Solid–fluid phase transitions under extreme pressures including negative ones

Upon heating or isotropic expansion, condensed matters (solids and liquids) can reach their stability limits, where the system must be stabilized by the appearance of a second phase. During isotropic expansion, the pressure can reach negative values. In auxetic materials, volume expansion is an inherent way of behavior, therefore, negative-pressure states can be reached easily during uni-axial stretch. In this paper, a comparison of various stability limits of pure and ordered one-component stretched solids will be mapped, with special focus on auxetic materials.     

Photo-Controllable Rotation of Cholesteric Double-Twist Cylinders

Abstract

We fabricated aggregates of cholesteric cylinders coexisting with the isotropic phase and investigated their dynamics under a temperature gradient. Each constituent cylinder possessed the double-twist (DT) structure, and when a heat flux was applied, the whole aggregates rotated as a rigid-body without changing the DT orientation. The angular velocity was proportional to the heat flux and the rotational direction was determined by the molecular chirality and the flux direction. The result suggests that the rigid-body rotation was driven by the thermomechanical cross-correlation in chiral LCs. We also succeeded in switching the rotation by changing the illumination onto the sample.     

New Mesogenic Compounds Exhibiting a Thermotropic Optically Isotropic Phase

Abstract

The only two series of carboxylic acids, 3-nitro- or 3-cyano-4-alkoxybiphenyl-4′-carboxylic acid, are known to exhibit the optically isotropic phase (S_D). Now we synthesised 4-(branched alkoxy)-anilinebenzylidene-4′-carboxylic acid series, all being racemic, and investigated their mesophase properties by means of DSC, optical microscopy and X-ray measurement. As a result, some branched azomethine derivatives were found to form a S_D phase. We also synthesised cinnamic acid derivatives with branched alkoxy tail that were turned out to exhibit either S_D phase or hexagonal columnar phase. We tried biphenyl or azobenzene core analogues which were found to produce a highly ordered smectic phase or no mesophase, respectively. At this stage, we suppose it plays an important role that the branch is introduced into the terminal chain and a certain dipole moment is located within the mesogenic core. These factors may allow the peculiar molecular packing that causes an optically isotropic property.     

Microscopic Observations of the Cholesteric Blue Phase in Mixtures of Varying Pitch

Theories for the blue phase proposed recently by Brazovskii and Dmitriev and by Hornreich and Shtrikman predict that this phase can exist only for cholesterics of sufficiently short pitch. In this article we demonstrate this dependence upon pitch through microscopic observations of three sets of binary mixtures, one set consisting of mixtures of cholesterics of opposite chirality and the other two consisting of cholesteric-nematic mixtures.

In the course of these studies we have developed techniques for growing particularly large platelets of the blue phase. We present photographs of these platelets demonstrating, for the first time, the optical anisotropy of the blue phase, which is evident when the platelets are sufficiently large. Characteristic twinning patterns are also evident in the photographs.     

Field-Induced Order in Nematic Liquid Crystals

The effect of an external magnetic field on the orientational order of a nematic liquid crystal has been examined using both Landau-de Gennes and Maier-Saupe theories. In the Maier-Saupe approach a rotationally invariant form of the pseudo-potential is introduced, which in the absence of an external field leads to three degenerate isomorphic solutions for the order parameter, corresponding to alignment along three principal axes; a similar result is obtainable from the Landau-de Gennes theory. Application of a magnetic field lifts the degeneracy of these solutions, and for materials having a positive diamagnetic susceptibility anisotropy, the uniaxial solution with alignment along the field direction is always energetically favorable. For materials with a negative susceptibility anisotropy, a biaxial solution minimizes the free energy at low temperatures, but on increasing the temperature there is a transition from a biaxial phase to an uniaxial phase. The field dependence of the transition temperatures is evaluated, and for positive materials there is a critical field, corresponding to a second order transition above which the nematic and isotropic phases are indistinguishable. A contrasting behavior is predicted for negative materials, and above a certain critical field the biaxial/uniaxial transition changes from first order to second order. For weakly ordered systems it is shown that the Landau-de Gennes expression for the free energy is identical to that obtained from the Maier-Saupe theory. However, for more ordered systems, the results of the two approaches differ, and in particular the Maier-Saupe theory predicts a susceptibility divergence temperature T* which increases with applied field, in agreement with recent experiments.     

Monte carlo simulations for blue-phase structure in liquid crystals

Blue-phase liquid crystals form three-dimensional structures in a self-organizing manner and are similar to living tissue structures such as the teeth of mice and collagen tissues. This study presents numerical results regarding the conditions under which blue-phase liquid crystals occur. The Monte Carlo simulations are performed by employing an improved Lennard–Jones potential that considers anisotropy and chirality. The conditions for the formation of the blue phase, which vary with respect to the chirality, are examined first. The relationship between the anisotropic parameters and the chiral parameter for the formation of the blue phase is discussed. Identical blue-phase structures are obtained, even when the cell size and molecular number are varied drastically. This discussion is useful for considering the scale-up problem, which is almost always a difficult issue for molecular-scale simulations.     

