Dielectric investigations in the nematic and hexatic smectic B phases of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

Temperature-dependent dielectric characterization of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl (HIEB), which exhibits smectic B and nematic phases, has been carried out over the frequency range of 1 Hz to 10 MHz for homeotropic and planar alignment of sample molecules. This compound shows positive dielectric anisotropy (Δε = ε _∥ ? ε _⊥ > 0) in the nematic (N) phase. One mode of dielectric relaxation showing Arrhenius behaviour has been detected in the hexatic smectic B (SmB) phase. Various electrical parameters, namely, dielectric anisotropy, relaxation frequency and activation energy, have been determined in the N and SmB phases.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was reinvestigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and smectic A (SmA) phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. Both the 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes were recognized, respectively.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was re-investigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and SmA phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, in which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes, respectively, were recognized.     

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.     

Influence of rhenium and ruthenium on the local mechanical properties of the γ and γ′ phases in nickel-base superalloys

The effect of rhenium and ruthenium on the hardness of the γ′ precipitates and the γ matrix in nickel-base superalloys was investigated using a nanoindenting atomic force microscope. The partitioning behaviour of the alloying elements and the lattice misfit between the γ and γ′ phase were determined in fully homogenised samples to explain the alloying effects. Rhenium strongly strengthens γ as it predominantly partitions to γ and has a strong solid solution-hardening effect. Ruthenium strengthens both γ and γ′ due to a more homogeneous partitioning behaviour. Ruthenium was found to cause less partitioning of rhenium to γ. This results in a stronger increase of the γ′ hardness. The change in the nanoindentation-derived hardness of both phases could be mainly attributed to the solid solution strengthening of Re and Ru.     

Molecular rotation in liquid crystals selective deuterium spin-lattice relaxation times in the nematic mesophase of 4-cyano-4′-d17-n-octylbiphenyl

The Gibbs ensemble is used to simulate the liquid–liquid equilibria of binary mixtures containing dipolar and non-polar components.The interactions of the dipolar fluid are calculated using the Keesom intermolecular potential. The liquid–liquid coexistence properties are reported for different pressures and different combinations of dipolar/non-polar molecules. The critical properties of the mixtures are estimated. The ability of a dipole to induce phase separation is influenced by the dispersion energy of the molecule. Phase separation is enhanced if the dipolar molecule is also the component with the greatest dispersion energy.     

Theoretical estimation of mesogenic characteristics of 4-methyl (2′-hydroxy,4′-n-hexadecyloxy) azobenzene – a nematic liquid crystal

The compound 4-methyl (2′-hydroxy,4′-n-hexadecyloxy) azobenzene was synthesized by Prajapati and co-workers (Mol. Cryst. Liq. Cryst. 369 (2001), pp. 37–46). Subsequent experiments (D. Pal, [PhD thesis], University of Lucknow, Lucknow, India, 2007) confirmed that the compound exists in nematic phase for a small range of temperature (72°C–80°C). In the present work, optimization of molecular geometry has been carried out by employing the Gaussian 03 suit of programs without any constraint using density functional B3LYP along with 6-31G** basis set and checked for imaginary frequencies. A detailed investigation on intermolecular interaction energy at various interacting configurations has been carried out. In order to study the mesogenic characteristics of the molecule, an attempt has been made to estimate the variation of order parameter with respect to the change in temperature as well as degrees of freedom. These studies will be helpful to understanding the mesogenic character of any molecule prior to synthesis and promises future application in molecular engineering.     

Dielectric properties of CaCu3Ti4O12–silicone resin composites

CaCu₃Ti₄O₁₂ (CCTO)–silicone resin composites with various CCTO volume fractions were prepared. Relatively high dielectric constant (ε=119) and low loss (tanδ=0.35) of the composites with CCTO volume fraction of 0.9 were observed. Two theoretical models were employed to predict the dielectric constant of these composites; the dielectric constant obtained via the Maxwell–Garnett model was in close agreement with the experimental data. The dielectric constant of CCTO–silicone resin composites showed a weak frequency dependence at the measuring frequency range and the loss tangent apparently decreases with increase in frequency.     

