Phase Behavior Of Liquid Crystals Research Articles

Phase behavior of lyotropic rigid-chain polymer liquid crystal studied by dissipative particle dynamics

The phase behavior of lyotropic rigid-chain liquid crystal polymer was studied by dissipative particle dynamics (DPD) with variations of the solution concentration and temperature. A chain of fused DPD particles was used to represent each mesogenic polymer backbone surrounded with the strongly interacted solvent molecules. The free solvent molecules were modeled as independent DPD particles, where each particle includes a lump of solvent molecules with the volume roughly equal to the solvated polymer segment. The simulation shows that smectic-B (S(B)), smectic-A (S(A)), nematic (N), and isotropic (I) phases exist within certain regions in the temperature and concentration parameter space. The temperature-dependent S(B)∕S(A), S(A)∕N, and N∕I phase transitions occur in the high concentration range. In the intermediate concentration range, the simulation shows coexistence of the anisotropic phases and isotropic phase, where the anisotropic phases can be the S(B), S(A), or N phases. Mole fraction and compositions of the coexisted phases are determined from the simulation, which indicates that concentration of rigid rods in isotropic phase increases as the temperature increases. By fitting the orientational distribution function of the systems, the biphasic coexistence is further confirmed. From the parameter α obtained for the simulation, the distribution of the rigid rods in the two coexistence phases is quantitatively evaluated. By using model and simulation methods developed in this work, the phase diagrams of the lyotropic rigid-chain polymer liquid crystal are obtained. Incorporating the solvent particles in the DPD simulation is critical to predict the phase coexistence and obtain the phase diagrams.

Four-dimensional structural dynamics of sheared collagen networks

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Phase Behavior of Lyotropic Liquid Crystals in Linear Alkylbenzene Sulphonate (LAS) Systems in the Presence of Dilute and Concentrated Electrolyte

A linear alkylbenzene sulphonate (LAS) system is studied in the presence of water and electrolyte (Na2SO4). The samples were studied, across a broad range of concentrations of surfactant and electrolyte, using optical microscopy, differential scanning calorimetry (DSC), and small angle x-ray scattering (SAXS). The results are contrasted with electrolyte free studies performed previously, and some startling differences are observed. An expected salting out phenomenon is observed as well as the presence of lateral phase separation. The latter phenomenon is remarkable, meaning that the lamellar phase consists of coexisting regions with different compositions rather than being homogeneous as previously thought. This behavior is dependent on the temperature and sodium sulphate concentration. This phase behavior has important implications for the formulation of detergents, and may be extended to help understanding of some biological phenomena. The phase diagrams are presented and the driving forces behind these phenomena are discussed, and a mechanism for lateral phase separation, as influenced by electrolyte, is proposed.

A single-site anisotropic soft-core model for the study of phase behavior of soft rodlike particles

A novel mesoscopic simulation model is proposed to study the liquid crystal phase behavior of the anisotropic rodlike particles with a soft repulsive interaction, which possesses a modified anisotropic conservative force type used in dissipative particle dynamics. The influences of the repulsion strength and the particle shape on the phase behavior of soft rodlike particles are examined. In the simulations, we observe the formation of the nematic phase and smectic-A phase from the initially isotropic phase. Moreover, we find that shorter soft rodlike particles with anisotropic repulsive interactions can form a stable smectic-B phase. Our results demonstrate that the soft anisotropic purely-repulsive potential between the rodlike particles can reflect the interaction nature between soft rodlike particles in a simple way and is sufficient to produce a range of ordered LC-like mesophases.