Change of the Prenematic Order in the Isotropic Phase Close to the Isotropic–Nematic Phase Transition with Increasing Aerosil Nanoparticles Density

The influence of the hydrophilic and hydrophobic aerosil nanoparticles density on the formation of the prenematic order close to the isotropic – nematic (I–N) phase transition is presented. The lowering of the activation energy, with the increase of aerosil nanoparticles density, suggests a change of the prenematic order in the isotropic phase. The temperature dependence of the static dielectric permittivity for 4–n–pentyl–4′–cyanobiphenyl (5CB) exhibits an anomaly near the I–N phase transition. With the increase of aerosil density, a substantial modification in the anomaly of the static permittivity was observed in the isotropic phase. Indicated changes are different for hydrophilic and hydrophobic aerosil as a result of different surface interaction between nematic molecules and aerosil nanoparticles.     

Optical Studies on Smectic-Isotropic Phase Transition Behavior of Two Thermotropic Liquid Crystals

The binary mixture of two compounds, viz., Cholesteryl laurate (CL) and diethyl 4, 4′-azoxy benzoate shows the cholesteric and smectic phases sequentially when the specimen is cooled from its isotropic phase. Refractive indices, birefringence, and optical transmittance have been measured by the optical technique. With the help of measured data, the macroscopic ordered parameter has been discussed. The temperature dependence of these parameters has also been discussed.     

NMR and X-ray Investigations of a Plastic Crystalline Phase in MBBA

Abstract

Wideline and high resolution NMR studies have been carried out on MBBA in its isotropic, nematic and solid phases. Isotropic and nematic phase spectra correspond to what has been reported earlier. In the solid phase, contrary to expectations, very intense narrow signals similar to signals of the isotropic phase have been observed for the first time at temperatures close to the solid ? nematic phase transition temperature. This indicates rapid reorientational or translational motion in the system. The X-ray results however confirm the existence of translational order. The results are interpreted as indicative of the existence of a plastic crystalline phase in MBBA.     

Mesomorphism dependence on central bridge (-COO-CH2-) and terminal end group (-Br)

A novel series of liquid crystalline (LC) ester materials has been synthesized and studied with a view to understanding the effects of molecular structure on LC behavior. The homologous series of eleven members is entirely enantiotropically smectogenic without exhibition of a nematic phase. Transition temperatures and the texture of smectic phase was determined by an optical polarizing microscope equipped with a heating stage (POM). Transition curves (Cr-Sm and Sm-I) showing phase behavior in a phase diagram behave in a normal manner. Textures of smectic phase are focal conic fan shaped of the type Smectic-A or Smectic-C. An odd–even effect is exhibited by the Sm-I transition curve. The average thermal stability for smectic is 91.2°C and the mesogenic phase length ranges between 3.6°C and 39.3°C. Thus, the novel smectogenic homologous series is a middle-ordered melting type whose LC phase is relatively middle ordered. The LC properties of the present series are compared with a structurally similar homologous series. Analytical and spectral data support the molecular structures.     

Theory of Systems of Rodlike Particles: I. Athermal systems

An improved treatment of the lattice model proposed in 1956 is presented for a system of hard rods, with axial ratio x, dispersed in a diluent. Interparticle forces, apart from repulsions on contact, are deliberately ignored within the scope of the present paper. The equilibrium distribution of orientations of the rodlike particles in a phase with nematic order is derived and explicitly taken into account. Thermodynamic properties in the asymptotic limit of high degree of order reduce approximately. to those obtained previously. Calculations carried out for equilibrium between anistropic (nematic) and isotropic phases yield ν′_x/ν_x = 1.4653 for the ratio of volume fractions in the respective phases in the limit x → ∞. The product xν_x, expressing the combined covolume of solute species in the isotropic phase at coexistence is 7.89 in the same limit. The calculated critical value of the axial ratio for coexistence of the two phases in the neat liquid is x_crit, = 6.417. Results are compared with those of other theories. Those that rely on the virial expansion are subject to errors implicit in treating the solvent as a continuum.     

Chiral Gay–Berne model for molecular dynamics computer simulations

Abstract

We have extended the chiral Gay–Berne (GB) pair potential of Memmer and co–workers [Liq. Cryst. (15), 345 (1993)] to the general case of biaxial ellipsoids, and we provide explicit expressions for the gradient and the torques to be used in molecular dynamics (MD) codes. To test our results against published results we have performed MD simulations of samples formed by N?=?1024 uniaxial GB ellipsoids with constant volume, and we have studied how the thermotropic behavior is affected by particle chirality. We have run temperature scans starting from isotropic samples and found clear signatures of the spontaneous formation of both lower temperature blue and cholesteric phases.     

