2D 129Xe EXSY of xenon atoms in a thermotropic liquid crystal confined to a controlled-pore glass

Two-dimensional (129)Xe exchange spectroscopy (EXSY) NMR measurements are presented for xenon atoms dissolved in a thermotropic nematic Liquid Crystal (LC), Merck Phase 4, confined to a mesoporous Controlled-Pore Glass (CPG) material with an average pore diameter of 81 A. Experiments were carried out as a function of mixing time at two different temperatures in which Phase 4 appears in nematic and isotropic phases. The exchange rate constants of xenon atoms between two different sites were determined utilizing the intensities of diagonal and off-diagonal signals measured in the EXSY spectra. In the studied system, the sites are: (a) xenon dissolved in the bulk LC between the CPG particles; and (b) xenon in the LC confined inside the pores. The diffusion rate of xenon atoms between the various sites was observed to be very slow.     

Effects of wetting and anchoring on capillary phenomena in a confined liquid crystal

A fluid of hard spherocylinders of length-to-breadth ratio L/D=5 confined between two identical planar, parallel walls--forming a pore of slit geometry--has been studied using a version of the Onsager density-functional theory. The walls impose an exclusion boundary condition over the particle's centers of mass, while at the same time favoring a particular anchoring at the walls, either parallel or perpendicular to the substrate. We observe the occurrence of a capillary transition, i.e., a phase transition associated with the formation of a nematic film inside the pore at a chemical potential different from micro(b)-the chemical potential at the bulk isotropic-nematic transition. This transition terminates at an Ising-type surface critical point. In line with previous studies based on the macroscopic Kelvin equation and the mesoscopic Landau-de Gennes approach, our microscopic model indicates that the capillary transition is greatly affected by the wetting and anchoring properties of the semi-infinite system, i.e., when the fluid is in contact with a single wall or, equivalently, the walls are at a very large distance. Specifically, in a situation where the walls are preferentially wetted by the nematic phase in the semi-infinite system, one has the standard scenario with the capillary transition taking place at chemical potentials less than micro(b) (capillary nematization transition or capillary ordering transition). By contrast, if the walls tend to orientationally disorder the fluid, the capillary transition may occur at chemical potentials larger than micro(b), in what may be called a capillary isotropization transition or capillary disordering transition. Moreover, the anchoring transition that occurs in the semi-infinite system may affect very decisively the confinement properties of the liquid crystal and the capillary transitions may become considerably more complicated.     

Modelling of the phase transition of nanoscale confined liquid crystal

By dividing the bulk melting entropy, a simple thermodynamic model without any adjustable parameter for the size-dependent melting transition temperature has been extended to interpret the melting and freezing transitions of liquid crystals (LCs) confined in nanopores. The results show that as the size of the nanopore decreases, the melting, clearing and freezing transition temperatures of LCs drop. The transition temperatures directly depend on the density of hydrogen bond at the interface between inner pore wall and LC molecules. The model predictions agree well with the corresponding experimental results of LCs p-azoxyanisole and 4-pentyl-4′-cyanobiphenyl confined in nanopores.     

Calorimetric determination of enthalpy changes in octylcyanobiphenyl (8CB) liquid crystal transitions

A specially designed differential scanning heat-flux calorimeter is used for the determination of enthalpy changes in the transitions between mesophases of the octylcyanobiphenyl (8CB) liquid crystal. Latent heats can be separated from pre-transitional effects in certain cases and higher-order transitions can be well identified experimentally.     

Structure of the B4 liquid crystal phase near a glass surface

The B4 liquid crystal phase of bent-core molecules, a smectic phase of helical nanofilaments, is one of the most complex hierarchical self-assemblies in soft materials. We describe the layer topology of the B4 phase of mesogens in the P-n-OPIMB homologous series near the liquid crystal/glass interface. Freeze-fracture transmission electron microscopy reveals that the twisted layer structure of the bulk is suppressed, the layers instead forming a structure with periodic layer undulations, with the topography depending on the distance from the glass. The surface layer structure is modeled as parabolic focal conic arrays generated by equidistant parabolas whose foci are defect lines along the glass surface. Nucleation and growth of toric focal conics near the glass substrate is also observed. Although the growth of twisted nanofilaments, the usual manifestation of structural chirality in the B4 phase, is suppressed near the surface, the smectic layers are intrinsically chiral, and the helical filaments that form on top of them grow with specific handedness.     

