Anomalous temperature dependence of elastic constants in NbMo alloys

An unusual positive temperature coefficient ofc₄₄ was observed in the Nb-rich Mo alloys, which appears to be connected with previously reported anomalies in neutron-diffraction and specific-heat data.     

The elusive thermotropic biaxial nematic phase in rigid bent-core molecules

The biaxial nematic liquid crystalline phase was predicted several decades ago. Several vigorous attempts to find it in various systems resulted in mis-identifications. The results of X-ray diffraction and optical texture studies of the phases exhibited by rigid bent-core molecules derived from 2,5-bis-(p-hydroxyphenyl)-l,3,4-oxadiazole reveal that the biaxial nematic phase is formed by three compounds of this type. X-ray diffraction studies reveal that the nematic phase of these compounds has the achiral symmetry D_2h, in which the overall long axes of the molecules are oriented parallel to each other to define the major axis of the biaxial phase. The apex of the bent-cores defines the minor axis of this phase along which the planes containing the bent-cores of neighboring molecules are oriented parallel to each other.     

Orientational order in liquid crystals exhibited by some binary mixtures of rod-like and bent-core molecules

We report measurements of the temperature variations of the optical birefringence in the nematic (N) and partial bilayer SmA (SmA_d) phases in 4-n-octyloxy 4^′ -cyanobiphenyl made of rod-like (R) molecules and five mixtures of this compound with 1,3-phenylene bis[4-(3-methylbenzoyloxy)] 4^′ -n- dodecylbiphenyl 4^′ -carboxylate, made of bent-core (BC) molecules. The birefringence decreases with the concentration x of the BC molecules but the macroscopic order parameter initially decreases upto 11mol% of BC molecules and subsequently increases with x . This is attributed to the possible formation of polar clusters of BC molecules. Orientation of BC molecules changes between the N and SmA_d phases and the birefringence data in the two phases imply that the kink angle of the BC molecules is ∼ 90^° rather than ∼ 110^° as obtained from calculations which minimize the energy of the molecule. IR spectroscopic measurements on the mixture with 11mol% of BC molecules have been used to estimate the molecular order parameter S of the R molecules, and to provide additional support for a relatively small kink angle of BC molecules.     

The temperature dependence of the elastic constants of MnO

We have measured the temperature dependence of the elastic constants of a monodomain single crystal of MnO, obtained by applying a unixial stress, from 4.2 to 300 K. Measurements were made by standard ultrasonic techniques and the acoustic waves were generated and detected by CdS transducers. Problems associated with the coupling between transducer and sample encountered by previous workers were therefore overcome. For propagation down the [111] direction, only the slow shear mode [$\text{1}\text{2}$(c₁₁?c₁₂)] was observable below the Néel temperature (T_N. The fast shear and longitudinal modes were heavily attenuated. Complex behaviour in the region of T_N and a further anomaly at 42 K were observed.     

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.     

Investigating the temperature dependence of elastic constants by thermal fluctuation formula

The differences between the calculated values of elastic constants of materials and the experimental data are consistently restricting the application of thermal fluctuation formula to the mechanical properties of materials. In this work, the temperature dependence of elastic constants of many-body potentials is studied by thermal fluctuation formula. The differences between the calculated values and the experimental data are investigated in detail. Our studies show that the differences come from the thermal expansion of the materials: the calculated zero-stress states are bigger than the experimental zero-stress states of the materials, and this deviation makes Born terms of the thermal fluctuation formula decrease sharply as the temperature increases, while the fluctuation terms and the kinetic terms change little. As a result, the elastic constants, which are the sum of these three terms, decrease faster than the experimental data as the temperature increases. Our studies show that when the experimental zero-stress states are used as the reference states in constant volume and constant energy (NVE) simulations, the elastic constants calculated by thermal fluctuation formula are in good agreement with the experimental values.     

Brillouin and ultrasonic study of the temperature dependence of the elastic constants in NaCN

The temperature dependence of the elastic constants of NaCN has been studied by propagation of ultrasonic waves at 15 MHz and by Brillouin scattering at 3 GHz over the temperature range from 287K to 355K. c₄₄ is observed to soften linearly with temperature as the order-disorder phase transition at 284K is approached from above. The other elastic constants also soften, except for c₁₂ which stiffens. Considerable dispersion is seen in the values of c₄₄ obtained ultrasonically and by Brillouin scattering. Measurements of the temperature dependence of the density are also reported.     

Phase transitions in binary mixtures of rodlike colloids and stiff polymers

A suspension of long rodlike colloids and long stiff polymers is modelled as a mixture of hard rods. The diameter of the colloid particle is finite, while the polymer is considered in the limit of zero diameter. Two types of first-order phase transition may occur in such mixtures: an isotropic-nematic phase transition if the density (or the pressure) is high enough, and a demixing transition involving two isotropic phases. The demixing transition has a critical point, and a triple point with one nematic and two isotropic phases may also exist. Phase diagrams are calculated. For the demixing isotropic-isotropic transition to be observed the ratio between the polymer length and the colloid length must exceed 0.36.     

Anomalous temperature dependence of third-order elastic constants in NH4Cl and NH4Br near the λ point

Second order elastic constants of NH₄Cl and NH₄Br crystals were measured under hydrostatic and uniaxial pressures near the λ-type phase transitions. Third order elastic constants were calculated from the pressure derivatives of the second order elastic constants. Results show that the temperature dependences of the third order elastic constants of NH₄Cl differ from those of NH₄Br dramatically. In addition, it is found that the coefficients $\text{1}\text{54}\text{(C}{}_{111}\text{+ 6C}{}_{112}\text{+ 2C}{}_{123}\text{)}$ and $\text{(}\text{1}\text{24}\text{√3)(C}{}_{111}\text{? 3C}{}_{112}\text{+ 2C}{}_{123}\text{)}$ of strains in the free energy of NH₄Cl show quite different temperature dependences from those of NH₄Br.     

