Structure of the Nematic Phase of Pbaba

X-ray diffraction investigations of the nematic phase (191°C - 276°C) of p-n-propyloxybenzylidene-p-amino benzoic acid have shown that this phase is a skewed cybotactic nematic phase. The diffraction patterns, obtained with aligned samples, reveal an additional surprising structural feature, - the presence of one dimensional molecular correlation in a direction parallel to the nematic director. At 192°C, it is found that the molecular unit, thus correlated, is about 37 Å in length (dimer length) and the correlation range extends up to about seven such units. This l-d correlation persists up to the N-I transition.     

A Study of 4 Nonanoate, 4’ Cyanobiphenyl Using Dielectric Relaxation Method

In this paper, the results of a dielectric absorption study for 4 nonanoate 4’ cyanobiphenyl are presented. For electric field E perpendicular to director n, a very distributed domain can be observed. It can be interpreted as resulting from the superposition of rotation and libration movements of the molecule and of intramolecular movements. For E parallel to n, the reorientational movement of the molecule is observed. The activation energy of this mechanism is lower in SmA phase at T > 30°C than in nematic phase. Moreover, if T < 25°C the activation energy increases. These variations seem to be characteristic of a partially bilayer SmA phase with the appearing of monolayer S_c domains at T < 25°C.     

Bipolar-homogeneous structural phase transition in nematic droplets formed in the polymer matrix in a magnetic field

The phase transition from the bipolar structure to the homogeneous structure in droplets formed from the nematic liquid crystal 4-n-pentyl-4′-cyanobiphenyl in poly(vinyl butyral) in the presence of a magnetic field has been investigated. The phase transition is associated with the expansion of the regions with a tilted orientation of the director in the vicinity of defects (the disappearance of boojums) and with the alignment of the nematic director lines in the bulk of the droplet in the direction of the magnetic field. In the temperature range T = 24−34°C, cyclic mutual transformations between the bipolar configuration of the nematic director and the homogeneous structure, which have a period of ∼0.5–3.5 s and result from thermal fluctuations of the order parameter, are observed in droplets 3–15 μm in size after the forming field is switched off.     

Study of Liquid Crystals in Flow: I. Conventional Viscometry and Density Measurements

Using the technique of conventional viscometry (Haake-Hoeffler Falling Ball and Ostwald-Poiseuille viscometers), we have measured the temperature dependence of the apparent viscosity of three liquid crystals: methoxybenzylidene butylaniline (MBBA), hexyloxybenzylidene amino benzonitrile (HBAB) and cyanobenzylidene octyloxyaniline (CBOOA). The measurements with the falling-ball show a small discontinuity in the apparent viscosity of (HBAB) at ～ 91°C, where the flow properties of this compound have been found to change from one flow regime in which the “classical” molecular alignment with the flow can be observed (T > 91°C) to another regime in which this alignment cannot be observed (T < 91°C). However, in spite of this small discontinuity, the apparent falling-ball viscosity which we measured for (HBAB) is still very close to the Miesowicz viscosity, η_B, obtained by constraining the director n to remain parallel to the velocity vector during the measurements. Measurements performed with the Ostwald-Poiseuille viscometer show: (i) that the apparent viscosity and the viscous heat of the nematic and smectic-A mesophases depend upon the radius of the capillary; (ii) that the apparent viscosity, in both the flow-alignment and the non-flow-alignment regimes, is very close to η_B and (iii) that there is no convincing evidence of a discontinuity in the apparent viscosity of (HBAB) at 91°C.

Our measurements of the temperature dependence of the density of the mesophases show that the isobaric coefficients of thermal expansion for (HBAB) and (CBOOA) are different in the flow alignment and in the non-flow-alignment regimes. This is consistent with the hypothesis that there is a greater degree of molecular association in the non-flow-alignment regime.     