Pressure dependence of confined liquid behavior subjected to boundary-driven shear

Non-equilibrium molecular dynamics simulations of boundary-driven sheared Lennard-Jones liquids at variable pressure up to 5 GPa (for argon) reveal a rich out-of-equilibrium phase behavior with a strong degree of shear localization. At the lowest apparent shear rate considered (wall speed ~1 m s(-1)) the confined region is an homogeneously sheared solid (S) with no slip at the walls. This transforms at higher shear rates to a non-flowing plug with slip at the walls, referred to as the plug slip (PS) state. At higher shear rate a central localized (CL) state formed in which the shear gradient was localized in the center of the film, with the rest of the confined sample in a crystalline state commensurate with the wall lattice. The central zone liquidlike region increased in width with shear rate. A continuous rounded temperature profile across the whole system reflects strong dynamical coupling between the wall and confined region. The temperature rise in the confined film is consistent with the Brinkman number. The transition from the PS to CL states typically occurred at a wall speed near where the shear stress approached a critical value of ~3% of the shear modulus, and also near the peak in the traction coefficient, μ. The peak traction coefficient values computed, ~0.12-0.14 at 1000 MPa agree with those found for traction fluids and occur when the confined liquid is in the PS and CL states. At low wall speeds slip can occur at one wall and stick at the other. Poorly wetting liquids manifest long-lived asymmetries in the confined liquid properties across the system, and a shift in solid-liquid phase co-existence to higher shear rates. A non-equilibrium phase diagram based on these results is proposed. The good agreement of the tribological response of the Lennard-Jones fluid with that of more complicated molecular systems suggests that a corresponding states scaling of the tribological behavior could apply.     

Dielectric relaxation in bulk and cylindrically confined octylcyanobiphenyl (8CB)

The dielectric relaxation spectrum over the frequency range 10² to 1.8×10⁹ Hz of 4-octyl-4'-cyanobiphenyl, 8CB, in bulk and confined to 200 nm diameter cylindrical pores is reported. We used matrices with parallel cylindrical pores, obtaining different alignments of the molecular director depending on the treatment. Results show that there are two relaxations in the isotropic phase and in the mesophases for parallel alignment and three for perpendicular alignment. The molecular origin of theses modes and the effect of the confinement on their dynamics are discussed. To compare properly the results for bulk and confined 8CB, a re-scaling of the experimental data is proposed.     

Dielectric relaxation in bulk and cylindrically confined octylcyanobiphenyl (8CB)

The dielectric relaxation spectrum over the frequency range 10² to 1.8×10⁹ Hz of 4‐octyl‐4′‐cyanobiphenyl, 8CB, in bulk and confined to 200 nm diameter cylindrical pores is reported. We used matrices with parallel cylindrical pores, obtaining different alignments of the molecular director depending on the treatment. Results show that there are two relaxations in the isotropic phase and in the mesophases for parallel alignment and three for perpendicular alignment. The molecular origin of theses modes and the effect of the confinement on their dynamics are discussed. To compare properly the results for bulk and confined 8CB, a re‐scaling of the experimental data is proposed.     

Restudy of the unusual phase behavior of the mesogen-jacketed liquid crystal polymers

1 Introduction Liquid crystals (LC) are a state of order between crystals and liquids. They have imperfect long range orders of orientation and position. Thus, they can be fluid like a liquid and they can have anisotropic prop-erties like crystals. For th…     

Aggregation behavior and chromonic liquid crystal phase of a dye derived from naphthalenecarboxylic acid

Polarizing microscopy, X-ray scattering, and absorption spectroscopy are used to investigate the aggregation process and chromonic liquid crystal of the anionic compound Bordeaux dye, a product of the sulfonation of the dibenzimidazole derivative of naphthalenetetracarboxylic acid. Polarizing microscopy reveals that the liquid crystal phase forms at room temperature when the concentration is only about 6 wt%, a value lower than what is found in many aggregating systems. The X-ray results indicate that the aggregation is via columns, with a cross-sectional area about 2.5 times larger than the individual molecule. Absorption spectroscopy shows a significant change in the absorption spectrum due to aggregation, which is nicely explained by a simple theory of isodesmic aggregation and excitonic coupling between the molecules in an aggregate. The "stacking free energy change" for a molecule in an aggregate relative to a molecule in solution is estimated to be about 9 kBT, a larger value than that found in the one other system where it has been estimated.     

Preconcentration of pentachlorophenol from sawdust using quinolin-8-ol immobilized on controlled-pore glass and determination by liquid chromatography

A method for quantitative evaluation of pentachlorophenol (PCP) in sawdust has been developed. Pentachlorophenol is extracted from the solid matrix with 0.5 M sodium hydroxide and preconcentration was carried out using quinolin-8-ol immobilized on controlled pore glass. Determination was carried out by using liquid chromatography with detection at 240 nm. Recoveries were between 84 and 97% at 1–3 μg/g.     