Anomalous dielectric behavior in the nematic and isotropic phases of a strongly polar–weakly polar binary system

We report permittivity studies in the isotropic liquid and anisotropic liquid crystalline (nematic or N) phases of a binary system, in which one component has molecules with a strongly polar longitudinal group, and the other has a weakly polar transverse group. The dielectric constant in the isotropic phase as well as its anisotropy in the N phase show, surprisingly, an anomalous non-monotonic dependence with concentration having a peak-like behavior for 10.2 mol% concentration of the weakly polar constituent. The transition between the two phases, being weakly first order, exhibits pretransitional effects signifying the appearance of the N-like regions in the isotropic phase. The coordinates of the maximum point of the convex shaped temperature-dependence of the dielectric constant in the isotropic phase, characteristic of strongly polar systems, also exhibit a non-monotonic dependence with concentration. Possible causes for these observations are discussed.     

Liquid-crystalline properties of 4-alkyl-, 4-alkyloxy and 4-halogene-4′-hydroxyazobenzene alkyloates

Twenty one esters, 4-alkyl-, 4-alkyloxy-, 4-nitro- and 4-halogene-4′-hydroxyazobenzne alkyloates have been synthesised. Basing on the DSC calorimetry and polarizing microscopy liquid- crystalline polymorphism was investigated. Five types of mesophases were identified: nematic, smectics A, C, F and unknown X (probably G).     

Effect of Pt on interdiffusion and mechanical properties of the γ and γ′ phases in the Ni–Pt–Al system

The effect of Pt on the growth kinetics of the γ′-[Ni(Pt)]₃Al ordered intermetallic phase and the γ-Ni(Pt, Al) solid solution diffusion rates of the species, hardness and elastic modulus was examined by employing the diffusion couple experimental technique. Experiments were conducted by using the β-Ni(Pt)Al phase and Ni(Pt) alloy couples, each of which had a fixed amount of Pt (5, 10 and 15 at. %) in both the end members so that the Pt content is more or less constant throughout the interdiffusion zone. The results suggest that the growth kinetics of both phases and the average effective interdiffusion coefficients of Ni and Al increase with the increase in Pt content. Nanoindentation studies across the compositional gradients show that the mechanical properties of the intermetallic phase in the superalloy are relatively insensitive to the presence of Pt but are more sensitive to the Ni/Al ratio. In contrast, the marked variation in the hardness of the γ phase were noted, increasing markedly with Al concentration in a given couple and also increasing with increasing Pt content. Possible causes for the observed variations are discussed.     

A radio-tracer study of self-diffusion in the smectic phases iso-butyl 4-(4′-phenylbenzylideneamino) cinnamate [IBPBAC]

Average translational self-diffusion coefficients, , have been determined in the smectic E, B and A phases of unaligned samples of iso-butyl 4-(4′-phenylbenzylideneamino) cinnamate. A radiotracer technique was employed which was based on the serial sectioning method used in the study of diffusion in solids. In the smectic E phase is about 1 × 10^-14 m² s^-1. The self-diffusion in the smectic B phase fits reasonably well to an Arrhenius law with an activation enthalpy of 82 kJ mol^-1. The transition from the smectic B to A phase results in a dramatic rise in . In the smectic A phase the results fit an activation enthalpy for self-diffusion of about 168 kJ mol^-1. Similarities between the diffusion in the smectic E and B phases and in plastic solids are observed.     

Electron beam irradiation induced changes in the dielectric and electro-optical properties of a room temperature nematic display material 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzoate (6CHBT)

Dielectric and electro-optical studies of a pure and electron beam irradiated liquid crystalline compound 4-(trans-4′-n-hexylcyclohexyl) isothiocyanatobenzoate have been carried out. Dielectric anisotropy, relaxation frequency, activation energy and distribution parameter of an observed non-collective mode corresponding to the molecular rotation about the short axes have been determined as a function of temperature and irradiation dose whereas threshold and switching voltages, splay elastic constant are determined as a function of irradiation dose. The relaxation frequencies initially decrease up to an irradiation dose of 40 kGy but thereafter increase due to irradiation. The activation energies are increased up to irradiation dose of 40 kGy but around 60 kGy dose of irradiation, we found decrease in the activation energy. Electro-optical measurements show the lowering of the threshold voltage with sufficient improvement in the steepness of the transmission voltage curves due to irradiation. The observed changes in the dielectric and electro-optical properties are related with the cis–trans isomerization due to electron beam irradiation.     

