Growing of local smectic C monocrystals from an initially twisted nematic phase

The growing of smectic C single local monocrystals was investigated from an initially twisted nematic phase with smectic C ordering (p-n-alkoxybenzoic acid). Characteristic longitudinal and transverse dislocation lines have been observed at growth in a thin liquid crystal cell, single local monocrystals are discussed. The evolution was studied of the smectic C phase from cybotactic groups in a nematic phase toward needlike nuclei near to the nematic-smectic C phase transition and after that after that toward the local single monocrystals.     

Induced smectic A phase by homeotropic orientation in 4, n-octyloxybenzoic acid (OOBA) at nematic-smectic C phase transition

Using homeotropic and quasi-homeotropic orientation in thin film of 4-n-octyloxybenzoic acid, we indicated intermediate smectic A-like state during the nematic-smectic C phase transition. Pseudoisotropic and focal conic textures are characteristic for homeotropic and quasihomeotropic orientations respectively. The smectic A-like state induced by the boundary conditions exists in a very short (about 0.5 °C) temperature region.     

Effect of polarity of smectic Ad molecules on the induction of the nematic phase in binary mixtures of smectics A1 and Ad

The phase diagrams are determined of binary mixtures composed of 4-n-alkylbiphenylates 4-cyanobiphenyl (n-CBB)-smectics A₁, for n < 8 and esters of 4-(trans-4′-n-alkylcyclohexyl)benzoic acid (10CPCHB, 10NPCHB, 10FOPCHB)-smectics A_d. The effect is studied of the smectic layer spacing ratio and polarity of the components on the induction of the nematic phase in the tested series of compounds. The virtual N S_Ad phase transition points in series n-CBB are estimated and the effect is discussed of the stability of the smectic phase and polarity of the molecules of the mixture components on the width and position of the nematic gap.     

The influence of the boundary conditions on the character of the phase transition nematic-smectic C

The possibility is investigated for inducing the intermediate smectic A structure in substances with nematic and smectic C phases by the boundary forces. Different geometries are used: homeotropic, homogeneous and tilted under a different angle toward the supporting substrates of the liquid crystal cell. At homeotropic and at tilted orientation where the molecules tilt toward the supporting substrates is different from the molecule tilt in the smectic layer, an intermediate smectic A structure is observed at the transition nematicsmectic C in a narrow temperature interval. In this case the phase transition nematicsmectic C extends and transforms into phase transition of second order. At homogeneous orientation and at tilted orientation of an angle equal to the molecule tilt in the smectic layer, the transition nematic-smetic C carried out in two stages, as partially it begins on the surface still in the nematic phase and terminates at the temperature of the phase transition N-Sc. The influence of the boundary forces depends essentially on the energy of the phase transition N-S_C of the substances.     

Calorimetric Study of Crystalline and Liquid-Crystalline Polymorphism in the Homologues of Terephthal-bis-n-alkylaniline

The phase sequences of the homologues with n (the number of carbon atoms in the terminal alkyl chains) from 2 to 8 are obtained. At low temperatures, i) several crystalline modifications are found in each of the members with n = 4, 5, and 6 and ii) the monotropic transitions between crystal and smectic phase are observed in almost all the members. At intermediate temperature, iii) between the smectic H and C phases, the smectic F phase is found in the homologues with n ≥ = 5 by morphological observation or by a rheological method. The constancy of the temperature of the S_H(or S_F) – S_c transition with respect to “and broadening of the temperature range of S_H with increasing n in the expense of nematic phase are worthy of note. The even-odd effect of the end chain length n is observed very distinctively on the crystal melting and clearing point. Proton NMR measurement reveals a large mobility in the terminal alkyl chains in the crystal of the member with n = 6.     

