Phase Behavior Of Liquid Crystals Research Articles

Molecular theory of a ferromagnetic nematic liquid crystal.

We employ a version of classical density functional theory to study the phase behavior of a simple model liquid crystal in an external field. The uniaxially symmetric molecules have a spherically symmetric core with superimposed orientation-dependent attractions. The interaction between the cores consists of a hard-sphere repulsion plus an isotropic square-well attraction. The anisotropic part of the interaction potential allows for the formation of a uniaxially symmetric nematic phase. The orientation of the molecules couples to an external polar field. The external field is capable of rotating the nematic director n[over ̂] in the x-z plane. The field is also capable of changing the topology of the phase diagram in that it suppresses the phase coexistence between an isotropic liquid and a nematic phase observed in the absence of the field. We study the transition from an unpolar to a polar nematic phase in terms of the orientation-distribution function (odf), nematic and polar order parameters, and components of n[over ̂]. If represented suitably the odf allows us to study orientational changes during the switching process between nonpolar and polar nematic phases. We also give a simple argument that explains why nematic order is lost whereas polar order persists up to the gas-liquid critical point along the coexistence curve. We also discuss the relevance of our theory for future experimental studies.

Liquid-crystal behavior in Fe(OH)3/palygorskite non-aqueous dispersion

In this paper, non-aqueous Fe(OH)3/palygorskite dispersion was prepared and its liquid crystal phase behavior was investigated. Positively charged Fe(OH)3 colloidal particles were put in to non-aqueous and organically modified palygorskite dispersion. The effects of organically treated palygorskite and Fe(OH)3 on the preparation of stable palygorskite dispersion were characterized with FT-IR, XRD, Contact Angle measurement, Zeta potential detection, Settlement measurement and SEM, respectively. The addition of Fe(OH)3 particles shifted the concentrations of the coexisting isotropic and nematic phases to higher values while at the same time markedly accelerated the phase separation. The influence of Fe(OH)3 particles on the dispersion in magnetic field was also discussed.

Polymorphic transitions mediated by surfactants in liquid crystal nanodroplet

ABSTRACTRecently, various techniques have been developed using photonic crystals. Liquid crystals (LC) confined in a nanodroplet mimicked photonic crystals, such as those of opal. Therefore, investigating the phase behaviour of LC molecules in nanodroplets is very important in the next-generation optical field. In this study, the chemical interaction between surfactants and LCs in nanodroplets is reproduced using a dissipative particle dynamics method. We identify the phase behaviour of LCs and investigate how the chemical interaction affect on the orientation of LCs. In particular, by adding surfactant molecules, various morphological behaviours were observed in the LC nanodroplet. The phase transition temperature varied depending on RND (amount of surfactant molecules). Furthermore, difference of the self-assembly structure also appeared inside the droplet depending on RND. Our simulation offers a theoretical guide to control morphologies of self-assembled LCs inside a nanodroplet, a novel system that may find applications in nanofluidic devices or in photonic crystal technology.

Rheological transition of an ethoxylated alkylamine emulsion induced by acetic acid and its application to drilling fluid

This work aims to investigate the changes in the shear and oscillation responses of an ethoxylated alkylamine emulsion with the addition of acetic acid and establishes their relationships with the emulsion phase inversion. The initial emulsion behaves as a non-Newtonian fluid exhibiting shear thinning with a viscoelastic gel structure (at rest). Upon the addition of acetic acid, the emulsion first transforms to a structureless (at rest) non-Newtonian fluid with lower viscosity and worse shear thinning compared with the initial state and then converts back to a non-Newtonian fluid with a higher gel strength, higher elasticity (at rest) and better shear thinning than the initial state as the phase inversion proceeds from an oil-continuous stage to a bicontinuous stage. This regained non-Newtonian character can be maintained throughout the whole bicontinuous stage and can even extend to the beginning of the water-continuous stage which is obtained from the bicontinuous stage by increasing the acetic acid content; however, it is ultimately replaced by a structureless (at rest) non-Newtonian fluid that exhibits lower viscosity and worse shear thinning compared with the initial state as the acetic acid content increases. The establishment of relationships among the interfacial moduli and deformation, geometrical factors (i.e., interfacial curvature, droplet shape and size and positional structure) and the liquid crystal phase behaviors help to elucidate the mechanisms that control the rheological transitions of emulsions. Based on these results, a novel water-washable viscoelastic emulsion drilling fluid is proposed.

Effect of the anchoring strength on the phase behaviour of discotic liquid crystals under face-on confinement

In this study we have performed molecular dynamics simulations to study a Gay–Berne discotic fluid confined in a slab geometry for a fixed confinement length. Four different anchoring strengths with a homeotropic (face-on) configuration were studied. We found that changing the anchoring strength changes the normal component of the stress tensor, which in turn changes the density of the system’s bulk. This phenomenon leads to a shift in the isotropic-nematic transition temperature. We observe that the temperature regions where the nematic phase is present diminishes as the anchoring strength increases. The anchoring strength also affects the nematic-columnar coexistence temperature-region: it spans over more temperatures at higher anchoring strengths.