Dielectric relaxation investigations of the isotropic and nematic phases of 4-n-Butyloxyphenyl-4-n-hexylbenzoate (BOHB)

Experimental values of the complex dielectric permittivity in a wide frequency range are analized for the isotropic and nematic phase of BOHB. The results are discussed from the point of view of different of molecular reorientation mechanisms which are related to the structure of the molecule. It can be concluded that the molecules in the nematic phase exhibit a stronger tendency to reorient as “rigid bodies”.     

The Behaviour of Contact Angles of Wetting for Liquid Crystalline Drops on Glass Near the Phase Transition

The experimental values of contact angles of wetting for pazoxyanisole - glass in the nematic and isotropic phase have been obtained. At the point the phase transition, a change in the value of contact angle of wetting is observed. The values of adhesion energy, have been calculated for different orientation of molecules with respect to the glass support.

It is well-known /I/that contact angles of drops on solid supports enable an information on interfacial energy γ_SL to be obtained. A change in the structure of liquid results in alteretion of the contact angle as it a has been shown recently for polymer solutions /2/. It seem to be quite possible that orientational ordering of liquid crystals has to affect the value of contact angles of wetting. Nevertheless, this value was not found to very upon phase transition from the isotropic to liquid crystalline state /3/.

We studied the behaviour of contact angle of wetting for a drop of a classical liquid crystalline compound p-azoxyanisole (PAA) in its nematic and isotropic phases.     

Surface and bulk residual stresses in Li2O · 2SiO2 glass–ceramics

In the present work surface and bulk residual stresses generated in partially crystallized Li₂O · 2SiO₂ glass–ceramics are analyzed after different heat treatments. The phase specific residual stresses in the crystalline Li₂Si₂O₅-phase are evaluated for the first time in the near-surface zone and the bulk of the samples using both medium and high energy synchrotron radiation. The results reveal that in the crystals within the bulk of the samples micro residual stresses generated by the thermal anisotropy of the isolated individual crystallites depend on the crystallographic direction. In contrast, the residual stress state in the near-surface zone is isotropic due to the superposition of thermal residual stresses in and around the crystals of the near-surface area. Residual stress calculations using a modified Selsing’s model yield a good estimate of the anisotropic residual stresses in the bulk crystallites, whereas the isotropic residual stress state in the crystallized surface layer can be described by an elastic stress model for thin films.     

ELECTRIC FIELD-INDUCED DIRECTOR ORIENTATION OF SMECTIC-A DOMAINS IN AN ISOTROPIC PHASE

Abstract

Electric field-induced director orientation of smeetic-A phase in an isotropic phase has been studied with a polarizing microscope using the binary mixture of octyloxycyanobiphenyl and dodecyl alcohol. Electric field is applied to the samples in which spherical smectic-A domains with and without defects in an isotropic phase are observed. Field-induced orientation of smectic-A director is observed for spherical smectic-A domains with defects but not observed for those without defects below electric field strength of 1.0 V/μm, indicating that the presence of defects facilitates the director orientation. The threshold field for the smectic-A director orientation varies from smectic-A domain to domain, suggesting that the threshold field is dependent on the structure of defects.     

Nematic-isotropic phase transition in polar liquid crystals. 1. Statistical theory

The theory of transition from the nematic to the isotropic phase for liquid crystals in the system of rodlike particles with large longitudinal dipoles has been developed with due regard for the equilibrium between monomers and antiparallel molecular pairs—dimers. The order parameters of monomers and dimers are determined as well as the dimer fraction. It is shown that, in accordance with the results obtained earlier, for low values of dipole moments, the temperature of the nematic-isotropic phase transition increases with an increase of the dipole moment. However, for large dipoles, the transition temperature starts decreasing with an increase of the dipole moment because of higher dimer concentration. This provides the interpretation of the recent computer simulation, which showed a destabilization of the nematic phase in the system of rigid rods with pronounced central dipoles. The temperature dependence of the dimer fraction is also studied. The qualitative relation between the sign of the jump in the dimer fraction at the transition point and the effect of dimerization on the transition temperature are established.     

Polarization effects in stretched copper cadmium chloride photochromic glasses

Weak polarization effects are reported in a stretched copper-cadmium-chloride photochromic glass. Details of the microstructure suggest that the observed dichroism may arise from interactions between isotropic particles, which are dispersed upon a second prolate phase. The glass compositions, details of preparation and resulting microstructure are described.     

Mesomorphic and Photoconducting Behavior of 2-(2-Hydroxy-4-alkoxybenzylideneamino)-9-methylcarbazoles

The mesomorphic properties of 2-(2-hydroxy-4-alkoxybenzylideneamino)-9-methyl-carbazoles were investigated and the photoconducting behavior of the crystalline, nematic and isotropic liquid phases were compared for the pentyloxy compound. It was found that the behavior in the nematic phase is comparable with that in the isotropic liquid phase, both being fluid, rather than that in the crystalline phase. The carrier transport mechanisms and the carrier species are implied to be ionic. The current-voltage characteristics showed a new behavior in the fluid states, being similar to that of the negative resistance.