Phase diagram of a ternary mixture of cholesterol and saturated and unsaturated lipids calculated from a microscopic model

We employ a molecular model to study a ternary mixture of saturated lipid, with tails of 16 carbons, a monounsaturated lipid with tails of 18 carbons, and cholesterol. The model, solved within mean-field theory, produces several forms of phase diagrams depending upon the relative strengths of interactions, but only one that shows the coexistence of two liquid phases observed in experiment. The lipids in the phase rich in cholesterol are more ordered than those in the other. The binary cholesterol, saturated lipid system also exhibits liquid, liquid coexistence.     

Floating liquid phase in sedimenting colloid-polymer mixtures

Density functional theory and computer simulation are used to investigate sedimentation equilibria of colloid-polymer mixtures within the Asakura-Oosawa-Vrij model of hard sphere colloids and ideal polymers. When the ratio of buoyant masses of the two species is comparable to the ratio of differences in density of the coexisting bulk (colloid) gas and liquid phases, a stable "floating liquid" phase is found, i.e., a thin layer of liquid sandwiched between upper and lower gas phases. The full phase diagram of the mixture under gravity shows coexistence of this floating liquid phase with a single gas phase or a phase involving liquid-gas equilibrium; the phase coexistence lines meet at a triple point. This scenario remains valid for general asymmetric binary mixtures undergoing bulk phase separation.     

The phase behavior of mixed lipid membranes in the presence of the rippled phase

We propose a model describing liquid-solid phase coexistence in mixed lipid membranes by including explicitly the occurrence of a rippled phase. For a single component membrane, we employ a previous model in which the membrane thickness is used as an order parameter. As function of temperature, this model properly accounts for the phase behavior of the three possible membrane phases: solid, liquid and the rippled phase. Our primary aim is to explore extensions of this model to binary lipid mixtures by considering the composition dependence of important model parameters. The obtained phase diagrams show various liquid, solid and rippled phase coexistence regions, and are in quantitative agreement with the experimental ones for some specific lipid mixtures.     

High temperature XRD studies of nanoscale AgI-CuI solid solutions

A preliminary high-temperature X-ray diffraction (HT-XRD) study of the nanometer-sized solid solution phases in the AgI-CuI system is reported through an extended range of temperatures (300-723K) covering phase transitions in both AgI and CuI. A major feature of this work is the observation of the coexistence of the zincblende and base-centred cubic phases of AgI over an extended range of temperatures the temperature width being a function of Cu content in the binary. The lattice parameters derived from HT-XRD data reflect systematics of phase transitions with progressive Cu substitution of AgI. The present results are discussed together with our earlier ionic conductivity, dilatometry and DSC data which have helped deduce phase diagrams for both the Ag-rich and Cu-rich regions of the binary.     

Demixing and nematic behaviour of oblate hard spherocylinders and hard spheres mixtures: Monte Carlo simulation and Parsons–Lee theory

Parsons–Lee approach is formulated for the isotropic–nematic transition in a binary mixture of oblate hard spherocylinders and hard spheres. Results for the phase coexistence and for the equation of state in both phases for fluids with different relative size and composition ranges are presented. The predicted behaviour is in agreement with Monte Carlo simulations in a qualitative fashion. The study serves to provide a rational view of how to control key aspects of the behaviour of these binary nematogenic colloidal systems. This behaviour can be tuned with an appropriate choice of the relative size and molar fractions of the depleting particles. In general, the mixture of discotic and spherical particles is stable against demixing up to very high packing fractions. We explore in detail the narrow geometrical range where demixing is predicted to be possible in the isotropic phase. The influence of molecular crowding effects on the stability of the mixture when spherical molecules are added to a system of discotic colloids is also studied.     

Wetting transitions in polydisperse fluids

The properties of the coexisting bulk gas and liquid phases of a polydisperse fluid depend not only on the prevailing temperature but also on the overall parent density. As a result, a polydisperse fluid near a wall will exhibit density-driven wetting transitions inside the coexistence region. We propose a likely topology for the wetting phase diagram, which we test using Monte Carlo simulations of a model polydisperse fluid at an attractive wall, tracing the wetting line inside the cloud curve and identifying the relationship to prewetting.     