Phase Behavior of Lipid–Based Lyotropic Liquid Crystals in Presence of Colloidal Nanoparticles

We have investigated the microstructure and phase behavior of monoglyceride-based lyotropic liquid crystals in the presence of hydrophilic silica colloidal particles of size comparable to or slightly exceeding the repeat units of the different liquid crystalline phases. Using small angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC), we compare the structural properties of the neat mesophases with those of the systems containing silica colloidal particles. It is found that the colloidal particles always macrophase separate in inverse bicontinuous cubic phases of gyroid (Ia3d) and double diamond (Pn3m) symmetries. SAXS data for the inverse columnar hexagonal phase (H(II)) and lamellar phase (L(α)) suggest that a low volume fraction of the nanoparticles can be accommodated within the mesophases, but that at concentrations above a given threshold, the particles do macrophase separate also in these systems. The behavior is interpreted in terms of the enthalpic and entropic interactions of the nanoparticles with the lamellar and hexagonal phases, and we propose that, in the low concentration limit, the nanoparticles are acting as point defects within the mesophases and, upon further increase in concentration, initiate nucleation of nanoparticles clusters, leading to a macroscopic phase separation.

Publisher’s Note: Effect of enantiomeric excess on the phase behavior of antiferroelectric liquid crystals [Phys. Rev. E83, 060701(R) (2011)

Publisher’s Note: Effect of enantiomeric excess on the phase behavior of antiferroelectric liquid crystals [Phys. Rev. E<b>83</b>, 060701(R) (2011)

Double Peak Specific Heat Capacity Anomaly in Mixtures of Liquid Crystals and Nanoparticles

The liquid crystal phase behaviour in the interval close to the isotropic-nematic phase transition and in the vicinity of wetting and dewetting interface has been analysed. For the theoretical study Landau-de Gennes mesoscopic model in terms of the tensor orientational order parameter has been used. It has been shown that in an appropriate interval of surface wetting interaction strengths, wetting and dewetting phenomena could take place. This phenomenon could be a reason behind the observed double peak anomaly in the specific heat capacity C p temperature dependence in a mixture of nanoparticles and liquid crystals.

Effect of enantiomeric excess on the phase behavior of antiferroelectric liquid crystals

Null transmission ellipsometry and resonant x-ray diffraction are employed to study the effect of enantiomeric excess (EE) on the phase behavior of antiferroelectric liquid crystal 10OTBBB1M7. Phase sequence, layer spacing, and pitch of the helical structures of the smectic-C(α)* and smectic-C* phases are studied as a function of temperature and EE. Upon reducing EE, a liquid-gas-type critical point of the smectic-C(α)* to smectic-C* transition is observed, as well as the disappearance of the smectic-C(d4)* and the smectic-C(d3)* phases. Results are analyzed in a mean-field model.

Phase Behavior and Rheological Analysis of Reverse Liquid Crystals and W/I2 and W/H2 Gel Emulsions Using an Amphiphilic Block Copolymer

This article reports the phase behavior determi-nation of a system forming reverse liquid crystals and the formation of novel disperse systems in the two-phase region. The studied system is formed by water, cyclohexane, and Pluronic L-121, an amphiphilic block copolymer considered of special interest due to its aggregation and structural properties. This system forms reverse cubic (I2) and reverse hexagonal (H2) phases at high polymer concentrations. These reverse phases are of particular interest since in the two-phase region, stable high internal phase reverse emulsions can be formed. The characterization of the I2 and H2 phases and of the derived gel emulsions was performed with small-angle X-ray scattering (SAXS) and rheometry, and the influence of temperature and water content was studied. The H2 phase experimented a thermal transition to an I2 phase when temperature was increased, which presented an Fd3m structure. All samples showed a strong shear thinning behavior from low shear rates. The elastic modulus (G') in the I2 phase was around 1 order of magnitude higher than in the H2 phase. G' was predominantly higher than the viscous modulus (G''). In the gel emulsions, G' was nearly frequency-independent, indicating their gel type nature. Contrarily to water-in-oil (W/O) normal emulsions, in W/I2 and W/H2 gel emulsions, G', the complex viscosity (|η*|), and the yield stress (τ0) decreased with increasing water content, since the highly viscous microstructure of the continuous phase was responsible for the high viscosity and elastic behavior of the emulsions, instead of the volume fraction of dispersed phase and droplet size. A rheological analysis, in which the cooperative flow theory, the soft glass rheology model, and the slip plane model were analyzed and compared, was performed to obtain one single model that could describe the non-Maxwellian behavior of both reverse phases and highly concentrated emulsions and to characterize their microstructure with the rheological properties.

