Orientational order in three nO.m liquid crystalline compounds

Refractive index and density measurements have been carried out on three nO.m liquid crystalline compounds, namely, 4O.2, 4O.3 and 1O.10 belonging to the N-(p-n-alkoxybenzylidene)-p-n-alkylaniline series. From the data, the orientational order parameter has been estimated using Vuks and Neugebauer local field models. Furthermore, the orientational order parameter has been calculated directly from refractive index data employing the Vuks scaling factor method, Neugebauer f(B) parameter, effective geometry parameter and a method proposed by Kuczyński et al. It is observed that order parameter values estimated from different methods agree well near the nematic–isotropic transition and diverge as the nematic phase attains equilibrium. The temperature gradient of refractive indices and the nematic crossover temperatures have also been estimated for these compounds. The results obtained are compared and discussed.     

Phase transition studies in polymesomorphic compounds

Summary The structural parameters of theS _A andS _B mesophases and the phase transitionS _G -S _B andS _B -S _A of the compound N-(p-n-octyloxybenzylidene)p-n-butyl aniline were investigated by X-ray diffraction. This work is complementary to the previous structural determination in the crystalline solid phase andS _G phase of the same compound. TheS _B hexagonal lattice parameters atT=66°C area=b=(5.03±0.01) ? andc=(27.6±0.2) ?. TheS _A structural data atT=80°C are layer thicknessd=(26.9±0.2) ? and intermolecular distanceD=(5.04±0.05) ?. The interlayer and the in-plane intermolecular distances were obtained as a function of temperature through all the mesophases. Pretransitional effects were observed at theS _G -S _B phase transition, which corresponds to a progressive reduction to zero of the molecule inclination angle with respect to the normal to the smectic layers. The layer thickness in theS _A phase appeared smaller than that in theS _B due to molecular axial fluctuations. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Birefringence and phase transitions in liquid crystals

The birefringence of liquid-crystalline phases is the result of the parallel order of molecules exhibiting a polarizability anisotropy. The magnitude and sign of the birefringence are determined by the structure and order of the liquid-crystalline phase types as well as by the polarizability properties of the constituent molecules. The characteristic change of the birefringence at phase transitions between liquid-crystalline phases indicates more or less pronounced structural changes. The temperature dependence of the birefringence is due to the temperature change of the molecular order.

It is shown that the structural variety of the liquid crystalline state is reflected by a big variety of their optical anisotropy properties.     

Low viscosity, high birefringence liquid crystalline compounds and mixtures

Two types of fast switching mixtures with high positive dielectric anisotropy were described. The first type, with a birefringence below 0.3, was designed for devices operating at room or lower temperatures and the second one, with a birefringence higher than 0.3 for devices operating at elevated temperatures.     

Ringed spherulitic and undulated textures in the nematic phase of a mixture of trans-4-hexylcyclohexanecarboxilic and benzoic acids

We present a polarizing optical microscopy study of a liquid-crystal mixture of trans-4-hexylcyclohexanecarboxilic (C6) and benzoic acids. Both materials have carboxylic groups that can form dimers through hydrogen bonding. The mixture is nematic at room temperature and has the clearing point at 88°C. The nematic phase shows ringed spherulites, sometimes looking like spiral structures, and undulated textures, which remain visible when heating the sample till 71°C. This is the temperature of a texture transition inside the nematic phase.     

Chromonic liquid crystalline phase transition involving a biphasic region of nematic and hexagonal phases

We report the results of our studies on the optical and thermal properties of binary mixture of two compounds viz. abietic acid and poly ethylene glycol (PEG). The mixture shows a very interesting co-existent biphasic region of lyotropic nematic (N + I) and intermediate hexagonal (M + I) phases, sequentially when the specimen is cooled from its isotropic phase at different concentrations of abietic acid in PEG. The aggregated molecular size has been confirmed by X-ray studies. The temperature variation of optical anisotropy, electrical conductivity, ultrasonic velocity, and molar and adiabatic compressibility has also been discussed.     