Synchrotron X-ray diffraction study of the structure of oral stratum corneum model lipid membranes

Membranes modeling the lipid fraction of the mucous membrane of the human oral cavity have been studied by X-ray synchrotron diffraction. Ternary systems, composed of a mixture of sphingomyelin, dipalmitoylphosphatidylcholine, and dipalmitoylphosphatidylethanolamine with component weight ratios of 1: 2: 2 and 1: 2: 1, have lamellar structures in the gel phase at the physiological temperature (37°C). An inverted hexagonal phase is formed in the system with 40% dipalmitoylphosphatidylethanolamine in the temperature range of 60–70°C. This phase coexists with the liquid-crystalline lamellar phase in a narrow temperature range and completely surpresses the lamellar phase with an increase in temperature to 80°C. Multi-component oral stratum corneum membranes are characterized by several lamellar phases at 20–37°C and the coexistence of one or several lamellar phases with inverted hexagonal phase at 80–90°C.     

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.     

Mesomorphism dependence on lateral substitution of functional groups and their position in series: 4(4′-n-alkoxy benzoyloxy)-3-chloro phenyl azo-2″-methoxy benzenes

Eleven homologues of the title series were synthesized. The methyl-to-pentyl derivatives are nonmesomorphic. The nematic mesophase commences from the sixth member of the series without any smectic phase. An odd–even effect in the nematic–isotropic transition curve is not observed. The nematic mesophase appeared as a threaded or a Schlieren-type texture as observed through a hot-stage polarizing microscope. The nematic–isotropic transition temperatures are between 89°C and 127°C with the mesomorphic range varying from 9°C to 44°C at the hexyl and tetradecyl derivative of the series, respectively. The nematic–isotropic transition curve initially rises and then falls in a normal manner as the series is ascended, but it abnormally rises beyond the 10th homologue. The series is enantiotropic nematic with a middle-ordered melting type. Analytical data support the structures of the molecules. The thermal stability and some other mesomorphic characteristics are compared with structurally similar homologous series. The average nematic–isotropic thermal stability is 105.4°C.     

Tilt Angle Determination of a Smectic C Phase by Field-Induced Freedericksz Transition and x ray Investigations

A smectic C liquid crystal exhibiting positive dielectric anisotropy was oriented with the director parallel to the glass substrates. When an electric field was applied normal to the director direction a dielectric reorientation (Freedericksz transition) occurred. Dissolving a dichroic dye in the smectic C phase and applying an electric field, a guest host effect similar to nematic phases was observed. From the dielectric reorientation the tilt angle of the smectic C phase was determined at different temperatures. The tilt angles obtained by the electrooptical measurements agree sufficiently with the values measured by x ray investigations.     

Synthesis and Liquid Crystal Behavior of a Novel Ester Homologous Series

A novel ester homologous series of 4-[4’-n-alkoxy cinnamoyloxy] benzyl benzoates has been synthesized. The series consists of 12 homologues. Liquid crystal properties commence from the sixth member to the last member of the series with the exhibition of an enantiotropic nematic phase without the exhibition of any smectogenic mesophase. The remaining homologues do not exhibit liquid crystal behavior. The texture of the nematic phase is of the threaded or Schlieren type. The solid-nematic or isotropic transition curve adopts a zigzag path and the nematic-isotropic transition curve steeply rises and then falls in the phase diagram and behaves in normal manner. An odd–even effect is absent in the nematic-isotropic transition curve with an alteration of transition temperatures. The average thermal stability for the nematic mesophase is 153.1°C, and the nematogenic temperature ranges vary from 12°C to 50°C. Analytical data confirm the molecular structures of the homologues. The Liquid Crystal properties and transition temperatures were observed through an optical polarizing microscope, equipped with a heating stage. The mesomorphic characteristics of the novel ester series are compared with other, known and structurally similar series. The novel series is predominantly nematogenic with the absence of any smectogenic character, with relatively short mesophase temperature ranges and of the middle ordered melting type.     

Optical and Dielectric Studies of Azobenzene and p-Methoxy Cinnamic Acid (p-MCA)

Compounds of azobenzene and p-methoxy cinnaraic acid were purified after repeated crystallization. In this paper studies of optical and dielectric properties of the compounds were carried out first in the solid state at room temperature (30°C). The temperature range of the nematic phase of p-MCA was found to be slightly different from the reported value. Azobenzene has a mesophase in the temperature range 66.4–68.6°C. Negative dielectric anisotropy was also observed.     