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.

Phytantriol and glyceryl monooleate cubic liquid crystalline phases as sustained-release oral drug delivery systems for poorly water soluble drugs I. Phase behaviour in physiologically-relevant media

Abstract Objectives The potential utility of liquid crystalline lipid-based formulations in oral drug delivery is expected to depend critically on their structure formation and stability in gastrointestinal fluids. The phase behaviour of lipid-based liquid crystals formed by phytantriol and glyceryl monooleate, known to form a bicontinuous cubic phase in excess water, was therefore assessed in physiologically-relevant simulated gastrointestinal media. Methods Fixed composition phase studies, crossed polarised light microscopy (CPLM) and small angle X-ray scattering (SAXS) were used to determine the phase structures formed in phosphate-buffered saline, simulated gastric and intestinal fluids in the presence of model poorly water soluble drugs cinnarizine, diazepam and vitamin E acetate. Key findings The phase behaviour of phytantriol in phosphate-buffered saline was very similar to that in water. Increasing concentrations of bile components (bile salts and phospholipids) caused an increase in the lattice parameter of the cubic phase structure for both lipids. Incorporation of cinnarizine and diazepam did not influence the phase behaviour of the phytantriol- or glyceryl monooleate-based systems at physiological temperatures; however, an inverse hexagonal phase formed on incorporation of vitamin E acetate. Conclusions Phytantriol and glyceryl monooleate have the potential to form stable cubic phase liquid crystalline delivery systems in the gastrointestinal tract. In-vivo studies to assess their sustained-release behaviour are warranted.

Enhanced skin permeation and hydration by magnetic field array: preliminary in-vitro and in-vivo assessment

The aim of the study was determine the effect of magnetic film array technology on the skin permeation of urea. A 5% urea gel was applied to human epidermal membrane in vitro and human skin in vivo. Application of gel with magnetic film array and plastic occlusive film was compared with application of gel with a plastic occlusive film and non-magnetic film. In-vitro epidermal penetration was determined using a Franz-type diffusion system. In-vivo permeation and changes in epidermal properties were visualised by optical coherence tomography. The mean cumulative permeation of urea over 2 h for magnetic film array application was 89.54 +/- 7.34 microg/cm(2) as compared with 20.83 +/- 2.02 microg/cm(2) for passive occluded application (mean +/- SEM, n = 9/8), representing greater than 4-fold increase over the 2-h application time period. Administration of urea with the magnetic film array resulted in the lag time being reduced from 40.58 +/- 3.98 to 21.13 +/- 6.27 min (P < 0.02), while steady state flux increased from 0.24 +/- 0.03 to 0.75 +/- 0.06 microg/cm(2) per min (P < 0.0001). Under active occlusion, the relative change in epidermal thickness as determined by optical coherence tomography increased by 16 and 11% at 30 and 60 min, respectively. Administration with a novel magnetic film array technology provided enhanced skin penetration of urea and increased epidermal hydration when compared with administration under an occlusive film only.

Phase behavior of ionic liquid crystals

Bulk properties of ionic liquid crystals are investigated using density functional theory. The liquid crystal molecules are represented by ellipsoidal particles with charges located in their center or at their tails. Attractive interactions are taken into account in terms of the Gay–Berne pair potential. Rich phase diagrams involving vapor, isotropic and nematic liquid, as well as smectic phases are found. The dependence of the phase behavior on various parameters such as the length of the particles and the location of charges on the particles is studied.