The influence of the lithium concentration on the low-temperature phase transition in phases LixV2O5 with shcherbinaite-structure

With high-resolution Guinier diffractometry the low-temperature stability of the intercalated lithium vanadium oxide bronzes ε - Li _x V₂O₅, with 0.32 ≤ x ≤ 0.80, was studied. In the course of these investigations a line of thermally induced structural phase transitions was detected in the x-T field. The reversible continuous phase transitions can be described in terms of a classical Landau-type theory. They are proper (potentially) ferroelastic with an one-dimensional order parameter transforming as the Γ⁺ ₃ irreducible representation of space group Pmmn. The symmetry is orthorhombic P2₁/m2₁/m2/n above T_c , but monoclinic P2₁ /m11 below T_c .

The transition temperatures depend strongly on the stoichiometry of the intercalated lithium ions. The critical exponent β, and, hence, the character of the phase transition do not change significantly with the lithium concentration. However, for x ≤ 0.52 corresponding phase transitions could not be detected, supporting the idea that the accepted stability field of ε - Li _x V₂O₅(0.32 ≤ x ≤ 0.80) should be subdivided into two fields, ε- and ε'-phase, according to whether the phase transition occurs, or not. The influence of the reduction rate of the intercalated phases on the critical parameters will be discussed in terms of a mean-field theory.     

Pressure induced phase transformations and band structure of different high pressure phases in tellurium

We report here high-pressure x-ray diffraction (XRD) studies on tellurium (Te) at room temperature up to 40 GPa in the diamond anvil cell (DAC). The XRD measurements clearly indicate a sequence of pressure-induced phase transitions with increasing pressure. The data obtained in the pressure range 1 bar to 40 GPa fit five different crystalline phases out of Te: hexagonal Te (I) → monoclinic Te(II) → orthorhombic Te (III) → Β-Po-type Te(IV) → body-centered-cubic Te(V) at 4, 6.2, 11 and 27 GPa, respectively. The volume changes across these transitions are 10%, 1.5%, 0.3% and 0.5%, respectively. Self consistent electronic band structure calculations both for ambient and high pressure phases have been carried out using the tight binding linear muffin tin orbital (TB-LMTO) method within the atomic-sphere approximation (ASA). Reported here apart from the energy band calculations are the density of states (DOS), Fermi energy (E _f) at various high-pressure phases. Our calculations show that the ambient pressure hexagonal phase has a band gap of 0.42 eV whereas high-pressure phases are found to be metallic. We also found that the pressure induced semiconducting to metallic transition occurs at about 4 GPa which corresponds to the hexagonal phase to monoclinic phase transition. Equation of state and bulk modulus of different high-pressure phases have also been discussed.     

Effects of copper nanoparticles on the thermodynamic,electrical and optical properties of a disc-shaped liquid crystalline material showing columnar phase

Thermodynamic, electrical and optical studies have been carried out on a discotic liquid crystal (DLC), namely 2, 3, 6, 7, 10, 11-hexabutyloxytriphenylene (possessing columnar phase) and its copper nanoparticles (0.6 wt%) based composite. The ionic conductivity of DLC–copper nanocomposite has increased by about two orders of magnitude as compared to the pure system. Dielectric permittivity has also increased. The absorption spectra for pure and nanocomposites have been studied by UV–Vis spectrophotometer. The optical study suggests that surface plasmon resonance has been introduced in DLC due to the incorporation of copper nanoparticles. It has been observed that the presence of nanoparticles has decreased the optical band gap to 3.3 eV from 4.2 eV of the pure DLC. Enhanced properties are useful for one-dimensional conduction and photovoltaic applications.     

Synthesis,TGA and EPR studies of phase transitions in Cu2+ doped (NH4)4ThF8 and (NH4)3ThF7

The paper presents the EPR evidence for the occurrence of phase transitions in (NH₄)₄ThF₈ and (NH₄)₃ThF₇. In both cases the Cu²⁺ probe occupies a NH⁴⁺ site and predominantly experiences a dynamic coordination, either due to dynamic Jahn-Teller effect, or due to fluxional behaviour of surrounding (ThF₈)^4- units in (NH₄)₄ThF₈. It is proposed that the structural phase transition in this compound at 214 K is associated with the transition of the dynamic coordination of Cu^2- into a static one, probably due to freezing of motion of (ThF₈)^4- units below this temperature. In (NH₄)₃ThF₇ the dynamic features of the Cu²⁺ EPR spectrum are absent and characteristics of a local orthorhombic symmetry are seen down to 77 K. However, in the high temperature range a change from orthorhombic to axial symmetry is observed at 524 K, possibly due to a phase transition.     

