Phase transition and some physical properties of binary mixtures of two nematogenic compounds showing induced smectic phase

The binary mixtures of nematogenic compounds 4-n-pentyl phenyl 4-n′-hexyloxy benzoate (ME6O.5) and 4-cyanophenyl 4-pentyl benzoate (CPPB) show the presence of induced smectic phase. In this article, we report the phase diagram and the results of refractive index, density, static dielectric permittivity and X-ray diffraction measurements of different binary mixtures of (ME6O.5?+?CPPB) throughout the entire composition range. The density and refractive index values have been analysed to obtain orientational order parameters. The various physical properties of the system have been discussed on the basis of the phase diagram.     

Optical and dielectric properties of the mesogen 4-cyano-4′-n–octyl biphenyl as a function of temperature

The effect of temperature on certain optical and dielectric properties of one member, namely 4-cyano-4′-n–octyl biphenyl (8CB) of the mesogenic series 4-cyano-4′-n–alkyl biphenyl (nCB), is reported. The dependence of the ordinary and extraordinary components of polarisability, α_o and α_e, on temperature is studied using a He–Ne laser beam, and the variation of orientational order parameter with temperature in the entire mesogenic phase determined from the optical studies. The dependence of the effective molecular dipole moment, μ_eff, in the liquid-crystal phase, and the angle of inclination, β, of the dipole moment with the preferred direction have been investigated. An experimental estimate of the correlation factor ‘g’, which is indicative of the nature of the molecular association in the mesophase, has been obtained.     

Dielectric spectroscopy of a high-polarization ferroelectric liquid crystal

Dielectric spectroscopy investigations in the frequency range 50?Hz to 1?MHz have been carried out on a new ferroelectric liquid-crystalline material (S-(-)-4-(2-n-hexylpropionyloxy)biphenyl-4′-(3-methyl-4-decyloxy)benzoate) possessing a relatively large spontaneous polarization (P _s?～?240?nC?cm^?2) and containing a lateral methyl group on the aromatic ring of the alkoxybenzoate unit. The effect of temperature on the dielectric relaxation modes has been investigated in the SmC* and N* phases. From dielectric dispersion data, relaxation frequency and dielectric strength of all detected relaxation modes have been evaluated and discussed. A new surface-like mode of relaxation frequency ～11?kHz and dielectric strength 3.8, is seen to appear in the SmC* phase.     

Induced twisted-grain-boundary phases in the binary mixtures of a cholesteric and a nematic compound

Thermodynamical, optical-texture and dielectric studies have been performed to study the phase diagram of the binary system of 5-cholesten-3β-ol-octanoate and 4-n-nonyloxybenzoic acid. It is observed that low concentrations of 5-cholesten-3β-ol-octanoate (2–30?mol?%) in 4-n-nonyloxybenzoic acid induce a mean-field phase diagram derived by Renn within the framework of the chiral Chen–Lubenski model. Various optical textures of the twisted-grain-boundary (TGB) phases under different conditions of molecular anchoring have been observed. Weak transitions related to the TGB phases have been detected by temperature dependent dielectric spectroscopy.     

On some liquid crystalline phases exhibited by compounds made of bent-core molecules and their mixtures with rod-like molecules

In most homologous series of compounds made of bent-core (BC) molecules, the B₂ B₁ and B₆ phases occur as the chain length decreases. We have studied binary mixtures of the compound 1,3-phenylene bis[4-(3-methylbenzoyloxy)]4-n-dodecylbiphenyl 4’-carboxylate (BC12) which exhibits the B₂ phase with the compound 4-biphenylyl 4’-n-undecyloxybenzoate (BO11) made of rod-like (R) molecules. We find the above sequence of occurrence of the B phases with increasing concentration of BOH. In this paper we describe the physical origin for the formation of these phases in both pure compounds and in the mixtures. We have also found the occurrence of the biaxial smectic A phase when the BO11 concentration is increased to 87–95.5 mol%. We also report on another binary system composed of BC12 and 4-n-octyloxy 4’- cyanobiphenyl (8OCB) made of R molecules. This system exhibits the biaxial smectic A phase down to 30°C. Using polarized infrared spectroscopy we find that the mutual orientation of the R and BC molecules in the SmA_db liquid crystal is such that the arrow axes of the BC molecules are along the layer normal of the partial bilayer smectic structure formed by the rods. We also describe unusual growth patterns obtained when the nematic phase transforms to the SmA_db phase in a mixture with 24 mol% of BC12.     