Melting and Crystallization Processes of EBBA III. Microscopic Observation

Melting and crystallization processes of EBBA (N-p-ethoxybenzylidene-p'-butyl aniline) have been studied by the method of microscopic observation. A solid sample obtained by rapid cooling (cooling rate: 40 K/min) from nematic to 5°C (sample A) shows granular texture. A band like crystal grows in sample A at room temperature. A solid sample obtained by quenching (cooling rate: 13 K/s) from nematic to about - 100°C (sample B) shows cloudy texture. In the heating process sample B transforms to a more stable crystalline form which shows mosaic texture. A needle crystal grows slowly in a supercooled nematic state, then smaller needle crystals grow rapidly around the needle crystal. The formation and transformation processes of solid modifications are explained on the basis of the idea of instability of them, and schematic phase diagram of those solid forms is presented.

Keywords: EBBA, liquid crystals, nematic, solids, crystal growth, microscopic observation     

Novel Cinnamate Esters—Synthesis and Mesomorphic Properties in Relation to Molecular Structure

A novel homologous series 4-[4′-n-alkoxy cinnamoyloxy] benzyl cinnamates consisting of 11 homologs was synthesized and studied with a view to understanding and establishing the relation between molecular structure and mesomorphic behavior of a substance. Mesomorphic behavior of the series commences from the third homolog and then continues until the last hexadecyloxy homolog. The first and second members of a series are non-mesomorphic. Nematogenic mesophase formation is observed from the propoxy homolog to the hexadecyloxy homolog, but the smectogenic mesophase formation is observed from the hexyloxy homolog to the tetradecyloxy homolog. All mesomorphic transitions are enantiotropic in nature. Transition temperatures were determined by an optical polarizing microscopy equipped with a heating stage. The textures of the nematic mesophase are threaded or Schlieren in type and that of the smectic mesophases are focal conic fan shaped of the smectic A or smectic C type. A phase diagram of the series shows a normal behavior of the transition curves with a minor abnormality of the last three homologs for the nematic-isotropic transition curve. The average thermal stability for smectic and nematic mesophases is 176.0°C and 219.3°C, respectively. Analytical and spectral data agree with the molecular structures of homologs. Mesomorphic phase length varies between 22°C and 76°C. Smectic phase length varies from 6°C to 33°C and nematic phase length varies from 22°C to 54°C. Thus, the novel present series is predominantly nematogenic and partly smectogenic. Mesomorphic properties of the novel series are compared with structurally similar other known homologous series.     

Liquid crystalline swallow-tailed compounds (II) dielectric relaxation

Dielectric investigations in the kHz-range on swallow-tailed liquid crystals show a strong decrease of the dielectric constant as well as of the dielectric loss parallel to the nematic director with decreasing temperature. In the perpendicular direction no strong anomaly has been observed. By consideration of X-ray data of the S_A phase the dielectric results can be interpreted by the dipole-dipole interaction which is forced by the anisotropy of repulsive forces of the respective molecules.     

Crystallization of amorphous Ni55Pd35P10 alloys

The crystallization of Ni₅₅Pd₃₅P₁₀ alloys was examined by isochronal resistivity and hardness measurements, along with observations of the phase transformation in the heating stage of a transmission electron microscope (TEM). The resistivity temperature coefficient between 26 and 250°C is low (9.38 × 10^?5/°C); a few metastable phases form on crystallization. The hardness-temperature curve shows the hardness to increase as the metastable phases appear.     

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.     

Spontaneous homeotropic alignment of nematic liquid crystals induced by a double-armed side chain liquid crystalline polymethacrylate

A liquid crystalline polymethacrylate having two cyclohexylphenyl mesogens on its side-chain (PMG0) was synthesized by the radical polymerization of the corresponding methacrylate monomer (MG0). PMG0 exhibited a smectic A phase around room temperature showing a focalconic fan texture in POM observations and a broad diffusion in a wide angle range of its WAXD profile. Upon slow cooling at ?1 °C min^?1 from the isotropic melt, PMG0 exhibited spontaneous homeotropic alignment between two native glass surfaces. A mixture of the commercial nematic liquid crystal (ZLI-4792) containing 1.0 wt% PMG0 also exhibited a homeotropic alignment, which easily covered hydrophilic surfaces such as glass or polyacrylamide.     