Thermal expansion and a new phase transition in pyroelectric LiKSO4

Single crystal macroscopic thermal expansion coefficient measurements have been made on uniaxial lithium potassium sulphate crystal both along and normal to the six fold axis, employing Fizeau’s interferometer method. Measurements were made in the range of −120°C to 500°C. The results show that lithium potassium sulphate exhibits two major anomalies in its expansion coefficients around −95°C and 422°C respectively, the one at −95°C has been observed for the first time. The nature of dimensional changes of the crystal at the upper and lower transition points are opposite in nature. The crystal shows considerable lattice anisotropy. Megaw’s tilt concept has been invoked to explain the relative magnitudes of expansion coefficients alonga andc directions. Structural features responsible for the absence of ferroelectricity in this crystal have been pointed out.     

PMRD investigations of molecular dynamics and phase transitions in the liquid crystal 6CHBT

Proton Magnetic Relaxation Dispersion (PMRD) measurements were carried out over a wide Larmor frequency range near the isotropic-nematic transition temperature (T _NI) and in the mid nematic phase of a low viscous liquid crystal 4-(trans-4′-hexylcyclohexyl)-isothiocyanatobenzene (6CHBT), with a view to examining the pre-transitional effects just above isotropic-nematic transition (T > T _NI) and the role of director fluctuations (DF) on the nematic phase stability of this system. The results near the transition indicate critical slowing down of the short-range nematic order modes just above T _NI with a mean field critical exponent characterizing the coherence length (ξ). The observed temperature independence of the correlation time associated with the reorientations (τ_R) and the extension of DF mode spectrum, in the mid-nematic phase, to relatively higher resonance frequencies seem to suggest fairly low hindering barriers for the tumbling of the molecules about their short axes.     

Shock adiabat features,phase transition macrokinetics,and spall fracture of iron in different phase states

Abstract

Results are presented of systematic experimental investigations of shock adiabat and evolution of multiwave configurations for a number of steels in the range up to 100GPa; of stress relaxation kinetics in the front of the elastic and phase precursor from different initial states: uσ_x = 15, 25, 49, and 59GPa; and of data on spa11 fracture of iron in α —, ε —, γ —, and liquid phases under conditions of uniaxial deformation as well as under volumetric omnidirectional tension. Changes in material microstructure and microhardness of samples subjected to shock wave loads of 15, 25, 200, and 1000 GPa are analyzed.

Investigations of steels with the initial state in α and γ phases of iron and with different original heat treatment show that, in stress waves of low intensity (σ_x? 10–25 GPa), as well as under quasi-static tension-compression tests and impact tests, differences in their behavior and properties are clearly displayed. As the amplitude of longitudinal stresses increases up to 200–250 GPa, differences in their compressibility and in the character of spal1 fracture begin to smooth down.     

Influence of hydrogen bonding on the generation and stabilization of liquid crystalline polyesters,poly(esteramide)s and polyacrylates

Induction and stabilization of liquid crystallinity through hydrogen bonding (HB) are now well-established. Interesting observations made on the influence of HB on LC behaviour of amido diol-based poly(esteramide)s, poly(esteramide)s containing nitro groups and azobenzene mesogen-based polyacrylates will be discussed. The use of amido diol as an important precursor for the synthesis of novel PEAs containing inbuilt di-amide linkage enabled generation of extensive hydrogen bondings between the amide-amide and amide-ester groups which stabilized the mesophase structures of the PEAs. The contributions of hydrogen bonding to the generation and stabilization of mesophase structures were plainly evident from the observation of liquid crystallinity even in PEAs prepared from fully aliphatic amido diols. Replacement of terephthaloyl units by isophthaloyl moiety totally vanquished liquid crystalline phases while biphenylene and naphthalene units did only reduce the transition temperatures as expected. The occurrence of the smectic phases in some of the polymers indicated possibly self-assembly through the formation of hetero intermolecular hydrogen bonded networks. A smectic polymorphism and in addition, a smectic-to-nematic transition, were observed in the monomers and polymers based on 1,4-phenylene[bis-(3-nitroanthranilidic acid)] containing nitro groups. A smectic polymorphism was also observed as a combined effect of hydrogen bonded carboxyl groups and laterally substituted alkyl side chains in the case of azobenzene mesogen containing side chain polyacrylates. It was further shown that the presence of the mesophase enhances the non-linear optical (NLO) response of these polymers.     

