing defects favour the planar orientation of nematic LC, whereas the LB films with fewer defects show homeotropic alignment. The defect in LB films may introduce splay or bend distortions in the nematic near the alignment layer which can govern the planar alignment of the bulk LC. The uniform layer of LB film facilitates the molecules of nematic to anchor vertically due to a strong van der Waals interaction between the aliphatic chains leading to a homeotropic alignment.     

Investigation of dielectric and electro-optical properties of nematic liquid crystal with the suspension of biowaste-based porous carbon nanoparticles

ABSTRACT

The effect of biowaste porous carbon nanoparticles (PCNPs) on the dielectric and electro-optical properties of nematic liquid crystal (LC) mixture (1823A) of 4-(4-alkyl-cyclohexyl) benzene isothiocyanates and 4-(4-alkyl-cyclohexyl) biphenyl isothiocyanates has been studied. The dielectric permittivity of nematic LC has been increased with the dispersion of carbon NPs. The dielectric anisotropy has been calculated and found to be decreased with the dispersion of PCNPs into the pure nematic LC. The response time and birefringence have been also observed with the variation of temperature, frequency as well as the concentrations of carbon NPs. After the dispersion of PCNPs achieved better birefringence and faster response in the dispersed system, which is the significant application in display devices. Threshold voltage splay elastic coefficient and rotational viscosity have been calculated for both pure and NPs dispersed nematic system. Its value is increased with the dispersion of NPs. Additionally, photoluminescence and figure of merit have investigated as a comparative study of nematic matrix as well the dispersed system. The experimental results have been found to have good agreement with the theoretical data of nematic LC. An effort has been made to explain these experimental results on the basis of interaction between nematic molecules and carbon NPs.     

Theoretical study of nematic to smectic transition in cylindrical porous media

Experimental observations show that the nematic–isotropic (N–I) transition temperature (T_NI) and nematic to smectic transition temperature (T_NA) for liquid crystal (LC) embedded in solid porous materials is lower compared to that of the bulk LC. To explain this, various theoretical studies have been proposed. We propose to use the mean field approach considering cylindrical pores. We have earlier modified the Maier–Saupe (M–S) mean field theory to include the disordering effects of porosity as a disordering surface potential. A molecule near the surface is assumed to feel the mean field potential (M–S type) and also the surface induced potential. Our earlier calculations of extension of M–S theory on the variation of T_NI with pore diameter agree with experimental data. In the present article, we propose the extension of McMillan theory to include the disordering effects of porosity as a disordering surface potential. Our calculations on the variation of TNA with different pore diameters agree qualitatively with experimental data.     

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.     

Free‐energy model of asymmetry in side‐chain liquid‐crystalline diblock copolymers

Side‐chain liquid‐crystalline‐b‐amorphous copolymers combine the thermotropic ordering of liquid crystals (LCs) with the physics of block copolymer phase segregation. In our earlier experiments, we observed that block copolymer order–order and order–disorder transitions could be induced by LC transitions. Here we report the development of a free‐energy model to understand the interplay between LC ordering and block copolymer morphology in an incompressible melt. The model considers the interaction between LC moieties, the stretching of amorphous chains from curved interfaces, interfacial surface contributions, and elastic deformation of the nematic phase. The LC block is modeled with Wang and Warner's theory, in which nematogens interact through mean‐field potentials, and the LC backbone is modeled as a wormlike chain. Free energy is estimated for various morphologies: homogeneous, lamellar, cylinder micelle, and spherical micelle. Phase diagrams were constructed by iteration over temperature and composition ranges. The resulting composition diagrams are highly asymmetric, and a variety of first‐order transitions are predicted to occur at the LC clearing temperature. Qualitatively, nematic deformation energies destabilize curved morphologies, especially when the LC block is in the center of the block copolymer micelle. The thermodynamics of diblocks with laterally attached, side‐on mesogens are also explored. Discussion focuses on how well the model captures experimental phenomena and how the predicted phase boundaries are affected by changes in polymer architecture. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2671–2691, 2001     

All‐aromatic liquid crystalline thermosets with high glass transition temperatures