A soft-core Gay–Berne model for the simulation of liquid crystals by Hamiltonian replica exchange

The Gay-Berne (GB) potential has proved highly successful in the simulation of liquid crystal phases, although it is fairly demanding in terms of resources for simulations of large (e.g., N>10(5)) systems, as increasingly required in applications. Here, we introduce a soft-core GB model, which exhibits both liquid crystal phase behavior and rapid equilibration. We show that the Hamiltonian replica exchange method, coupled with the newly introduced soft-core GB model, can effectively speed up the equilibration of a GB liquid crystal phase by frequent exchange of configurations between replicas, while still recovering the mesogenic properties of the standard GB potential.

Phase Behavior of Liquid Crystals Formed in [C12mim]CI/H2O and [C12mim]CI/Alcohols Systems

Phase behaviors of different binary systems involving 1-dodecyl-3-methylimidazolium chloride ([C12mim]Cl) and H2O, [C12mim]Cl and different alcohols (1-butanol, 1-pentanol, 1-hexanol and 1-octanol) are investigated at 25 C. Hexagonal liquid crystal phase (H1) is identified in [C12mim]Cl/H2O system, and lamellar liquid-crystalline (L) phase is found in [C12mim]Cl/alcohols systems by using polarized optical microscopy and small-angle X-ray scattering techniques. The formation of such phases is considered as a synergetic result of the solvatophobic force and the hydrogen-bonded network comprising an imidazolium ring, chloride ion and water (or alcohols), which can be confirmed by Fourier transform infrared spectra. It is noticeable that in [C12mim]Cl/1-octanol system, the lattice spacings of lamellar phase increase with increasing C12mimCl concentration, which is opposite to the results of [C12mim]Cl/H2O system. This may result mainly from stronger static repulsion among hydrophilic headgroups of imidazolium salts arranged in the bilayers of lamellar structures. Further measurements by differential scanning calorimetry indicate that the lamellar phase is stable within a wide temperature range above room temperature. However, the lattice spacings decrease with the increase of temperature, which may be due to the softening of the hydrocarbon chain of [C12mim]Cl molecules. In different alcohols systems, it is found that the lamellar lyotropic liquid crystal structure is easier to be formed when the carbon chain length becomes longer.

Liquid Crystal Phase Transitions in Systems of Colloidal Platelets with Bimodal Shape Distribution

We have studied a system of polydisperse, charged colloidal gibbsite platelets with a bimodal distribution in the particle aspect ratio. We observe a density inversion of the coexisting isotropic and nematic phases as well as a three-phase equilibrium involving a lower density nematic phase, an isotropic phase of intermediate density, and a higher density columnar phase. To relate these phenomena to the bimodality of the shape distribution, we have calculated the liquid crystal phase behavior of binary mixtures of thick and thin hard platelets for various thickness ratios. The predictions are based on the Onsager-Parsons theory for the isotropic-nematic (I-N) transition combined with a modified Lennard-Jones-Devonshire cell theory for the columnar (C) state. For sufficiently large thickness ratios, the phase diagram features an I-N density inversion and triphasic I-N-C equilibrium, in agreement with experiment. The density inversion can be attributed to a marked shape fractionation among the coexisting phases with the thick species accumulating in the isotropic phase. At high concentrations, the theory predicts a coexistence between two columnar phases with distinctly different concentrations. In experiment, however, the demixing transition is pre-empted by a transition to a kinetically arrested, glassy state with structural features resembling a columnar phase.

Oleoylethanolamide-Based Lyotropic Liquid Crystals as Vehicles for Delivery of Amino Acids in Aqueous Environment