Orientational phase transition and the solvation force in a nematic liquid crystal confined between inhomogeneous substrates

A nematic liquid crystal confined between two identical flat solid substrates, with an alternating stripe pattern of planar and homeotropic anchoring, is studied in the framework of the Frank-Oseen theory. By means of numerical minimization of the free energy functional we study the effect of the sample thickness D on the location of the phase transition between a uniform alignment, either planar or homeotropic, and a distorted nematic texture. The solvation force f due to distortions of the nematic director is also studied. It is found that f is always attractive, and for D small compared to the periodicity of the surface structure it exhibits two distinct asymptotic behaviors: f ∼ - D ^-1/2 or f ∼ - D ^-1, depending on the relation between D and the extrapolation lengths. Received 12 November 2002 Published online: 16 April 2003     

The Raman noncoincidence effect of the ν(CO) band of ME6N liquid crystal across the nematic–isotropic phase transition studied by a micro‐spectroscopy experiment

The Raman spectroscopic noncoincidence effect (NCE) of the ν(CO) band of the liquid crystal ME6N (4‐cyanophenyl‐4′‐hexylbenzoate) has been measured at different temperatures (47–52 °C) around the nematic‐isotropic phase transition (47.8 °C) employing a micro‐Raman experiment under confocal conditions and performed on a homogeneously aligned thin sample. The low value of NCE (0.9 cm⁻¹) obtained over the whole temperature range suggests that the orientational structure of the liquid crystal in both phases is governed by the steric hindrances in the proximity of the carbonyl group, rather than by dipolar interactions. This hypothesis is supported by the results of a supplementary investigation of the NCE of the ν(CO) Raman band in liquid ketones and esters, made progressively more hampered by the insertion of bulky (phenyl) groups in proximity of the carbonyl group. The NCE of the ν(CO) band, in fact, decreases from 5.5 cm⁻¹ in acetone (the less hampered) to 0.7 cm⁻¹ in benzophenone (the most hampered among the studied ketones), and from 6.2 cm⁻¹ in methyl acetate (the less hampered) to 2.2 cm⁻¹ in phenyl benzoate (the most hampered among the studied esters). To our best knowledge, this represents the first attempt to analyze the NCE in terms of steric hindrance of the substituents around the target oscillator. A parallel analysis of the difference between the anisotropic and the isotropic bandwidths of the ν(CO) Raman band in these molecular liquids indicates that reorientational dynamics plays only a marginal role, if any. Copyright © 2006 John Wiley & Sons, Ltd.     

Field-temperature phase diagrams in chiral tilted smectics,evidencing ferroelectric and ferrielectric phases

Usual ferroelectric compounds undergo a paraelectric-to-ferroelectric phase transition when the susceptibility of the electric polarization density changes its sign. The temperature is the only thermodynamic field that governs the phase transition. Chiral tilted smectics may also present an improper ferroelectricity when there is a tilt angle between the average long axis direction and the layer normal. The tilt angle is the order parameter of the phase transition which is governed by the temperature. Although the electric susceptibility remains positive, a polarization proportional to the tilt appears due to their linear coupling allowed by the chiral symmetry. Further complications come in when the chirality increases, as new phases are encountered with the same tilt inside the layers but a distribution of the azimuthal direction which is periodic with a unit cell of two (SmC(A)*, three (SmC(Fi1)*, four (SmC(Fi2)* or more (SmC(alpha)* layers. In most of these phases, the layer normal is a symmetry axis so there is no macroscopic polarization except for the SmC(Fi1)* in which the average long axis is tilted so the phase is ferrielectric. By studying a particular compound with only a SmC(Fi2)* and a SmC(alpha)* phase, we show that we recover the uniformly tilted ferroelectric SmC* when applying an electric field. We are thus led to build field-temperature phase diagrams for this class of compounds by combining different experimental techniques described here.     