Smectic polymorphism of 4-decyloxybenzylidene- 4′-alkyloxyanilines and their mixtures with polar standards of mesophases

This article describes liquid crystalline properties of the homologous series of 4-decyloxybenzylidene-4′-alkyloxyanilines. Based on the polarization microscopy (POM and TOA methods) and the calorimetric (DSC) measurements a rich polymorphism has been detected. Investigated compounds exhibit nematic, smectic A, smectic C, smectic B, smectic I and G (smectic G) mesophases with their characteristic configurations. The presence of these mesophases was confirmed by the miscibility method, using 4-heptyloxybenxylidene-4′-pentylaniline as a mesophase reference. Nine other smectic standards with different polarity have been applied in order to investigate their influence on the mesophase stability.     

Dielectric properties of PIN–PT ceramics under compressive stress

Lead indium niobate, Pb(In_1/2Nb_1/2)O₃ or (PIN), is an interesting ferroelectric material, because it can be changed from a disordered state to ordered state by long-time thermal annealing. However, the temperature related to the maximum dielectric constant (T_max) of PIN in relaxor phase is low (at 1 kHz, T_max = 66 °C). In this study, to increasing T_max of PIN, lead titanate, PbTiO₃(PT) was thus added to PIN with compositions (1 − x)PIN–xPT (for x = 0.1–0.5). The influence of stress on the dielectric properties of (1 − x)PIN–xPT ceramics was then investigated. The dielectric properties were measured under various uniaxial compressive stress up to 400 MPa. The results showed that the superimposed compression load reduced the dielectric constant in 0.9PIN–0.1PT. For the other compositions, the dielectric constants first increased with the compressive stress, and then decreased when the stress was further increased up to 400 MPa. The dielectric loss tangent of all composition was found to decrease with increasing compressive stress.     

Spectral properties of naphthalimide dyes mixed with 4-heptyl-4′-cyanobiphenyl (7CB) in Langmuir-Blodgett films

Langmuir-Blodgett (LB) films formed of some fluorescent dyes, namely derivatives of 4-aminonaphthalimide, and their binary mixtures with the liquid crystal 4-heptyl-4′-cyanobiphenyl (7CB) have been studied. The electronic absorption and fluorescence spectra were recorded. On the basis of these spectra, the spectral properties of the dyes and the intermolecular interactions in ultrathin ordered films were determined. The conclusions about the tendency to the creation of aggregates by dye molecules in LB films have been drawn. The measurements of absorption by using linearly polarised light have allowed us to determine the arrangement of the dye and liquid crystal molecules on the air-solid substrate interface.     

Dielectric and orientational properties of nematogenic 4-<Emphasis Type="Italic">n</Emphasis>-octyl(4′-cyanophenyl)benzoate

Experimental studies of the dielectric properties in the nematic and isotropic phases of 4-cyanophenyl-4′-n-octylbenzoate (8CPB) have been performed in the frequency range from 50 kHz to 100 MHz. The relaxation process related to the rotation around the short molecular axis has been analysed. The results obtained have revealed that in the vicinity of the I-N phase transition, the molecular subdiffusional rotation process occurs. It is connected with the pretransitional effects which are observed both in the static and dynamic dielectric measurements. On the basis of the temperature dependence of the relaxation time in the nematic and isotropic phases, the orientational order parameter 〈P₂〉 has been determined. The values of 〈P₂〉 obtained in this way have been compared with those evaluated from the measurements of the polarized electronic absorption of the dichroic dye, dissolved as guest probe in the mesogenic host.