Mesomorphism dependence on molecular rigidity with reference to ‒CH˭CH‒ unit of central bridge

A novel ester homologous series of rich mesomorphism and low temperatures with unexpected phase behaviors of eleven homologues was synthesized and studied with a view to understanding and establishing the relation between mesomorphic behaviour and the molecular structure of a series 4-(4′-n-alkoxybenzoyloxy)-4″-chlorobenzyl cinnamates. All the members of the novel series are enantiotropically smectogenic and the octyloxy (C₈) to hexadecyloxy (C₁₆) homologues are enantiotropically nematogenic, in addition to smectogenic. Odd–even effect is observed for Sm?I/Sm?N transition curve but it is absent for N?I transition curve. Textures of nematic phase are threaded or Schlieren and that of the smectic phase are fan shaped or batonates of smectic-A type phase or Smectic-C type for C₁₆ homologues as judged directly from a heating stage of an optical polarizing microscopy. Analytical and spectral data confirmed the molecular structures of novel homologues. Mesomorphic properties of present series are compared with the structurally similar other known series. The average smectic and nematic thermal stabilities are 92.78°C and 100.8°C, respectively. Mesophase length minimum to maximum for smectic and nematic are 21.0°C to 31.1°C and 8.4°C to 42.6°C respectively. Thus, the present novel series is partly nematogenic and fully smectogenic with considerable degree of mesomorphism and low melting type.     

Observation of Intermediate Smectic A Structure at the Phase Transition Nematic-Smectic C in 4,4′-di-n-Heptyloxyazoxybenzene

Using different boundary conditions in thin film of 4,4′-di-n-heptyloxyazoxy benzene and studying the microscopic textures as well as the depolarized Rayleigh light scattering, an intermediate smectic A-like state during the nematic-smectic C phase transition was observed.     

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.     

The Order-Disorder Phase Transition in Liquid Crystals as a Function of Molecular Structure. I. The Alkyl Cyanobiphenyls

The pretransitional behaviour of a homologous series of mesomorphic compounds, the alkyl cyanobiphenyls (CNρρC _n H _{2n + 1}) for n = 5–12, has been studied as a function of temperature by light scattering in the isotropic phase. The higher homologues, n = 8–12, exhibit a smectic A phase that becomes increasingly important at the expense of the nematic phase for increasing n and for n = 10 and 12 no nematic phase is observed. We have shown from light scattering and differential scanning calorimetry measurements that the presence of the smectic A phase changes markedly the pretransitional behaviour, and gives rise to two distinct pretransitional regions. The first region is for temperatures greater than ～3°C above the clearing temperature T_c where the systems exhibit a typical pretransitional behaviour adequately described by the phenomenological Landau-de Gennes model of a second order phase transition with an intervering first order transition at T_c . The constants of this model for this region are given and show a distinct odd-even effect. The second region is close to T_c where a strong divergence from the already critical behaviour is observed. This secondary divergence is observed to be a function of the alkyl chain length and its conformation, and is attributed to coupling between smectic A like layers and the orientational order parameter in the isotropic phase.     

Dielectric behaviour of the smectic I phase

The dielectric behaviour of 4-n-butyl-4′-n-dodecyloxyazobenzene was investigated in the smectic A, C and I phases from 10² to 3 ṁ 10⁶ Hz. In all phases a dielectric relaxation process could be found which is connected with the reorientation of the molecules around their short molecular axes. At the phase transition S_C/S_I a step of one decade was observed in the relaxation frequencies.     

Phenomenological model of phase transitions between isotropic, nematic, and smectic phases in liquid crystals

The existence of the biaxial smectic phase SmA _b has been proved in the model of the Landau potential with two (nematic and smectic) interacting order parameters.     

Phase Transition Studies of the Liquid Crystal Pentyloxybenzylidene Phenylazoaniline

Phase transition studies of the liquid crystal pentyloxybenzylidene phenylazoaniline are investigated with density and ultrasonic velocity measurements. The density variation with temperature confirms that the isotropic liquid-nematic, nematic-smectic A and smectic A-smectic B transitions are of first order. The temperature variation of ultrasonic velocity confirms all the phase transitions. The adiabatic compressibility (β_ad), Rao number (R_n) and Molar compressibility (B) are estimated from density and ultrasonic velocity.     

Dielectric relaxation in nematic,smectic A and C phases in the MHz region

The dielectric properties of four 4-n-alkyloxyphenyl 4-n-alkyloxybenzoates with nematic, smectic C and partly additional S_A phases were investigated. In 2 substances for ϵ′ reproducible values also in the smectic phases resulted allowing to conclude on a good orientation in the samples. In all 4 substances the dielectric relaxation in the MHz region was measured and the respective activation energies were determined. The molecular mobility in the S_C phases is higher than in the S_A phases, however comparable with that of the nematic phases. In all 3 phase types a single relaxation mechanism exists, which is explained as rotation of the molecules around a short axis.     

