Director orientation of a ferroelectric liquid crystal on substrates with rubbing treatment: The effect of surface anchoring strength

One of the most important problems with ferroelectric liquid crystals is obtaining homogeneous as well as bistable alignment, not only to study their physical characteristics but also for their application to optical devices. In this connection it was predicted that the formation of homogeneous alignment requires strong surface anchoring, whereas bistability requires weak anchoring. We have therefore developed a method to determine the surface anchoring strength, and have tried to clarify whether there is a suitable anchoring range. It was found that A/K₂₂ (A is the surface anchoring and K₂₂ is the twist elastic constant of liquid crystal) of 4 × 10^-2 to 2 μm^-1 satisfies the contradictory requirements for homogeneous as well as bistable alignments for the material studied, and the bookshelf structure is successfully formed with this condition.     

The polar anchoring energy of nematic liquid crystals with polyvinylidene fluoride alignment layer

It has been proved that the high dielectric polyvinylidene fluoride (PVDF) could be used as an alignment layer in liquid crystal device. In this paper, the transmittance, pretilt angle and the polar anchoring energy of the substrates with PVDF alignment layer were researched. Theoretical results and the experimental results about the reflectivity R_SS (polarisation-conserving signals) recorded by full-leaky guided mode in liquid crystal technique are analysed to evaluate the anchoring energy of PVDF alignment layer. The result shows that the polar anchoring energy between PVDF alignment layer and liquid crystal molecules is 2.80 × 10^?4 J/m².     

An experimental investigation of electromechanical coupling in cholesteric liquid crystals

Abstract

Cholesteric liquid crystals which have a helical arrangement of oriented chiral molecules are expected to show novel cross couplings between fluxes and forces. The most convincing demonstration of these couplings is through a dynamical effect on the structure. Though Lehmann found a rotation of the structure under a temperature gradient in 1900, there has been no subsequent experiment confirming the same. We argue that it is very difficult to obtain a sufficiently weak anchoring of the director at the solid-cholesteric interface which is a necessary condition for the occurrence of Lehmann rotation. In order to achieve a practically zero anchoring energy at the surface, we have devised a simple technique of floating essentially flat cholesteric drops in the isotropic phase. Using this configuration we study the electromechanical coupling which produces a rotation of the structure under the action of a DC electric field. Using measurements on samples with different values of the pitch the relevant electromechanical coefficient of the materials investigated is found to satisfy the relation v _E = ?0·6 × 10^?12(q/m^?1)J m^?2, where q is the wavevector of the helix, whose sign is positive (negative) for a right (left) handed structure, confirming that v _E is hydrodynamic in origin.     

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.     

Polar anchoring strengths of nematic liquid crystal on high-density polymer brush surfaces

ABSTRACT

Herein, the polar anchoring energy coefficient (A_θ) of nematic liquid crystal (NLC) was examined for high-density polymer brushes via capacitance measurements. The A_θ is 10^?4 J m^?2 for the brushes of poly(methyl methacrylate), poly(ethyl methacrylate) and poly(styrene). The value decreases to 10^?5 J m^?2 for poly(n-butyl methacrylate) and poly(hexyl methacrylate) with lower glass transition temperatures. However, each polymer brush displays a constant A_θ value over a temperature range of ?15°C to 90°C, which is hardly affected by the graft density and brush thickness. At 25°C, A_θ is 10 times greater than the corresponding azimuthal anchoring energy coefficient (A_φ); therefore, NLCs on polymer brushes can be preferentially aligned along the in-plane component of the applied field.     

A simple method to measure the twist elastic constant of a nematic liquid crystal

We demonstrate a simple method for measuring the twist elastic constant (K₂₂) of a nematic liquid crystal (LC). By adding some chiral dopant to an LC host, the LC directors rotate 180° in a homogeneous cell, which is known as 180° super-twisted nematic (STN) cell. By preparing two such STN cells with different chiral concentrations and measuring their Fréedericksz threshold voltages, we can obtain the K₂₂ and helical twisting power simultaneously. In the whole process, there is no need to measure the pitch length. Our obtained K₂₂ values agree well with those reported by using other methods.     