We have synthesized and characterized a new family of low melting all‐aromatic ester‐based liquid crystal oligomers end‐capped with reactive phenylethynyl end groups. In a consecutive, high‐temperature step, the reactive end groups were thermally activated and polymerization was initiated. This reactive oligomer approach allows us to synthesize liquid crystal thermosets with outstanding mechanical and thermal properties, which are superior to well‐known high‐performance polymers such as PPS and PEEK. We have modified an intractable LC formulation based on hydroquinone and terephthalic acid, with M_n = 1000, 5000, and 9000 g mol^?1, and varied the backbone composition using isophthalic acid, resorcinol, 4‐hydroxy‐benzoic acid, 6‐hydroxy‐2‐naphthoic acid, and chlorohydroquinone. All fully cured polymers showed glass transition temperatures in the range of 164–275 °C, and high storage moduli at room temperature (～ 5 GPa) and elevated temperature (～ 2 GPa at 200 °C). All oligomers display nematic mesophases and in most cases, the nematic order is maintained after cure. Rheology experiments showed that the phenylethynyl end group undergoes predominantly chain extension below 340 °C and crosslinking above this temperature. Highly aligned fibers could be spun from the nematic melt, and we found that the order parameter 〈P₂〉 was not affected by the chain extension and crosslink chemistry. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1368–1380, 2009     

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.     

Superior electro-optic properties of liquid crystal system using cobalt oxide nanoparticle dispersion

In this article, we study the electro-optical (EO) properties of the homogeneous aligned nematic liquid crystal (N-LC) doped with cobalt oxide (Co₃O₄) nanoparticles (NPs). The EO characteristics of Co₃O₄ doped N-LC are higher performance, indicating lower threshold voltage (1.33 V), faster rising time (1.479 ms), and faster falling time (9.343 ms) than pure liquid crystal (LC) cells. We have demonstrated these results by investigating the relationship between dielectric constants and LC device properties. Furthermore, we proved NPs doped N-LC cells drive low power operation without capacitance hysteresis. Our experimental results were verified by software simulation based on general physical properties.     

Phase equilibrium of poly(n-butyl acrylate) and E7

The experimental equilibrium phase diagram of mixtures of linear poly(n-butyl acrylate) of molecular mass M_w = 112000 g mol^-1 and the low molecular mass LC mixture E7 has been established using polarized optical microscopy and light scattering techniques. The diagram is found to be reminiscent of an upper critical solution temperature system. Two independent series of samples with the same composition were studied, yielding consistent results. A region of nematic and isotropic coexisting phases and a region of a single isotropic phase were identified in the composition-temperature phase diagram. The results were analysed within a theoretical model combining the Flory-Huggins lattice theory for isotropic mixing and the Maier-Saupe theory for nematic ordering. Interestingly, no region of isotropic coexisting phases was observed in our experiments. This is probably due to the fact that the nematic interaction overwhelms the isotropic interaction in the region where (I + I) coexisting phases could appear. A preferential solubility of certain constituents of the LC mixture in the polymer could possibly be a reason for this behaviour.     

Fluorescent and photo-optical properties of hydrogen-bonded polymer liquid-crystalline composites based on derivatives of stilbazole and crown ethers

New hydrogen-bonded photochromic stilbazole- and crown-ether-containing polymer LC composites are prepared and characterized. A smectic homopolymer with p-oxybenzoic groups, a nematic homopolymer carrying phenylmethoxy benzoate groups, and a nematic copolymer containing p-oxybenzoic and phenylmethoxy benzoate groups are synthesized and used as polymer matrices for these composites. The phase behavior and photo-optical properties of LC composites of various compositions are studied. A marked difference is observed in the fluorescence spectra for hydrogen-stabilized LC mixtures and model mixtures not forming hydrogen bonds. This effect is explained by the reversible transfer of proton of carboxyl groups involved in hydrogen bonding. It is shown that the complexation of crown-ether-containing groups of LC composites with potassium ions leads to a dramatic reduction in the intensity of fluorescence. This phenomenon may be used for creation of a new generation of sensors for metal ions.     

Hydrogen-bonded LC nanocomposites: characterisation of nanoparticle-LC interactions by solid-state NMR and FTIR spectroscopies

Although the molecular-level nanoparticle-liquid crystal (NP-LC) interactions are key for forming stable NP dispersions in LC, characterisation of these interactions is scarce in the literature. Recently, we have developed hydrogen-bonded LC nanocomposites based on mesogenic carboxylic acids and NPs functionalised with hydrogen-bond acceptor/donor groups. Here, we apply solid-state ¹H and ¹³C NMR and Fourier transform infrared spectroscopies to model systems consisting of mixtures of trans-4-n-butylcyclohexanecarboxylic acid (4-BCHA), 4-hexylbenzoic acid (6BA) and 4,4?-bipyridine. The binary mixture, 4-BCHA:6BA, was also studied. The results were compared to monolayer quantities of 6BA and 4-BCHA adsorbed on pyridine functionalised zirconia NPs (ZrO₂-n₃-pyridine) to understand the different effects of the functionalised NPs on the LC properties.     