Pretransitional dielectric properties of nematogenic 4-cyanophenyl-4′-n-heptylbenzoate

This article presents results of the static and dynamic dielectric studies performed for mesogenic 4-cyanophenyl-4′-n-heptylbenzoate in the isotropic (I) and nematic (N) phases. Pretransitional phenomena are observed in the vicinity of I–N phase transition as an anomalous temperature behavior of both the static and the dynamic dielectric properties of the compound. The temperature dependence of the static permittivity is correlated with the entropy change induced by the probing electric field while an anomalous behavior of the dielectric relaxation directly points out for a subdiffusional Brownian rotation of mesogenic molecules in the vicinity of the phase transition.     

Critical behavior in the vicinity of nematic to smectic A (N–SmA) phase transition of two polar–polar binary liquid crystalline systems

Phase diagram, critical behavior and order of the nematic (N)–smectic A (SmA) phase transition of two polar–polar binary systems (i) 4-n-heptyloxy-4′-cyanobiphenyl (7OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB); (ii) 4-n-octyloxy-4′-cyanobiphenyl (8OCB) and 4-n-nonyloxy-4′-cyanobiphenyl (9OCB) by means of a high-resolution temperature scanning measurement of birefringence have been reported in this work. A simple power law analysis has been adopted to extract the specific heat critical exponent (α′) at N–SmA transition from birefringence data. The α′ for N–SmA transition indicates a uniform crossover behavior and has appeared to be non-universal in nature. With increasing concentration of the higher homologues for both the binary systems, the N–SmA transition reveals a strong tendency to be driven towards the tricritical nature. The 3D-XY limit (i.e. α′ = ?0.007) for N–SmA transition reaches at the concentration x_8OCB = 0.28 corresponding to the McMillan ratio 0.914, whereas the tricritical point has been found to appear near x_9OCB = 1.0 corresponding to McMillan ratio 0.992.     

(1-x)MgAl2O4-xTiO2 dielectrics for microwave and millimeter wave applications

The MgAl₂O₄ ceramics were prepared by the conventional solid-state ceramic route and the dielectric properties studied in the microwave frequency region (3–13 GHz). The phase purity and crystal structure were identified using the X-ray diffraction technique. The MgAl₂O₄ spinel ceramics show interesting microwave dielectric properties (ε_r=8.75, Q_uxf=68900 GHz (loss tangent = 0.00017 at 12.3 GHz), τ_f=-75 ppm/°C). The MgAl₂O₄ has high negative τ_f, which precludes its immediate use in practical applications. Hence the microwave dielectric properties of MgAl₂O₄ spinels were tailored by adding different mole fractions of TiO₂. The ε_r and Q factor of the mixed phases were increased with the molar addition of TiO₂ into the spinel to form mixtures based on (1-x)MgAl₂O₄-xTiO₂ (x=0.0-1.0). For x=0.25 in (1-x)MgAl₂O₄-xTiO₂, the microwave quality factor reaches a maximum value of Q_uxf=105400 GHz (loss tangent = 0.00007 at 7.5 GHz) where ε_r and τ_f are 11.035 and -12 ppm/°C, respectively. The microwave dielectric properties of the newly developed 0.75MgAl₂O₄-0.25TiO₂ dielectric is superior to several commercially available low loss dielectric substrates. PACS 77.22.-d; 84.40.-x; 81.05.Je     

Orientational order and distribution function in nematic 1-(4-trans hexylcyclohexyl)-4-[(2-4-isothiocyanato phenyl)ethyl] benzene

The refractive indices (n _e,?n _o) and density have been measured as a function of temperature in the liquid-crystalline and liquid phases of nematic 1-(4-trans hexylcyclohexyl)-4-[(2-4-isothiocyanato phenyl)ethyl] benzene. The molecular polarizability and orientational order parameter have been computed using the Neugebauer anisotropic local field model. The distribution function f(β), and hence the higher order parameter ?P ₄?, and nematic pair-potential have been computed at different temperatures in the nematic phase.     