The Application of Cryptand 22 as a Bifunctional Stationary Phase for Ion Chromatography

Poly (styrene/divinyl benzene) with cryptand 22 as an anchoring group was synthesized and applied as a bifunctional packing material for the separation of both cations and anions. At pH < 2, the resin can be protonated and applied as an anion exchanger for the separation of anions; with water as eluent, inorganic anions such as F^?, Cl^?, Br^?, NO₃^?”, I^? were well separated. After deprotonation at pH> 10, the resin became a cation exchanger and successfully separated alkali metal ions such as Li⁺, K⁺ and Cs⁺ with methanol as eluent. The effects of solvents, flow rate and temperature on the separation of various ions were also investigated.     

Anchoring Properties of Nematic Liquid Crystals Studied Using the Attenuated Total Reflection Method

Abstract

By using the attenuated total reflection method associated with the excitation of surface plasmons, the tilt angle of the liquid crystal director and its gradient at the surface are measured in a planar nematic cell as a function of the applied voltage. The surface anchoring anisotropy δπ of the liquid crystal and the surface elastic constant k_s , are found to be δπ = 0.288 erg/cm and k_s , = 9·12 × 10^-11 erg, respectively, when the boundary condition suggested by Barbero et al is used. The theoretical and experimental values obtained with this boundary condition and that of Mada are discussed. The results show that the boundary condition proposed by Barbero et al is in better agreement with the experiment.     

Calorimetric study of the glassy state XII. Plural glass-transition phenomena of ethanol

Ethanol was found to give a metastable crystalline phase (crystal-II) when the liquid was cooled at a moderate rate. Glassy states of liquid and of newly found crystal-II were obtained in the calorimeter cell by controlling the cooling rate of the liquid. The heat capacities of these phases as well as that of the stable crystal-I were measured by an adiabatic calorimeter in the temperature range between 14 and 300 K. The glass transition temperature T_g, the heat-capacity jump at T_g, and the residual entropy were found to be 97 K, 35.3 J K^?1 mol^?1, and 8.93 J K^?1 mol^?1 for the glassy liquid, and 97 K, 22.8 J K^?1 mol^?1, and 4.24 J K^?1 mol^?1 for the glassy crystal-II, respectively. The values for the residual entropy are referred to the third-law entropy for crystal-I.The heat capacities reported previously for the supercooled liquid by Gibson et al. and by Parks and Kelley agree well with those for the metastable crystal-II. Those of the supercooled liquid connect smoothly with those obtained for the liquid above the melting temperature. Thus, ethanol is found to be another example of a low-molecular-weight compound which shows multiple glass-transition phenomena.     

Surface anchoring of nematic liquid crystal 8OCB on a DMOAP‐silanated glass surface

Dynamic light scattering spectroscopy has been used to determine the temperature dependence of the anchoring strength of the nematic liquid crystal 8OCB on DMOAP‐silanated glass surfaces inducing homeotropic alignment. Wedge‐type glass cells with known thickness profile starting from 150 nm to several microns have been used in the experiments. The relaxation rates of the nematic fluctuations with the wave vector perpendicular to the confining surfaces have been measured as a function of the cell thickness. Fitting of the thickness dependence of the relaxation rate allows for straightforward determination of the surface extrapolation length and therefore also the strength of the surface anchoring, which is 1×10^?4 J m^?2. The overall experimental accuracy of the experiments is discussed.     

Dielectric and elastic properties of a nematic phase induced by charge transfer interaction in a binary system containing disc-shaped molecules

Abstract

The dielectric constants and the elastic coefficients for splay (K ₁) and bend (K ₃) of the charge transfer induced nematic (N_c) phase of tridecyl pentakis(phenylethynyl)phenyl ether (1) doped with different amounts of 2,4,7-trinitrofluorenone (2) were determined by studying the electric field induced bend deformation using the capacitance method. A negative dielectric anisotropy was observed. For the bend elastic constant K ₃ values up to 22 × 10^?12 N are found which are one order of magnitude higher than the respective values of discotic nematic (N_D) phases. Values of 0·6–0·8 are obtained for the ratio K ₁/K ₃; these show a minimum for the equimolar complex.     

