Density and Ultrasonic Velocity Measurements in Hexyloxybenzylidene Phenylazoaniline

The temperature variation of density and ultrasonic velocity of the liquid crystal hexyloxybenzylidene phenylazoaniline are reported. The density across the smectic A—smectic B transition is more predominant than the other transitions. The density variation with temperature and the calculated thermal expansion coefficients suggest that the transitions isotropic liquid—nematic, nematic—smectic A and smectic A—smectic B are of first order. Anomalous behaviour of ultrasonic velocity is observed across the isotropic liquid—nematic transition and prominent dips in velocity are observed at the nematic—smectic A and smectic A—smectic B transitions. The adiabatic compressibility (β _ad ) Rao number (R _a ) and molar compressibility (B) are estimated using the experimental density and ultrasonic velocity.     

Heat Capacity and Thermodynamic Properties of p'-Substituted p-n-Hexyloxybenzylideneaniline I I I. p-n-Hexyloxybenzyl ideneam i no-p'-fluorobenzene (HBAF)

Abstract

The heat capacity of HBAF has been measured between 15 K and 385 K. Four phase transitions were found at 328.07 K (crystal-smectic B); 330.33 K (smectic B-smectic A); 334.88 K (smectic A-nematic); and 336.33 K (nematic-isotropic liquid), respectively. The enthalpies and entropies of these transitions were determined to be 23.22 kJ mol^?1/70.7 JK^?1 mol^?1; 3.05/9.2; 3.41/10.2; and 1.17/3.5, respectively. The total transition entropy of HBAF agreed well with those previously reported for the present homologues. The standard thermodynamic functions were estimated up to 385 K. The heat capacity curve of HBAF in the transition region had a close resemblance to that of p-n-hexyloxybenzylideneamino-p'-chlorobenzene. The entropies of the smectic A-nematic and nematicisotropic liquid transitions were compared with those theoretically derived by McMillan. The smectic B-smectic A transition entropy was interpreted in terms of order-disorder phase transition associated with the orientation of molecule.     

Bilayered Super-Structures of Antiferroelectric Mesogens

Abstract

Crystal structures of two antiferroelectric mesogens, TFMHPBC and MHPBC-10, were analysed by an X-ray diffraction method. In both crystals, mesogen molecules formed a herringbone structure which was essentially the same as that proposed for the antiferroelectric liquid crystal phase. Because of the crystallographic 2₁-symmetry along the b-axis, only the b-axis component of the dipole moment remains in a smectic layer. Since the dipole moment in the next layer has the same magnitude but the opposite direction, both crystals show no dipole moment as a whole. These structural features observed in their crystal states seem to be conserved in their antiferroelectric liquid crystal phases which are just above their crystal phases.     

Optic Effects of Smectic-Cholesteric Mixed Liquid-Crystals

Light transmission characteristics in optic effects of smectic-cholesteric mixed liquid-crystals are experimentally investigated. Cholesteric addition to a smectic liquid crystal changes greatly transmission characteristics in a cholesteric phase. Although a smectic liquid crystal alone is transparent, the mixed liquid crystals become opaque. However, this opaque state isconverted to the transparent state with applied fields. After the fields are removed, the transparent state is stored in case of then n-type mixture, e.g., BBBA:CN = 90:10 in weight, but returns to the original opaque state in case of thep-type mixture, e.g., C0B:CN = 90:10 in weight. In the smectic phase, the n-type mixture hardly responds to applied fields. but thep-type mixtureeasilyresponds. The response is dependent on a cell temperature: higher field is required in lower temperature. This temperature characteristic can be used for display application of liquid-crystal light valve.     

X-ray Measurements of the Bulk Modulus of the Myofilament Liquid Crystal in Striated Muscle

Low-angle X-ray diffraction measurements of the distance between myosin filaments comprising the smectic B₁ liquid crystal found in skinned crayfish striated muscle were made. The interfilament distanceas a function of applied compressive osmotic pressure wasdetermined and the bulk modulus of this myofilament liquid crystal ascertained. Under compression the behavior of this myosin filament lattice is shown to be predicted well by the Murnaghan equation of state. The isothermal bulk modulus, B _o, of this myosin filament liquid crystal is 1.51 × 10⁵ dynes/cm² at 2°C and at 46% actin overlap.     