Emergent O(4) symmetry at the phase transition from plaquette-singlet to antiferromagnetic order in quasi-two-dimensional quantum magnets

Recent experiments [Guo et al., Phys. Rev. Lett. 124 206602(2020)] on thermodynamic properties of the frustrated layered quantum magnet SrCu_2(BO_3)_2-the Shastry–Sutherland material-have provided strong evidence for a lowtemperature phase transition between plaquette-singlet and antiferromagnetic order as a function of pressure. Further motivated by the recently discovered unusual first-order quantum phase transition with an apparent emergent O(4) symmetry of the antiferromagnetic and plaquette-singlet order parameters in a two-dimensional "checkerboard J-Q" quantum spin model[Zhao et al., Nat. Phys. 15 678(2019)], we here study the same model in the presence of weak inter-layer couplings. Our focus is on the evolution of the emergent symmetry as the system crosses over from two to three dimensions and the phase transition extends from strictly zero temperature in two dimensions up to finite temperature as expected in SrCu_2(BO_3)_2.Using quantum Monte Carlo simulations, we map out the phase boundaries of the plaquette-singlet and antiferromagnetic phases, with particular focus on the triple point where these two ordered phases meet the paramagnetic phase for given strength of the inter-layer coupling. All transitions are first-order in the neighborhood of the triple point. We show that the emergent O(4) symmetry of the coexistence state breaks down clearly when the interlayer coupling becomes sufficiently large, but for a weak coupling, of the magnitude expected experimentally, the enlarged symmetry can still be observed at the triple point up to significant length scales. Thus, it is likely that the plaquette-singlet to antiferromagnetic transition in SrCu_2(BO_3)_2 exhibits remnants of emergent O(4) symmetry, which should be observable due to additional weakly gapped Goldstone modes.     

Synthesis,characterization and mesomorphic behaviour of lanthanide (III) 4-alkoxybenzoates

The lanthanide (III) 4-alkoxybenzoates [Ln(C_nH_2n?+?1OC₆H₄CO₂)₃, Ln?=?La (III), Pr (III), Nd (III), Eu (III), Gd (III), Tb (III) and Dy (III) and n?=?6, 8, 10, 12 and 16] have been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, and IR and electronic spectroscopy. Hot-stage polarizing optical microscopy and differential scanning calorimetry have been used to investigate the mesomorphic behaviour. The chain length influences the structure and hence the thermal behaviour of these compounds. All the lanthanide complexes except decyloxy derivatives exhibit smectic A mesophase. The decyloxy-containing complexes are non-mesomorphic. The differential scanning calorimeter traces do not display the exothermic peak for all the compounds except for the hexadecyloxy derivatives, which exhibit enantiotropic smectic A phase. The influence of the lanthanide ions on the phase transition has also been clearly demonstrated.     

Raman light scattering,infrared absorption and DSC studies of the phase transition and vibrational and reorientational dynamics of H2O ligands and ClO4– anions in [Ba(H2O)3](ClO4)2

[Ba(H₂O)₃](ClO₄)₂ between 90 and 300 K possesses two solid phases. One phase transition of the first‐order type at: = 211.3 K (on heating) and = 204.6 K (on cooling) was determined by differential scanning calorimetry. The entropy change value (ΔS ≈ 15 Jmol^–1 K^–1), associated with the observed phase transition, indicates a moderate degree of molecular dynamical disorder. Both, vibrational and reorientational motions of H₂O ligands and ClO₄^– anions, in the high‐temperature and low‐temperature phases, were investigated by Fourier transform far‐infrared and middle‐infrared and Raman light scattering spectroscopies. The temperature dependences of the full‐width at half‐maximum values of the bands associated with ρ_w(H₂O) mode, in both infrared (~570 cm^–1) and Raman light scattering (~535 cm^–1) spectra, suggest that the observed phase transition is not associated with a sudden change of a speed of the H₂O reorientational motions. Ligands reorient fast, with correlation time of the order of several picoseconds, with a mean activation energy value E_a = 5.1 kJ mol^–1 in both high and low temperature phases. On the other hand, measurements of temperature dependences of full‐width at half‐maximum values of the infrared band at ~460 cm^–1, associated with δ_d(OClO)E mode, and Raman band at ~1105 cm^–1, associated with ν_as(ClO)F₂ mode, revealed the existence of a fast ClO₄^– reorientation in phase I and in phase II, with the E_a(I) and E_a(II) values equal to 8.0 and 6.5 kJ mol^–1, respectively. These reorientational motions of ClO₄^– are slightly distorted at the T_C. Fourier transform far‐infrared and middle‐infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at T_C, which suggested lowering of the crystal structure symmetry. All these experimental facts suggest that the discovered phase transition is associated with small change of H₂O ligands and somewhat major change of ClO₄^– anions reorientational dynamics, and with insignificant change of the crystal structure, too. Copyright © 2012 John Wiley & Sons, Ltd.