Optical and thermal studies on viscous lamellar smectic phases in binary mixture of DTAC and ortho-phosphoric acid

The binary mixture of two non-mesogenic compounds, namely, dodecyl trimethylammonium chloride (DTAC) and ortho-phosphoric acid (H₃PO₄) exhibits very interesting liquid crystalline smectic phases at large range of concentrations and temperature. The mixture with lower and higher concentrations of DTAC exhibits SmA, SmD, SmB and SmE phases, sequentially when the specimen is cooled from its isotropic phase. Different liquid crystalline phases observed in the mixture were studied using optical microscopic techniques. The temperature variations of optical anisotropy and electrical conductivity have also been discussed. Helfrich potential and elastic moduli have also been estimated in the smectic phase using the Helfrich model.     

Continuous freezing in three dimensions

We analyze the freezing transition in a system of hard particles with a very long-ranged repulsion. The long-range repulsion makes first-order freezing transitions continuous, but leaves the initial stages of the crystallization unchanged: the crystal phase must still nucleate. The coexistence between bulk phases is replaced by microphase separation.     

Macroscopic description of the ferromagnetic superconductors

We present an improved analysis of the phase transitions in spin-triplet ferromagnetic superconductors within Ginzburg–Landau theory. We put special emphasis on the phase transitions from normal phase to the mixed phase of coexistence of ferromagnetism and unconventional superconductivity. We present a detailed analysis of the different phases that can occur and analyze the question under which conditions the phase transitions from normal phase to the mixed phase of coexistence of ferromagnetism and unconventional superconductivity are possible when compared to other phase transitions. The conditions for the phase transitions and the stability conditions are calculated. On the basis of this model, it is argued that the transition from normal phase to the mixed phase of coexistence is always of first order. It was observed from the theoretical calculations that the transition from the ferromagnetic phase to the coexistence phase can cross over from the first to the second order at the tricritical point.     

Quantum phase transitions in matrix product states of one-dimensional spin-1 chains

We present a new model of quantum phase transitions in matrix product systems of one-dimensional spin-1 chains and study the phases coexistence phenomenon. We find that in the thermodynamic limit the proposed system has three different quantum phases and by adjusting the control parameters we are able to realize any phase, any two phases equal coexistence and the three phases equal coexistence. At every critical point the physical quantities including the entanglement are not discontinuous and the matrix product system has long-range correlation and N-spin maximal entanglement. We believe that our work is helpful for having a comprehensive understanding of quantum phase transitions in matrix product states of one-dimensional spin chains and of certain directive significance to the preparation and control of one-dimensional spin lattice models with stable coherence and N-spin maximal entanglement.     

The synthesis of the chiral non-mesogenic d-seco estrone derivatives and their influence on the phase transitions of cholesteric liquid crystals

The synthesis of new chiral seco-estrone derivatives is presented, as well as their influence on the phase transition of binary mixtures of cholesteryc liquid crystals. The new chiral derivatives do not posses any liquid crystalline phases and were synthesized in several synthetic steps, starting from estrone. We have studied the mixtures of cholesteryl non-anoate (40%) with cholesteryl myristate (40%) and addition of new chiral derivatives 3 4, or 5 (20%). It was concluded that the addition of chiral derivative 3 to the binary mixture stabilizes smectic A and cholesteric phase and shifts the phase transition temperature with respect to pure binary mixture for about 5°C towards lower temperatures. The extension of the temperature range of the cholesteric phase from 5°C to 15°C was established in the case when the derivatives 3 and 4 are added to the binary mixture of cholesteryl nonanoate with cholesteryl myristate. The phase diagrams of investigated compounds are formed on the basis of data obtained by the optical microscopy. Using X-ray diffraction on the crystalline powder of unoriented samples we have determined the molecular parameters: the thickness of smectic and cholesteric layers and average distance between the long axes of neighboring molecules.     