Mesophase design: I. Molecular structure and crystal packing motifs of 4-alkylcyanobiphenyls

A comparative study of the crystal and molecular structures of 4-alkylcyanobiphenyls (ACB-n) C _n H_{2n + 1}-C₆H₄-C₆H₄-CN (n = 2, 4–12) belonging to liquid-crystal compounds revealed no direct relationship between the molecular geometry of these compounds and their liquid-crystalline properties. Mesogenic properties are determined by the alternation of the loosely packed aliphatic and closely packed aromatic regions in the crystals. Graphs describing the crystals and mesophases were designed for ACB-n. The graph for nematic mesogens of ACB-n (n = 5−7) has one structure-forming element. The graph for smectic-nematic (n = 8 and 9) and smectic (n = 10−12) mesogens have more than one structure-forming element. If different types of secondary bonds in the smectic mesophase have equal energies, the disruption of these interactions caused by the temperature rise occurs simultaneously and the system undergoes a transition from the smectic phase to the isotropic liquid. If the energies of different types of secondary bonds are different, the destruction of the mesophase occurs in steps and the phase transitions are more complicated (smectic-nematic-isotropic transitions).     

Liquid Crystal Polymers: Conformation of Deuterated Parts by SANS

Comb like liquid crystal polymers are polymers on each monomer is grafted a hanging liquid crystal molecule. The bulk state has the classical liquid crystal phases (nematic, smectic); what is the conformation of a chain in these phases is the problem to solve with the help of small angle neutron scattering. The values of the global sizes R _|| and R _‖ of a chain (in the direction parallel and perpendicular to the director) are discussed as a function of the chemical species and the temperature. Strange results are discussed in terms of segregation of labelled parts.     

Measurement of the Refractive Index and Estimate of the Order Parameter in Oriented Liquid Crystals

The refractive indices of a cholesteric liquid crystal, cholesteryl dodecyl carbonate (CDC), and a smectic liquid crystal, p-n-octoxybenzilidene-p-n-butylaniline (OOBBA), have been measured as a function of temperature in the transition temperature regions. The measurements were made on oriented liquid crystals with an Abbe refractometer. By combining the data on ordinary and extraordinary refractive indices, the relative order parameter, α_aS/α, is plotted as a function of temperature. The behavior of the order parameter near the cholesteric to isotropic transition of CDC is similar to a nematic liquid crystal, whereas, the order parameter in OOBBA shows only a slight temperature variation like many solids.     

Energy criteria for orientation of smectic C* liquid crystals in electrooptic elements

Energy analysis of the types of orientation of smectic C* liquid crystals is performed. Criteria for the type and quality of their orientation in electrooptic elements with surfaces of orientants of different nature are revealed. An energy parameter of the optical quality of planar orientation of a smectic C* liquid crystal is proposed, which determines the contrast ratio of electrooptic elements independent of the type and nature of the smectic C* liquid crystal and the orientant.     

Studies on the Smectic Phase of Some Schiff's Bases With a Terminal Trifluoromethyl Group

Some terminally substituted trifluoromethylbenzylideneanilines have been synthesized with a view to investigate an unidentified smectic phase which exhibits an unusual texture as observed under the polarizing microscope. This phase was first reported by Griffin et al.² for the compound N-(4-n-decyloxybenzylidene)-4'-trifluoromethylaniline. In a comparable compound but with reversed imine linkage the nature of this smectic phase remains unchanged. Also if the terminal n-decyloxy group is replaced by an n-decyl group the nature of the smectic phase remains the same except that it is observed at a considerably lower temperature. We observe that this smectic phase has uniaxial symmetry when studied with a polarizing microscope as well as with NMR techniques; the latter showing an order parameter S = 0.8 for this phase. X-ray diffraction patterns show this phase to be crystal smectic B.     