The stability diagram of a nematic liquid crystal confined to a cylindrical cavity

Different nematic structures confined to a long cylindrical cavity with homeotropic surface anchoring are studied using a numerical minimization of the free energy of the uniaxial nematic liquid crystal. The stability of escaped radial structures and planar polar structures (with and without line defects) is analysed in terms of the ratio of elastic constants K₂₄/K₁₁, K₃₃/K₁₁, anchoring strength and external magnetic field applied perpendicular to the symmetry axis of the cylinder. We draw the analogy between the stability diagram of the cylindrical structures and structures in a spherical droplet. In particular, a simple way extracting the value of the saddle-splay elastic constant K₂₄ from the stability studies is discussed.     

Preconcentration of pentachlorophenol from sawdust using quinolin-8-ol immobilized on controlled-pore glass and determination by liquid chromatography

A method for quantitative evaluation of pentachlorophenol (PCP) in sawdust has been developed. Pentachlorophenol is extracted from the solid matrix with 0.5 M sodium hydroxide and preconcentration was carried out using quinolin-8-ol immobilized on controlled pore glass. Determination was carried out by using liquid chromatography with detection at 240 nm. Recoveries were between 84 and 97% at 1-3 microg/g.     

Effect of external electrical field on phase behavior and morphology development of polymer dispersed liquid crystal

Phase diagrams for mixtures of liquid crystal (LC)/monomer with and without an external electrical field applied have been established using polarized light microscope (PLM).The (isotropic + nematic) coexistent phase region and (isotropic + isotropic) phase boundary of LC/monomer mixtures were observed to shift upward to higher temperatures when the external electrical field exists. It was found that the electrical field applied during the cross-linking polymerization has a significant influence on the phase diagrams for the LC/polymer mixtures by rendering the coexistent phase regions shift upward to higher temperatures. The influence of the external electrical field on the processes of the isotropic-isotropic phase separation and liquid crystal ordering in PDLC formation has also been investigated. The results revealed that both the processes could be highly accelerated by the electrical field.     

FTIR study of E7 liquid crystal orientations confined to cylindrical cavities of Anodisc membranes

The orientation of E7 liquid crystal (LC) confined within 200 nm diameter cylindrical cavities of Anodisc membranes was investigated by FTIR dichroism techniques. The cavity walls of the confining pores were chemically modified with different length aliphatic acids (C_nH_2n+1COOH, n=5, 6, 7, 9) at 2 and 4% concentrations. From the FTIR spectra of the aliphatic acid-treated alumina Anodsic membranes, we found salt formation between the -COOH group of the aliphatic acids and the Anodisc membranes. From the FTIR spectra of LC-filled Anodisc membranes, we found an abrupt alignment direction change, from parallel to perpendicular, of the LC molecules along the long axis of the cavities between n=6 and n=7 for the 2% concentration of aliphatic acid. However for the 4% concentration of aliphatic acid the parallel to perpendicular alignment direction of LC molecules changed between n=5 and n=6. The same trend was previously observed for ²H NMR measurements by other researchers.     

A bilayer to monolayer phase transition in liquid crystal glycolipids

Investigations of the thermotropic liquid-crystalline properties of 6,6'-di-O-stearoylsucrose show, for the first time, that glycolipids can exhibit phase transitions within the smectic A phase.     

Liquid crystal phase behavior of sterically-stabilized goethite

The liquid crystalline phase behavior of sterically-stabilized goethite particles in toluene was studied using small-angle X-ray scattering. The results were compared with those from charged particles in water, with and without magnetic field: similarly rich phase behavior was found. Furthermore, the special magnetic properties were retained after coating the particles with amino-functionalized polyisobutylene chains. A remarkable difference between the aqueous and toluene samples is the latter's tendency to form gels. Smaller domains of the different liquid crystalline phases were observed and the columnar phase does not fully develop, furthermore a higher field is needed to align the full sample.     

Photo-polymerization of liquid crystalline monomer in oriented liquid crystal phase

<正>A new approach to synthesize liquid crystalline polymer with narrow polydispersity index(PDI) was developed.Photopolymerization of 4-cyanophenyl-4'-(6-acryloyloxyhexyloxy)benzoate(RM23) in nematic liquid crystals with macroscopic orientation was studied.The effects of the monomer concentration on the molecular weight and PDI of the resulting polymers were studied through gel permeation chromatography(GPC) and polarized optical microscopy.The low PDI of 1.19 and 1.22 was obtained in the reverse and normal modes,respectively.The PDI and molecular weight increased with monomer concentration.