Study of mesomorphism dependence on molecular flexibility of an azoester series containing a napthyl unit

A novel azoester homologous series of liquid crystalline (LC) compounds: RO?C₆H₄-COO?C₁₀H₆-N:N-C₆H₄?OC₄H₉(n) without lateral substitution has been synthesized and studied with a view to understanding and establishing the effects of molecular structure on thermotropic LC substances with reference to tailed-end group. The novel homologous series consists of 13 homologs (C₁ to C₁₈) whose nematogenic and smectogenic mesomorphism commences enantiotropically from C₆ and C₁₂ members of the series, respectively. The C₁₂–C₁₈ homologs are smectogenic and C₆–C₁₈ are nematogenic, of which C₁₂–C₁₈ homologs are smectogenic plus nematogenic. The C₁–C₅ homologs are nonmesogenic. Transition temperatures and the textures of the homologs were determined and identified by an optical polarizing microscope (POM) equipped with a heating stage. Textures of a nematic phase are threaded or Schlieren and that of the smectic phase are of the type A or C. Transition curves Cr-M/I, Sm-N and N-I of a phase diagram behaved in normal manner except N-I transition temperature of C₁₀ homolog which deviated by 9°C–10°C from normal behavior. N-I transition curve exhibited odd-even effect. Analytical, spectral, and thermal data confirms the molecular structures of homologs. Thermal stability for smectic and nematic are 115.5°C and 138.5°C, respectively whose corresponding mesophaselengths are varied from 10.0°C to 16.0°C and 13.0°C to 24.0°C, respectively. Group efficiency order for smectic and nematic are derived from comparative study of structurally similar analogous series; as smectic: ?OC₄H₉ (n) > ?CH₃ > ?H; Nematic: ?H > ?OC₄H₉ (n) > ?CH₃     

Mesomorphism dependence on molecular rigidity and flexibility

A novel homologous series of liquid crystalline properties is synthesized and studied with a view to understand the effect of molecular structure on its thermotropic properties. Novel homologous series consisted of thirteen homologs. All the homologs are enantiotropically smectogenic with absence of nematic property even in the monotropic condition. Textures of the homologs as observed through an optical hot stage polarizing microscopy. The mesophase temperature range vary minimum from 6.0°C to a maximum 37.0°C at the methyloxy and propyloxy derivatives of a series respectively with its thermal stability (Sm–I) 127.0°C. Transition curves of a phase diagram behaved in normal manner. Odd–even effect is observed for Sm–I transition curve.     

Mesomorphism Dependence on the Position of Substitution of a Pair of Esters

A novel homologous series of ethylene derivatives of thermotropic liquid crystals has been synthesized. The methoxy to octyloxy derivatives are nematogenic, the decyloxy to tetradecyloxy derivatives are smectogenic, in addition to nematogenic, and the hexadecyloxy homologue is smectogenic only. All the members of the series are enantiotropically mesogenic. Thermotropic behavior was determined by an optical polarizing microscope equipped with a heating stage and Differential Scanning Calorimetry (DSC) study. Analytical and spectral data confirm the molecular structures of homologues (infrared, nuclear magnetic resonance, mass spectra, X-ray, and DSC data). Textures of the nematic phase are threaded or Schlieren and that of smectic phase are focal conic fan-shaped of smectic A or C. Transition curves of the phase diagram behave in a normal manner except one or two deviations from the normal trend. The mesophase range (Sm+N) varies from 3°C to 44°C. The average thermal stability for smectic is 93°C and that for nematic 117.4°C. The LC behavior of the novel series is compared with a structurally similar known series.     

Influence of TiO2 and ZnO nanoparticles on orientational order parameter of LC compounds – An optical study

In the present paper ZnO and TiO₂ nano particles are dispersed in Cyano-biphenyl liquid crystalline compounds (n?=?7, 12). The thermal polarizing microscopy and differential scanning calorimetry techniques are employed to measure the transition temperatures. The Nematic transition temperatures are decreased by 2.34?°C and 1.53?°C in Heptylbiphenyl, 1.07?°C and 1.12?°C in dodecylbiphenyl compounds due to the dispersion of nanoparticles. The refractive indices and Newton’s rings methods are exploited to measure birefringence at different temperature in nematic phase. The orientational order parameters are estimated by finding the birefringence in perfect order. The orientational order parameter is increased in nanoparticles dispersed liquid crystals when compare to pure liquid crystalline compounds.