DISTORTIONS INDUCED BY A MAGNETIC FIELD IN PLANAR ALIGNED SAMPLES OF SMECTIC-C LIQUID CRYSTALS

Abstract

This article presents some preliminary theoretical results for the onset of the Helfrich-Hurault transition in smectic-C liquid crystals induced by a magnetic field applied parallel to the smectic layers. An energy in terms of the smectic layer displacement u is minimized via averaging to enable the calculation of a critical field strength H _c for the onset of layer distortions.     

Trans−1,2-Difluorostilbenes: Promising Materials for High Dielectric Biaxiality Ferroelectric Mixtures

Abstract

A range of two- and three-ring liquid crystals have been synthesised that incorporate a trans?1,2-difluoroethene linking group. Some of the materials have surprisingly low melting points and high smectic C phase stability, and they exhibit the ideal phase sequence for ferroelectric hosts of smectic C to smectic A to nematic. The synthesis was accomplished in a convergent manner through the use of low-temperature lithiations to generate organometallics based on boron and tin. Palladium-catalysed cross-couplings and Michael-type reactions were used to generate the final mesogenic materials. The polar fluoro substituents enable the generation of ferroelectric mixtures with a high dielectric biaxiality which is very important in τV minimum driving schemes. The alkenic linking group in stilbenes normally confers instability, but the difluoro-substituted analogues are stable compounds.     

Phase transition of nematic to smectic C through an intermediate boundary induced smectic A structure

An intermediate phase has been observed at the transition nematic to smectic C where a smectic A structure induced by the boundaries and a nematic phase exist simultaneously. The temperature interval of existence of the intermediate phase is of the order of one tenth of degree. Several conditions are necessary for its appearance: the latent heat L of the phase transition nematic-smectic C of the liquid crystal should be sufficiently small (L < k_BT_c); the nematic phase should undergo a bend deformation by the boundaries (possibly a twist one as well) and the transition nematic-smectic C should be carried out as slower as possible.     

Synthesis and Mesomorphic Characterisation of Chiral Homologues

Abstract

Chiral liquid crystals have attracted considerable interest as they exhibit a good variety of modulated phases. We have synthesised a homologous series viz., 4-(4^!-n-alkoxy benzoyloxy) benzylidene-4^!!?1-(s)-methyl propoxy anilines, incorporating a terminal chiral centre, inorder to obtain better understanding of the relationship between molecular structure and appearance of SmC* phase in the molecules. It is observed that, in the present series the lower members upto butyl are pure nematogens, while pentyl to hexadecyl derivatives exhibit classical smectic as well as nematic mesophases. An additional smectic C* phase is observed in the middle octyl to dodecyl homologues. The homologues have been characterised by IR, NMR and DSC. Their mesomorphic properties have been compared with structurally related homologous series.     

Fluid Biaxial Banana Smectics: Symmetry at Work

Abstract

Perhaps one of the most surprising results in the past 10 years was the prediction of Brand et al. [1] that fluid biaxial smectics made from comopunds without asymmetric carbons could, by symmetry, have a spontaneous polarization, P, in the layer plane. They called this construct, which can be either ferroelectric or antiferroelectric, smectic C₉. Advances gained from their prediction include the development of highly efficient electrets for broad-band telecommunications [2, 3] as well as a basic non-linear model [4] for TLAFs, thresholdless antiferroelectrics [5], now seen in beatiful, CMOS compatible, active matrix liquid crystal displays [6] (figure 1).     

Effects of electrohydrodynamic instability in smectic C liquid crystals

The effects of electrohydrodynamic instability (EHDI) in smectic C liquid crystals in an electric field are studied. The objects of study are oriented layers of para-hydroxybenzoic acid possessing a smectic phase. The observed effects are divided into three groups according to the character of the motion of molecular centers of mass and the orientation of the director and the smectic C liquid crystal layers. The instabilities of the azimuthal and Kapustin-Williams domains are experimentally found. The experimental cell consists of two glass plates with tin dioxide electrodes separated by Mylar spacers of a specified thickness. Various schemes of domain rotation are considered. The EHDI is found to depend on the layer geometry.     