Influence of saddle-splay deformation on lyotropic chromonic liquid crystals confined between two coaxial cylinders

ABSTRACT

A striking feature of lyotropic chromonic liquid crystals confined in cylinder model exhibit double-twist director configurations. Evidence suggests that saddle-splay deformation is among the most important factors for the distortions of director. Previous researches limit the director to distort at a fixed plane (r-? plane) by using specific boundary conditions such as degenerate planar anchoring condition. In this work, we consider lyotropic chromonic liquid crystals confined between two coaxial cylinders with free-surface boundary conditions and Rapini-Papoular-type anchoring conditions. By using finite-difference iterative method to solve the numerical solution of Euler equation, we find that saddle-splay deformation leads to double-twist director configurations under free-surface boundary conditions, which consist of the result under degenerate planar anchoring conditions. Furthermore, at Rapini-Papoular-type anchoring conditions, saddle-splay deformation has a great influence on the director in the radial direction (r direction) and the director distorts in three-dimensional space. Remarkably, our method provides a more accurate theory basis for the measured values of saddle-splay elastic constant K_24。     

Adsorption of phenols from contaminated water through titania-silica mixed imidazolium based ionic liquid: Equilibrium,kinetic and thermodynamic modeling studies

The present study describes the synthesis and characterization of titania-silica mixed imidazolium based ionic liquid (Ti-Si-IL) as well as evaluation of its adsorption behavior towards the 2,4-dinitrophenol (2,4-DNP) and 2,4,6-trichlorophenol (2,4,6-TCP). Synthesized Ti-Si-IL adsorbent was characterized by Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), BET surface area Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA) and elemental analysis (CHN). The adsorption of 2,4-DNP and 2,4,6-TCP on Ti-Si-IL was investigated systematically by evaluating the effects of adsorbent dosage, initial pH, contact time and temperature. Satisfactory adsorption 95% and 65% for 2,4-DNP and 2,4,6-TCP was observed at pH 4 and 6, respectively. The kinetic results for 2,4-DNP and 2,4,6-TCP on Ti-Si-IL indicated that the kinetic data follows pseudo-second-order model (R² = 0.9985 and 0.9750, respectively). Adsorption isotherms were fitted well by the Langmuir model for 2,4-DNP (q_m = 44.64 mg g^?1 at 318 K) and Freundlich model for 2,4,6-TCP (K_F = 0.63 mg g^?1 at 318 K). The +ΔH° and -ΔG° values demonstrated that the adsorption of 2,4-DNP was endothermic and spontaneous in nature. While the -ΔH° and +ΔG° values for 2,4,6-TCP adsorption demonstrated exothermic and comparatively nonspontaneous. During the removal process, the role of different functional groups, cyclic structure was monitored and found that the ionic property as well as π-π interactions of host molecules played important role in the extent of adsorption.     

The formula of anchoring energy for a nematic liquid crystal

The interface energy for a nematic liquid crystal (NLC) is considered as the sum of potential energy between LC molecules and molecules of the substrate surface, and a formula for anchoring energy is derived by elementary principles. The anchoring energy for a NLC should have two terms, the first term is the same as the Rapini–Papoular expression, the second is related to the normal of interface and resultes from the biaxial property of a NLC induced by interface. Hence there are two anchoring coefficients, W ₁ and W ₂. We demonstrate that W ₁ is equal to the tilt angle strength A_θ , and W ₂ corresponds to the difference between A_θ and the azimuthal strength A_? . Thus A_θ –A_? is due to the biaxial property of the NLC near the interface. Applying this formula to the twisted NLC cell, we discuss the threshold and saturation field, as well as the maximal tilt angel θ _m with respect to A_θ /A_? . Previously proposed formulae are discussed from our point view.     

Influence of weak anchoring on flow instabilities in nematic liquid crystals

We analyse the homogeneous instabilities in a nematic liquid crystal subjected to plane steady Couette or Poiseuille flow in the case when the director is prealigned perpendicular to the flow plane taking into account weak anchoring at the confining surfaces. The critical shear rate decreases for decreasing anchoring strength and goes to zero in the limit of torque-free boundary conditions. For Poiseuille flow two types of instability arise depending on the values of the azimuthal (W _a) and polar (W _p) surface anchoring strengths. The critical line in (W _a,W _p) space which separates the two instabilities regimes is obtained.     

Alignment control of liquid crystals on surface relief gratings

Liquid crystal alignment layers of a high T _g polymer containing an azobenzene moiety are prepared by photofabrication of a surface relief grating (SRG). The interference pattern of a circular and linearly polarized Ar⁺ laser beam generated the surface relief grating and the morphology was detected by atomic force microscope. The optical anisotropy of the films was investigated by polarizing optical microscopy. The orientation of the optical axis of the film mainly depends on the direction of the initial polarization plane. Nematic liquid crystals were aligned parallel to the direction of the grating, but the pretilt angles of the liquid crystals were nearly zero. Irradiation with homogeneous linearly polarized light could also align liquid crystals, but this alignment capability was weaker than that of the SRG film.     