Thermal and Optical Properties of Some Hydrogen-Bonded Liquid Crystal Mixtures

Phase transition properties of the mixtures of hydrogen-bonded nematic liquid crystals (HBLC) 4-hexylbenzoic acid (6BA), 4-(octyloxy)benzoic acid (8OBA), and 4-(decyloxy)benzoic acid (10OBA) have been investigated by means of differential scanning calorimetry (DSC) and polarize optic microscope (POM). The DSC and POM results clearly indicate the existence of smectic and nematic phase transitions in binary mixtures. The phase transition temperature values of 6BA/10OBA mixtures have clearly increased with increasing heating rate. The activation energies were calculated for the phase transitions of 6BA/10OBA liquid crystal (LC) mixture. The optical transmittance of these mixed hydrogen-bonded nematic liquid crystals was investigated in terms of temperature variations through electrooptic methods. The electrooptic experiments indicate that, while low in the nematic phase, the optical transmittance is very high at the nematic-isotropic phase transition. The transmitted light intensity values of 6BA/8OBA mixture are somewhat higher than those of other binary mixtures, 6BA/10OBA and 8OBA/10OBA, a result associated with the different alkyloxy chain lengths.     

Smectic A-C-A Liquid Crystal Reentrance: A Photon Transmission Study

Ultraviolet/visible photon transmission measurements were applied to study liquid crystal phase transitions in the binary BOPDOB-BOPOOB mixture. A sequence exhibiting a new reentrant, namely isotropic-nematic-smectic A-C-A as temperature is lowered, is identified. For the smectic A-C transition, the critical exponent g is seen to cross over from the mean-field 0.501 - 0.008 to the helium-like 0.336 - 0.012 as the transition is approached. The reentrant C-A transition is first-order, signalling a tricritical point in the phase diagram.     

Texture transitions in binary mixtures of 6OBAC with compounds of its homologous series

Recently the authors have observed in compounds of the 4,n-alkyloxybenzoic acid series, with the homologous index n ranging from 6 to 9, a texture transition in the nematic range which subdivides the nematic phase in two sub-phases displaying different textures in polarised light analysis. To investigate a persistence of texture transitions in nematic phases, we prepared binary mixtures of 4,6-alkyloxybenzoic acid (6OBAC) with other members (7-, 8-, 9-, 12-, 16OBAC) of its homologous series. Binary mixtures exhibit a broadening in the temperature ranges of both smectic and nematic phases. A nematic temperature range of 75°C is observed. In the nematic phase, in spite of the microscopic disorder introduced by mixing two components, the polarised light optics analysis of the liquid crystal cells reveals a texture transition. In the case of the binary mixture of 6OBAC with 12OBAC and with 16OBAC, that is of compounds with monomers of rather different lengths, the texture transition temperature is not homogeneous in the cell, probably due to a local variation in the relative concentrations of compounds.     

Phase behaviour of <Emphasis Type="Italic">n</Emphasis>-hexane/perfluoro-<Emphasis Type="Italic">n</Emphasis>-hexane binary thin wetting films

We present X-ray reflectivity investigations of the concentration distribution in binary liquid thin films on silicon substrates. The liquid-vapor coexistence of the binary mixture investigated, hexane and perfluorohexane, is far from criticality. Therefore, a sharp interface separates the liquid film from the vapor. The data reveal a separation of the film in layers parallel to the substrate. A phase diagram is constructed as a projection to the (composition difference, temperature) space, covering a temperature range corresponding to the one-phase and the two-phase regime of the bulk liquid. Although the composition data indicate a mixing gap similar to that of the bulk system, there are two major differences: i) only the near-surface phase changes its composition significantly, and ii) a composition gradient in the film exists also at higher temperatures where in the bulk system the one-phase regime exists.Received: 28 April 2004, Published online: 21 September 2004PACS: 61.10.Kw X-ray reflectometry (surfaces, interfaces, films) - 64.75. + g Solubility, segregation, and mixing; phase separation - 68.15. + e Liquid thin films     