Dielectric and pyroelectric studies of an antiferroelectric liquid crystal

Polymorphism and polar properties of an antiferroelectric (R)-2-methylheptyloxycarbonylphenyl-4-[(4-decyloxy-3-fluoro)benzoyloxy]benzoate liquid crystal are studied. The phases are identified, and the phase transition points are determined. Dielectric constant, dielectric losses, and pyroelectric properties are studied for the orthogonal smectic SmA and tilted smectic, SmC _α ^* , SmC ^*, SmC _γ ^* , and SmC _A ^* phases. The temperature dependence of spontaneous polarization is measured by the repolarization current technique and integration of the pyroelectric constant.     

Electrical Conductivity of Liquid Crystal Mixtures with Induced Smectic Phases

The electrical conductivity of the two liquid crystal mixtures N-(4-ethoxybenzylidene)-4′-amino benzonitrile (PEBAB)/4,4′-di-n-hexyloxy-azoxybenze (HEXOAB) and 4-n-heptyloxy-4′-cyanobiphenyl (7 CBP)/HEXOAB, which exhibit induced smectic A phases is investigated. In the smectic phases, the conductivity anisotropy of the PEBAB/HEXOAB mixtures is negative at the lowest PEBAB concentrations; this behaviour is usually expected for a smectic layer structure. With increasing PEBAB concentration the anisotropy increases and becomes positive. Possibly, this is an indication for a growing double layer structure, which was observed in polar smectic phases. In the nematic phases the conductivity anisotropy of the pure HEXOAB is considerably reduced by adding a relatively small amount of the polar component. An addition of 10 mole% 7 CBP reduces the anisotropy ratio of the electrical conductivity to V = K_∥/K ₁ ≈ 0.2, which probably is the lowest value observed in a nematic phase so far. Besides the negative conductivity anisotropy, these mixtures also exhibit a positive anisotropy of the dielectric constant. They thus fulfil the conditions for inverse dynamic scattering.     

Vibrational Spectra of Liquid Crystals. XII

Abstract

Recent papers by Gray et al.¹ have discussed the synthesis, structure, and properties of the mesomorphic 4-cyano, 4′-alkyl (or alkoxy) biphenyls. The reports on these materials have made mention of the existence of solid state dimorphism for certain homologs. This paper discusses this dimorphism as it manifests itself in the Raman spectrum of the octyloxy homolog (hereinafter referred to as 80CB) in the CN stretching region.

The approach used involves direct measurement of the Raman spectrum as a function of temperature, as well as computation of a correlation function obtained from the Raman band envelope by means of Fourier transformation. The application of this correlation function technique to this system has been discussed by us recently in detail.^2,3

Gray and Mosley,⁴ in a recent study of the Raman spectrum of 4-cyano, 4′-pentylbiphenyl note that the CN stretch of this compound is a doublet in the solid phase (2224 and 2233 cm^?1), but only the 2224 cm^?1 band appears in the nematic phase. They further report that only a single band appears in the CN stretching spectrum of solid 4'-heptyl-, -hexyl-, and -butyl-derivative. They speculate that the doublet might appear in the spectrum of the metastable solid phase of the heptyl homolog.

In this work, we show that for 80CB this is not the case. Rather, a doublet is observed for the stable solid but not for the metastable. The origin of this doublet is discussed, and all of the CN stretches for stable solid, metastable solid, and smectic liquid crystal are analyzed from the viewpoint of the vibrational relaxation correlation function.     

Synthesis and Liquid Crystal Behaviour of Further 4,4″-Disubstituted 2'-Fluoro-1,1':4',1”-Terphenyls

Further to earlier work on the liquid crystal properties of fluoro-1,1':4',1”-terphenyls¹ we have now extended this series to include terminally fluoro-and cyano-substituted 2'-fluoro-1,1':4',1″-terphenyls, chiral 2'-fluoro-1,1':4',1″-terphenyls, and esters derived from 2'-fluoro-1,1':4',1”-terphenyls and incorporating the alkylcyclobutyl group. The preparations and transition temperatures for these series of compounds are presented and their transition temperatures and mesophase types are discussed. An interesting result from this work was the appearance of an S^* _C phase for one chiral homologue and of S _c phases for the esters incorporating the alkylcyclobutyl group. The S _c formation is attributed to the presence of the fluoro-substituent.

Keywords: terphenyls, fluoroterphenyls, smectic C phases, cyclobutyl esters