Determination of elastic constants of a binary system (7CPB+9.CN) showing nematic,induced smectic Ad and re-entrant nematic phases

The temperature variation of the splay and bend elastic constants of a binary system exhibiting nematic-induced smectic A_d and re-entrant nematic phases measured by electric field-induced Freedericksz transition method has been reported. As bend deformation is not permitted in the smectic A phase, bend elastic constant (K₃₃) could only be determined in the nematic and re-entrant nematic phases. In both the nematic phases, the splay elastic constant has the same order of magnitude and does not show any pretransitional effect. However, in the induced smectic A_d phase, the value of K₁₁ is about one to two orders higher than that in the nematic phases. The bend elastic constant shows a strong pretransitional effect near the nematic–smectic and smectic–re-entrant nematic phase transitions. The influence of the presence of the induced smectic phase is observed even in those mixtures which have no induced smectic phases. As the smectic phase is approached, the ratio K₃₃/K₁₁ increases rapidly and diverges to infinity.     

Photoluminescence and electrical conductivity measurement of liquid crystal doped with ZnO nanoparticles

We report the effect of dispersion of zinc oxide (ZnO) nanoparticles (NPs) on the conductivity, birefringence and fluorescence properties of commercially available room temperature nematic liquid crystal (LC) with the variation of dopant concentration. Significant changes have been observed in transition enthalpy, DC conductivity, photoluminescence and birefringence values of the LC material by the addition of ZnO NPs. While the inclusion of NPs enhances the electrical conductivity of the composite system, it results in a reduction in the birefringence value, which can be attributed to a decrease in the order parameter of the system due to the perturbed geometry of the LC. This also results in the increase in threshold voltage value, which has been speculated as due to the piezoelectric nature of the ZnO NPs. The analysis of the fluorescence spectrum indicates that ZnO NPs enhance the intensity in the LC phase along with a small blue shift.     

Anisotropic shear viscosity in nematic liquid crystals: new optical measurement method

We propose a new optical method and the experimental set-up for measuring the anisotropic shear viscosities of nematic liquid crystals (LCs). LC shear viscosities can be optimized to improve liquid crystal display (LCD) response times, e.g. in vertical aligned nematic (VAN) or bistable nematic displays (BND). In this case a strong back-flow effect essentially determines the LCD dynamic characteristics. A number of shear viscosity coefficients defines the LCD response time. The proposed method is based on the special type of a shear flow, namely, the decay flow, in the LC cell with suitably treated substrates instead of magnetic or electric field application. A linear regime of a quasi-stationary director motion induced by a pressure difference and a proper configuration of a LC cell produces decay flow conditions in the LC cell. We determine three principal shear viscosity coefficients by measuring relative time variations of the intensity of the light passed through LC cells. The shear viscosity coefficient measurements provide a new opportunity for the development of new LC mixtures with fast response times in VAN, BND and other important LCD types.     

Anisotropic shear viscosity in nematic liquid crystals: new optical measurement method

We propose a new optical method and the experimental set-up for measuring the anisotropic shear viscosities of nematic liquid crystals (LCs). LC shear viscosities can be optimized to improve liquid crystal display (LCD) response times, e.g. in vertical aligned nematic (VAN) or bistable nematic displays (BND). In this case a strong back-flow effect essentially determines the LCD dynamic characteristics. A number of shear viscosity coefficients defines the LCD response time. The proposed method is based on the special type of a shear flow, namely, the decay flow, in the LC cell with suitably treated substrates instead of magnetic or electric field application. A linear regime of a quasi-stationary director motion induced by a pressure difference and a proper configuration of a LC cell produces decay flow conditions in the LC cell. We determine three principal shear viscosity coefficients by measuring relative time variations of the intensity of the light passed through LC cells. The shear viscosity coefficient measurements provide a new opportunity for the development of new LC mixtures with fast response times in VAN, BND and other important LCD types.