We have investigated the phase behavior of self-assembled lyotropic liquid crystals (LC) formed by ternary mixtures of oleoylethanolamide (OEA), water and arginine. OEA, a natural analog of the endogenous cannabinoid anandamide involved in the peripheral regulation of feeding, was selected as a main component due to its capacity to induce efficient decreases in food intake and gains in body mass. Arginine was selected as representative hydrophilic amino acid and added to the OEA-water mixture at different concentrations. The phase diagrams were determined by combining cross-polarized optical microscopy and small angle x-ray scattering. First, the phase diagram for the OEA-water system was determined. It was shown that these two compounds give rise to reverse Ia3d double gyroid and reverse Pn3m double diamond cubic phases existing in bulk over a large window of temperature and composition, and that for water content beyond 25% Pn3m coexisted with excess water. Successively, the influence of arginine as guest molecule in the water channels of the reverse LC was investigated. For the sake of comparison, results for the OEA-water-arginine system were compared with analog series of OEA-water-glucose. The results showed that, at a fixed water content and temperature, the phase behavior of the liquid crystalline phases is strongly dependent on arginine concentration. In more detail, arginine could be encapsulated in the bulk OEA-water LC up to 2.0% wt, whereas transitions from Ia3d to Pn3m cubic phase were observed with increasing arginine concentration. Interestingly, upon an increase of water concentration beyond 20–25%, Pn3m phase started to coexist with excess water releasing the arginine in external water solution. Quantitative measurements of arginine content inside the LC water channels and in the excess external water solution revealed a complete release of the amino acid, demonstrating that the investigated lyotropic liquid crystalline systems can be used as ideal vehicles for the delivery of functional hydrophilic active molecules in aqueous environment.

Chiral-nematic self-ordering of rodlike cellulose nanocrystals grafted with poly(styrene) in both thermotropic and lyotropic states

Graft copolymers of rodlike cellulose nanocrystals (CNC) with poly(styrene) (PSt) were synthesized through atom transfer radical polymerization (ATRP). The hydroxyl groups on CNC were esterified with 2-bromoisobutyrylbromide to yield 2-bromoisobutyryloxy groups, which were used to initiate the polymerization of poly(styrene). The graft copolymers were characterized by thermogravimetric analysis (TGA), fourier transform infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). The size of the original CNC is 10–40nm in width and 100–400nm in length, which was characterized by atomic force microscopy (AFM). The thermal and liquid crystalline properties of the graft copolymers were investigated by differential scanning calorimeter (DSC) and polarizing optical microscope (POM). The graft copolymers exhibit fingerprint texture in both thermotropic and lyotropic states. In thermotropic state, the PSt-grafted CNC orient spontaneously in isotropic melt (PSt side chains acting as a solvent). The thermotropic liquid crystal phase behavior is similar to the lyotropic phase behavior.

Chromonic nematic phase and scalar order parameter of indanthrone derivative with ionic additives

We investigate influence of different ionic additives on the phase behaviour and scalar order parameter of lyotropic chromonic nematic liquid crystals formed by the molecules representing derivatives of indanthrone. KI, (NH4)2SO4 and NaCl salts increase biphasic nematic region on the temperature-concentration phase diagram, whereas the scalar orientational order parameter is hardly sensitive to their presence. We suggest that these changes are attributed to increase in the aggregate length and polydispersity of the latter, while the interaction between aggregates remains unaffected. The Na2SO4 salt lowers anomalously the measured value of the scalar order parameter to 0.42, for which the nematic phase should not exist. We address this anomaly to modification of the shape of chromonic aggregates due to growing of side chains within the rod-like aggregates. The NH4Cl salt does not affect the phase diagram and the scalar order parameter of Blue 250 chromonematic. PACS: 78.20.Ci, 87.15.Mi, 78.20.Fm, 42.79.Kr, 61.30.Gd. UDC: 535.34

Effective free-energy method for nematic liquid crystals in contact with structured substrates

We study the phase behavior of a nematic liquid crystal confined between a flat substrate with strong anchoring and a patterned substrate whose structure and local anchoring strength we vary. By first evaluating an effective surface free-energy function characterizing the patterned substrate, we derive an expression for the effective free energy of the confined nematic liquid crystal. Then we determine phase diagrams involving a homogeneous state in which the nematic director is almost uniform and a hybrid aligned nematic state in which the orientation of the director varies through the cell. Direct minimizations of the free-energy functional were performed in order to test the predictions of the effective free-energy method. We find remarkably good agreement between the phase boundaries calculated from the two approaches. In addition, the effective free-energy method allows one to determine the energy barriers between two states in a bistable nematic device.