Temperature‐Dependent Prediction of the Liquid Entropy of Ionic Liquids

Modeling of the temperature‐dependent liquid entropy of ionic liquids (ILs) with great accuracy using COSMO‐RS is demonstrated. The minimum structures of eight IL ion pairs are investigated and the entropy, calculated from ion pairs, is found to differ on average only 2 % from the available experimental values (119 data points). For calculations with single ions, the average error amounts to 2.6 % and stronger‐coordinating ions tend to give higher deviations. Additionally, the first parameterization of the standard liquid entropy for ILs is presented in the context of traditional volume‐based thermodynamics (S_l⁰=1.585 kJ mol^?1 K^?1 nm^?3?r_m³+14.09 J mol^?1 K^?1), which sheds light on the statistical treatment of ionic interactions. The findings provide the first direct access to accurate predictions of liquid entropies of ILs, which are tedious and time‐consuming to measure.     

Experimental and computational investigations on the high binding-selectivity of pyrimidine derivatives by a pillar[5]arene

The binding selectivity of an adenine-monofunctionalized pillar[5]arene (H) with a series of pyrimidine derivatives were investigated through ¹H NMR experiments and density functional theory (DFT) study. High binding-selectivity was demonstrated. Typically, H displayed very strong binding strength with 6-(2,4-dioxo-3, 4-dihydropyrimidin-1 (2H)-yl)hexanenitrile (G1) [K_a >10⁵ M^?1], up to about 3000-fold as compared with 1-hexylpyrimidine-2,4(1H, 3H)-dione (G5) [K_a = 31 M^?1]. The strong binding ability of H with G1 was due to the cooperative multiple hydrogen bond, dipole-dipole, C-H···π and π···π interactions. The high binding-selectivity was also verified by calculation results. The calculated interaction energy (ΔE_i) of G1?H was ?12.92 Kcal·mol^?1 while that of G5?H was ?2.85 Kcal·mol^?1.     

Computer simulations of nematic droplets

Abstract

Nematic droplets are intimately connected with disclinations, because in nematic droplets, point and line-shaped defects, as well as surface defects, are not generated at random, but inevitably by topological constraints. Thus, droplets provide a good means for investigating nematic defects. There is a growing interest in both topics due to the applications in polymer dispersed liquid crystal devices [1–3], but also in classical display modelling, where nematic defects are to be avoided. Various types of droplets are investigated theoretically with the aid of a previously developed numerical algorithm [4,5], which is based on a dynamic equation for the alignment tensor a _μv. The rotational diffusion, the influence of an orienting external field, and the Frank elasticity (in the one-coefficient approximation) are taken into account, but flow processes are neglected. For the application to nematic droplets, a new type of boundary conditions had to be used, which I have called ‘true planar anchoring’. I simulate the relaxation of the director field of nematic droplets from the isotropic state and vice versa for various types of anchoring and cavity shapes. Contrast pictures, as if viewed under crossed Nicols, are computed and compared to experiment. The results obtained elucidate the nature of the surface disclinations of strength one (boojums). In particular, it is found that their occurrence can be understood as a consequence of the planar anchoring, without any further assumptions. Moreover, a phase transition-like transformation of the director configuration is predicted which is temperature controlled and occurs, as the blue phases do, close to the nematic-isotropic transition temperature T_c.     

Homogeneous liquid crystal orientation on ion beam exposure TiO2 surfaces depending on an anisotropic dipole field

We studied homogeneous liquid crystal (LC) alignment properties on ion-beam (IB) irradiated TiO₂ films deposited by the electron beam evaporation method. Stable homogeneous LC alignment on a TiO₂ surface resulted from IB irradiation energy over 1800 eV. X-ray photoelectron spectroscopy analyses showed that Ti⁴⁺ 2p_3/2 and Ti⁴⁺ 2p_1/2 peaks were increased with increasing IB energy. Assuming that the increased peaks produced anisotropy dipole fields in the direction of the IB exposure process, we confirmed that the increasing IB energy induced strengthened the surface energy for entirely clear and stable LC molecule orientation. The voltage-transmittance characteristics of the twisted-nematic cell on the TiO₂ surface indicate that the TiO₂ film has potential for use as the LC alignment layer.