Electric field dependence of phase equilibria of binary Stockmayer fluid mixtures

A perturbation theory based study of the effect of an external electric field on the phase equilibrium properties of binary Stockmayer fluids is presented. The dipole–dipole interaction and the applied field are treated as independent perturbations to a Lennard–Jones mixture, and the reference fluid is treated by the van der Waals one-fluid approximation. A third-order free energy expression in the electric field strength is established, and the dielectric constant is calculated for a needle-shaped sample parallel to the field direction. We present and discuss vapour–liquid and liquid–liquid equilibrium curves at a given temperature for some dipolar mixtures exposed to an electric field, including chlorodifluoromethane +?difluoromethane and acetonitrile +?methanol. A sufficiently high electric field may result in massive shifts of vapour pressures and critical or azeotropic points, and can considerably alter the properties of coexisting phases. The vapour pressure decreases with increasing field strength.     

The formation of biaxial nematic phases in binary mixtures of thermotropic liquid-crystals composed of uniaxial molecules

ABSTRACT

Monte Carlo simulations in the isothermal-isobaric ensemble are used to investigate the formation of an ordered, biaxial nematic phase in a binary mixture of thermotropic liquid crystals. The orientational dependence of the interaction between molecules of each pure component is the same as in the well-known Maier-Saupe model; each pure component of the mixture is therefore capable of forming a uniaxial nematic phase. For the interaction between molecules of different components, we use the same Maier-Saupe model but change the sign of the coupling constant. As a consequence a T-shaped arrangement of these molecules is energetically favoured. The formation of the biaxial phase occurs in two steps. At higher temperatures T, one of the components forms a uniaxial nematic phase whereas the other is in a quasi two-dimensional restricted isotropic liquid state. We develop a simple theoretical model to understand the high degree of (ostensible) nematic order in the latter. At lower T, the second component becomes nematic and then the entire mixture of the two compounds has biaxial symmetry. The biaxial nematic phase does not demix into domains rich in molecules of one or the other species.     

Order parameter and its critical exponent for some binary mixtures showing induced nematic phase

Refractive index measurements as a function of temperature have been performed for an induced nematic binary system by means of thin prism technique. The temperature dependence of the birefringence (Δn) has been assessed from the measured refractive index data. A direct extrapolation method has been employed to determine the orientational order parameter for the investigated mixtures and the order parameter so obtained has also been compared with the mean field values. The Haller type fitting expression results in a relatively lower value of the order parameter critical exponent (β) compared to the theoretically predicted values. Therefore, a four-parameter power law expression, consistent with the mean field theory as well as the first-order character of the nematic–isotropic (N-I) phase transition have been used to explore the critical behavior of the order parameter near the N-I transition.     

Strongly anisotropic elastic moduli of nematic elastomers: Analytical expressions and nonlinear temperature dependence

Exact formulae for the elastic moduli of the nematic elastomers are obtained by the implicit function method based on somewhat general energy functions. The formulae indicate that both the moduli parallel and perpendicular to the director of the nematic elastomers are smaller than the modulus of the classical elastomers because of the mechanical-nematic coupling. Moreover, the moduli are generally anisotropic due to the biaxiality induced by stretching the nematic elastomers perpendicular to the director. Then we get the explicit analytical expressions of the parallel and perpendicular moduli by making use of the Landau-de Gennes free energy and the neo-classical elastic energy. Very different from the classical elastomers, they are both strongly nonlinear functions of the temperature in the nematic phase. Furthermore, their ratio, the degree of anisotropy, changes with the temperature as well. The results agree qualitatively with some experiments. Better quantitative agreement is obtained by some modifications of the constitutive relation of the elastic energy.     

Statistical theory of the elastic constants of nematic liquid crystals

A statistical mechanical theory of the Frank elastic constants is formulated. The free energy functional is constructed for the deformed sample and the free energy density is defined for the case of small spatial gradients. The Frank constants are expressed in terms of the direct correlation function c(1, 2) and the orientational single particle distribution function. For the example of Onsager spherocylinders three constants K ₁, K ₂ and K ₃ are calculated. The results of these calculations are similar to those given by Priest and by Straley.     

Temperature dependence of the elastic constants of aluminum

The single crystal elastic constants of aluminum have been measured using a piezoelectric composite oscillator from room temperature to just 20 K below the melting point. The elastic moduli differ markedly from previous high temperature results, but match in well with previous cryogenic results. Over the temperature range investigated the isothermal bulk modulus and the two shear moduli have a simple exponential dependence on isobaric volume, and the cryogenic data indicate this dependence may be preserved down to absolute zero. As has been found previously for a wide range of materials, the isothermal bulk modulus and the shear modulus $\text{(c}{}_{11}\text{– c}{}_{12}\text{)}\text{2}$ appear to be continuous functions of volume through the melting expansion, and melting seems to find its origin in the mechanical instability associated with this shear modulus vanishing at the volume of the melt at the freezing point. Grüneisen's parameter divided by the molar volume is very nearly independent of isobaric volume.     

Temperature dependence of the elastic constants of aluminium

Published results for the temperature variation of the elastic constants of single crystal aluminium are discussed with special reference to the possibility that error propagation in the conversion of compliances to stiffness may contribute to the discrepancies between the different sets of data for the stiffnesses.