Liquid-crystal phase equilibria of Lennard-Jones chains

Liquid-crystal phase equilibria of Lennard-Jones chain fluids and the solubility of a Lennard-Jones gas in the coexisting phases are calculated from Monte Carlo simulations. Direct phase equilibria calculations are performed using an expanded formulation of the Gibbs ensemble. Monomer densities, order parameters, and equilibrium pressures are reported for the coexisting isotropic and nematic phases of: (1) linear Lennard-Jones chains, (2) a partially-flexible Lennard-Jones chain, and (3) a binary mixture of linear Lennard-Jones chains. The effect of chain length is determined by calculating the isotropic-nematic coexistence of linear Lennard-Jones chain fluids made of 8, 10, and 12 segments (8-, 10-, 12-mer). The effect of molecular flexibility on the isotropic-nematic equilibrium is studied for a Lennard-Jones 10-mer chain fluid with one freely-jointed segment at the end of the chain. An isotropic-nematic phase split and fractionation are reported for a binary mixture of linear 7-mer and 12-mer chains. Simulation results are compared with theoretical results as obtained from a recently developed analytical equation of state based on perturbation theory. Excellent agreement between theory and simulations is observed. The solubility of a monomer Lennard-Jones gas in the coexisting isotropic and nematic phases is estimated using the Widom test-particle insertion method. A linear relationship between solubility difference and density difference at isotropic-nematic coexistence is observed. It is shown that gas solubility is independent of the nematic ordering of the fluid, at constant temperature and density conditions.     

Miscibility phase diagrams of giant vesicles containing sphingomyelin

Saturated sphingomyelin (SM) lipids are implicated in lipid rafts in cell plasma membranes. Here we use fluorescence microscopy to observe coexisting liquid domains in vesicles containing SM, an unsaturated phosphatidylcholine lipid (either DOPC or POPC), and cholesterol. We note similar phase behavior in a model membrane mixture without SM (DOPC/DPPC/Chol), but find no micron-scale liquid domains in membranes of POPC/PSM/Chol. We delineate the onset of solid phases below the miscibility transition temperature, and detail indirect evidence for a three-phase coexistence of one solid and two liquid phases.     

Phase behaviour of lyotropic liquid crystals in external fields and confinement

This mini-review discusses the influence of external fields on the phase behaviour of lyotropic colloidal liquid crystals. The liquid crystal phases reviewed, formed in suspensions of highly anisotropic particles ranging from rod- to board- to plate-like particles, include nematic, smectic and columnar phases. The external fields considered are the earth gravitational field and electric and magnetic fields. For electric and magnetic fields single particle alignment, collective reorientation behaviour of ordered phases and field-induced liquid crystal phase transitions are discussed. Additionally, liquid crystal phase behaviour in various confining geometries, e.g. slit-pore, circular and spherical confinement will be reviewed.     

A phase diagram near the NAC* point in liquid crystals

We study here a mean field model to obtain the phase diagram (concentration versus temperature) near the NAC* point in a binary mixture of liquid crystal. We have fitted our phase line equations to the experimental data for the mixture of SCE9 + SCE10 liquid crystals. We deduce from our analysis that there should exist a tricritical point close to the NAC* point on the AC* phase line.     

Gibbs ensemble simulation of nematic-isotropic coexistence in a liquid crystal mixture

The results are presented of Gibbs ensemble Monte Carlo (GEMC) simulations examining the nematic–isotropic (N–I) coexistence envelope of a liquid crystal mixture. The system studied is a 50:50 mixture of 1000 generalized Gay–Berne particles with axial ratios 2.0:1 and 2.5:1. For this system, stable N–I coexistence is observed over run lengths in excess of 5 x 10⁵ GEMC sweeps. There is unambiguous evidence of fractionation, the mole fractions of long particles in the coexisting phases typically differing by 11%. The measured coexistence envelope does not conform to the lens shape predicted by Onsager theory; qualitative finite size arguments are given in explanation of this distortion.