Effect of aerosil dispersions on the nematic-to-isotropic interface

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil ρ_s ( ≤0.1 g/cm^3) regime, the calculated values of the interface velocity v(T,ρ_s), the interface thickness κ(T,ρ_s), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4^′- cyanobiphenyl and 4-n-heptyl- 4^′- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1     

Phase transitions in sol-gel derived Eu-doped PZT ceramics

Polycrystalline samples of Pb_1-z Eu _z (Zr_0.60Ti_0.40)_1-z/4O₃ (z = 0.07, 0.08 and 0.10) (abbreviated as PEZT) were prepared through the metal-alkoxide sol-gel route. X-ray diffraction analysis indicates that the PEZT compounds (nearly single phase) or solid-solution can be formed at 500°C through this route. The pellet samples sintered at 1300°C for 7 h have high density. SEM study shows the uniform distribution of spherical grains on the sample surface. Detailed dielectric studies of the compounds as a function of temperature (30–450°C) at two frequencies (10³ and 10⁴Hz) show that the broadening of the permittivity peak and transition temperature depend on Eu-ion concentration. Analysis of diffusivity (γ) of the dielectric peaks of the crystals provides its value between 1 and 2, indicating the different degrees of substitution disordering in the system. The values of remanent polarisation and coercive field decrease with increase in Eu concentration.     

Pulsed-periodic UV emitter tunable near the main absorption maximum of a DNA molecule

The spectral characteristics of a pulsed-periodic lamp with three dielectric barriers are presented for the range 220–250 nm. As the active media of the lamp, krypton (Kr)-sulfur hexafluoride (SF₆) and krypton-carbon tetrachloride (CCl₄) mixtures are tested. The use of Kr-SF₆ and Kr-CCl₄ binary mixtures in two noncommunicating volumes is shown to be more effective than the use of a Kr-SF₆-CCl₄ ternary mixture with the same amount of Kr, SF₆, and CCl₄ constituents. The emission spectrum of the lamp near the maxima of the KrF(X-B) 248-nm and KrCl(X-B) 222-nm bands can be controlled by varying the partial pressures of halogen carriers and krypton.     

Phase transitions in liquid crystal 6O.4 (p-<Emphasis Type="Italic">n</Emphasis>-hexyloxybenzylidine-p′-<Emphasis Type="Italic">n</Emphasis>-butylaniline)

DSC measurements on p-n-hexyloxybenzylidine-p′-n-butylaniline (6O.4) showed that the crystalline to liquid crystalline (K-S _H) transition at 33.7°C observed in the heating cycle does not revert even when the sample is cooled down to −100°C. Hence it is inferred that a physically stable supercooled liquid crystalline phase is formed on cooling 6O.4. To investigate the K-S _H transition further the techniques of polarized microscopy and X-ray diffraction were used which concurred with the DSC results. Quasielastic neutron scattering measurements carried out to study the re-orientational motions in the ordered phases of 6O.4 (K and S _H) show that while in the crystalline phase (at RT) the re-orientational motion is found to involve only the core of the molecule, in the S _H phase (at 45°C) the dynamics involves the whole molecule and this motion is found to persist even when the sample cools back to room temperature corroborating the results of the DSC, microscopy and X-ray diffraction.      

Ab initio studies of dielectric,piezoelectric, and elastic properties of BaTiO 3 /SrTiO 3 ferroelectric superlattices

The phonon spectrum; crystal structure of the polar phase; spontaneous polarization; dielectric constant, piezoelectric, and elastic moduli tensors for free_standing and substrate_supported superlattices mBaTiO₃/nSrTiO₃ (with m = n = 1–4) were calculated within the density functional theory. The simulation of properties of the disordered Ba_0.5Sr_0.5TiO₃ solid solution using two special quasirandom SQS-4 structures and their comparison with the properties of the superlattices revealed a tendency of the BaTiO₃-SrTiO₃ system to superstructure ordering and showed that the superlattices are thermodynamically quite stable. The ground state of the free-standing superlattice corresponds to the monoclinic polar phase Cm, which transforms to the tetragonal polar phase P4mm under in-plane compressive strain of the superlattice and to the orthorhombic polar phase Amm2 under in-plane tensile strain. With a change in the in-plane lattice parameter, in the vicinity of boundaries between neighboring polar phases, some optical and acoustic modes soften and some components of the static dielectric constant, piezoelectric, and elastic moduli tensors diverge critically.     