Mesomorphism dependence on molecular rigidity

A novel ester homologous series of thermotropic liquid crystal (LC) has been studied with a view to understanding and establishing the relation between LC property and the molecular structure. The series consists of 11 members, the C₁–C₅ and C₁₆ members of the series are nonliquid crystals. LC properties commence from the C₆ homolog and continue up to the C₁₄ homolog as enantiotropic nematic and smectic in addition to nematic. Transition temperatures of the homologs were determined by an optical polarizing microscope equipped with a heating stage. Textures of nematic phase are threaded or Schlieren and that of smectic is focal conic of the type-A. Analytical and spectral data confirm the structures of homologs. Thermal stability for nematic is 93 °C and 136 °C, respectively. The N–I and Sm–N transition curves of phase diagram do not exhibit odd-even effect. The N–I transition curve partly behaves in an abnormal manner. The Cr–I and Sm–N transition curves behave in normal manner. The LC behavior of the present series is compared with structurally similar known homologous series.     

Smectic C-to-Nematic Transition in p-n-Heptyloxybenzylidene-p-aminobenzoic Acid

The results on the phase transitions in p-n-heptyloxybenzylidene-p-aminobenzoic acid are reported. The microscopic and X-ray studies show that the compound goes over from smectic C to nematic phase directly. The transition entropies and specific heat are determined using differential scanning calorimetry. The translational order parameter is determined using low angle X-ray intensity measurements. The tilt angle in smectic C phase is found to be 56° and is independent of temperature. The X-ray data also lead to the conclusion that the compound exists as a dimer.     

The Structure of Lyotropic Nematic Decylammoniumchloride and Bromide Systems by PMR of Monomethyltin Complexes and by Microscopic Studies

The pmr spectrum of methyltintrichloride in aqueous micellar solutions of decylammoniumchloride and KCl, and of decylammoniumbromide and KBr was investigated. The large scalar SnH couplings of 134.0 Hz and 130.2 Hz respectively indicate the formation of six coordination complexes CH₃SnCl₅ ^{- -} and CH₃SnBr₅ ^{- -} in the micellar solutions, but the geometrical structure of the CH₃Sn moiety is little affected by the complex formation. The complexes orient with their symmetry axis preferably parallel to the nematic axis.

In microscopic studies on selected mixtures a reversible first order phase transition was observed between nematic and isotropic micellar solution at about 45°C and a reversible transition between a lamellar smectic phase and the nematic phase at about 30°C that appears to be of second order. The optical observations and the orientation of the methyltin complex indicate that the nematic solutions have micelles of a bilayer structure.     

Magnetic Field Dependence of Laser Light Scattering through CBOOA in Nematic Phase

In the nematic phase of homeotropically aligned liquid crystals which have the smectic A phase at lower temperature, interference rings have been observed above some threshold magnetic field H_c which nearly coincides with the ocurrence of Freedericksz transition, only for the light polarized parallel to the direction of magnetic field. This interference ring disappears with increasing magnetic field above second threshold H_s . The origin of these interference rings is explained tentatively by a periodic deformation of bulk directors.

The bend elastic constant of CBOOA estimated from the measurements of the interference ring as a function of temperature, diverges with the critical exponent (0.5 ± 0.02) near the smectic A-nematic transition temperature and agrees well with a recent suggestion of McMillan based on the mean field theory.     

The Effect of Trifluoromethyl and Difluoromethoxy Groups on Mesomorphic Properties

Abstract

This paper describes the effect of terminal substituent on the mesomorphic properties in 3-and 4-(4-alkoxyphenoxycarbonyl)phenyl 3- and 4-R-benzoate and 4-(4-alkoxybenzoyloxy)phenyl 2-, 3-, and 4-R-benzoates (R = CF₃, OCF₃, OCF₂H). The meta-trifluoromethoxy and para-difluoromethoxy compounds tend to show a smectic C phase, as well as smectic A and nematic ones, and introduction of a chiral carbon in the alkoxyl group induces the chiral smectic C one.