Dependences of the dielectric and pyroelectric properties of (1 ? x)PbFe1/2Nb1/2O3?xPbTiO3 ferroelectric ceramics solid solutions on the PbTiO3 content in a compositional range of 0 ≤ x ≤ 0.08

(1 − x)PbFe_1/2Nb_1/2O_3−x PbTiO₃ (PFN-xPT) ferroelectric ceramics with low dielectric loss and pronounced anomalies of dielectric and pyroelectric properties near the ferroelectric-ferroelectric phase transition was obtained by doping with lithium. The temperature dependence of the position of the morphotropic boundary between the rhombohedral (monoclinic) and tetragonal phases in the x-T phase diagram of the PFN-xPT system was determined for the first time.     

Flexoelastic properties of polar liquid crystals

Structural properties of liquid crystals, such as the order parameters and the orientational, radial, and direct correlation distribution functions of polar liquid crystals 4-n-heptyloxy-4′-n-cyanobiphenyl (7OCB) and 4-n-hexyloxy-benzylidene-4′-n-aminobenzonitrile (HBAB) have been calculated using a combination of numerical simulation and statistical mechanics methods. It has been shown that the calculated values of both the Frank elastic coefficients K _i (i = 1, 2, 3) corresponding to the splay, twist, and bend deformations and the flexoelectric coefficients e _i (i = 1, 3) agree with the experimental data for 7OCB. The calculated values of the same coefficients for HBAB have been published for the first time.     

银团簇上吸附氧原子与氢气作用的研究

The interactions between Ag_nO^-(n=1-8) and H₂ (or D₂) were explored by combination of the mass spectroscopy experiments and density function theory (DFT) calculations. The experiments found that all oxygen atoms in Ag_nO^-(n=1-8) are inert in the interactions with H₂ or D₂ at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation (PROX) of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between Ag_nO^-(n=1-8) and H₂ were explored using DFT calculations. The results indicated that adsorption of H₂ on any site of Ag_nO^-(n=1-8) is extremely weak, and oxidation of H₂ by any kind of oxygen in Ag_nO^-(n=1-8) has an apparent barrier strongly dependent on the adsorption style of the "O". These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts.     

Bent-shaped mesogenic oxadiazoles and thiadiazoles with terminal methyl group

Rod-shaped 4-methylbenzoic acid-N′-(4′-n-alkoxybenzoyl) hydrazide (series I) have been synthesized by the Schotten–Baumann reaction of 4-methylbenzhydrazide with 4-n-alkoxy benzoyl chloride using dry pyridine, as a solvent. The series I compounds have been cyclized to bent-shaped mesogenic 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-oxadiazoles (series II) and 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-thiadiazole (series III) using POCl₃ and Lawesson's reagent, respectively. The synthesized compounds are characterized by the combination of elemental analysis and standard spectroscopic methods. In series II, lower and middle members are non-mesogenic. n-Dodecyloxy to n-hexadecyloxy derivatives exhibit enantiotropic nematic mesophase. In series III, all the compounds synthesized exhibit enantiotropic nematic mesophase. n-Tetradecyloxy and n-hexadecyloxy derivatives also exhibit enantiotropic SmA mesophase. The mesomorphic properties of the series II and III used in this study are compared with each other and with other structurally related compound to evaluate the effect of different heterocyclic moieties as well as terminal substituents on mesomorphism.     

Time Dependence of the Capacitance of a MOS Silicon Tunnel Diode under the Influence of Hydrogen

The results of theoretical and experimental investigations into the time dependence of the capacitance of MOS silicon diodes with a thin tunnel dielectric and a palladium field electrode under the influence of a gas hydrogen-containing mixture are presented. Analytical expressions are derived that describe the time dependence of the capacitance of the space charge region (SCR) of the MOS tunnel diode operating in depletion and enrichment regimes. It is demonstrated that the time dependence of the SCR capacitance of the MOS diode placed in the gas mixture is caused by diffusion of hydrogen atoms from the field electrode to the SiO _x –n-Si interface. The relaxation time of hydrogen atom accumulation at the interface is 47 s for the diode with a SiO _x layer thickness of 3.7 nm placed in the gas mixture with 0.3 vol.% of H₂. It has been established that the flat band voltage and the SCR capacitance of the MOS diode change under the influence of the gas mixture due to the decreased density of surface acceptor states at the SiO _x –n-Si interface, the increased positive charge density in the dielectric, and the decreased contact potential difference.