Collective orientational order and phase behavior of a discotic liquid crystal under nanoscale confinement.

The phase behavior and molecular ordering of hexakishexyloxy triphenylene (HAT6) DLCs under cylindrical nanoconfinement are studied utilizing differential scanning calorimetry (DSC) and dielectric spectroscopy (DS), where cylindrical nanoconfinement is established through embedding HAT6 into the nanopores of anodic aluminum oxide (AAO) membranes, and a silica membrane with pore diameters ranging from 161 nm down to 12 nm. Both unmodified and modified pore walls were considered. In the latter case the pore walls of AAO membranes were chemically treated with n-octadecylphosphonic acid (ODPA) resulting in the formation of a 2.2 nm thick layer of grafted alkyl chains. Phase transition enthalpies decrease with decreasing pore size, indicating that a large proportion of the HAT6 molecules within the pores has a disordered structure, which increases with decreasing pore size for both pore walls. In the case of the ODPA-modification, the amount of ordered HAT6 is increased compared to the unmodified case. The pore size dependencies of the phase transition temperatures were approximated using the Gibbs–Thomson equation, where the estimated surface tension is dependent on the molecular ordering of HAT6 molecules within the pores and upon their surface. DS was employed to investigate the molecular ordering of HAT6 within the nanopores. These investigations revealed that with a pore size of around 38 nm, for the samples with the unmodified pore walls, the molecular ordering changes from planar axial to homeotropic radial. However, the planar axial configuration, which is suitable for electronic applications, can be successfully preserved through ODPA-modification for most of the pore sizes.

Rich liquid crystal phase behavior of novel alkyl-tri(ethylene glycol)-glucoside carbohydrate surfactants

Carbohydrates are appealing non-ionic surfactant head-groups as they are naturally abundant, generally biocompatible and biodegradable, and readily functionalized. Herein, we explore the phase behavior of seven novel carbohydrate-based surfactants (CBS) containing a tri-ethylene glycol (TEG) linker between a glucose head-group and alkyl tail-group, with linear saturated (C8–18) and cis-unsaturated (C18:1) alkyl chains. At high aqueous concentrations, these glycolipid-like surfactants transition into a variety of lyotropic liquid crystalline phases following an expected concentration phase sequence: hexagonal (H1) → bicontinuous cubic (V1) → lamellar (Lα). Using polarizing light microscopy (PLM), a binary (surfactant–water) phase diagram for each surfactant was constructed across a temperature range (25–80 °C) revealing thermotropic behavior and a broadening of liquid crystal phase regions with increasing alkyl chain length. There was also a significant difference between saturated and unsaturated alkyl chains, due to the cis-unsaturated ‘statistical bend’ lowering the melting point. Small-angle X-ray scattering (SAXS) measurements were performed to characterize the liquid crystal phases, identifying highly-ordered p6m,Ia3d, and Lα crystallographic space-groups with up to 7 resolved Bragg peaks, likely due to the highly anisometric nature of the TEG-linked surfactants. The phases were shown to be more numerous and exhibited greater thermal-stability compared to well-characterized alkyl glucoside surfactants lacking an oligoethylene spacer in the literature. Finally, the characteristic dimensions of each phase were determined to enable visualization of the internal microstructures, providing insight into the impact of molecular shape and the distribution of hydro-philicity/phobicity on the formation and stability of liquid crystalline mesophases.

Novel lanthanidomesogens based on poly(ethylene glycol) cholesterol ether: Liquid crystal phase behavior and luminescence properties

Biocompatible systems with luminescent properties attract significant interest as they are broadly used in bioanalysis and medical diagnostics. This paper describes new lanthanide liquid crystals based on an oxyethylated amphiphile with a cholesterol fragment (CholEO10). The complex of physicochemical methods (polarizing optical microscopy (POM), X-ray powder diffraction, FTIR-spectroscopy and luminescent analysis) was used to study liquid crystalline, structural and optical properties of these new biomesogens. Their phase behavior was compared with the behavior a lanthanum-containing analogue without a cholesterol fragment in its structure. A rigid hydrophobic fragment was found to exert a strong influence on lyotropic mesomorphism in aqueous media. The phase transition from a lamellar mesophase to a hexagonal one was observed with decrease of the CholEO10/La3+ complex concentration and addition of water. The study of luminescent properties of CholEO10/Ln3+ complexes, where Ln3+ is Dy3+, Tb3+, or Eu3+, revealed that their characteristic emission occurs in the yellow, green and red spectral ranges. Optical characteristics of new mesogens were estimated. Mesogenic CholEO10/Tb3+ and CholEO10/Eu3+ complexes demonstrate longer lifetime of their excited state as compared with the C12EO10/Ln3+/H2O complex.

Liquid crystal phase behavior of a DNA dodecamer and the chromonic dye Sunset Yellow

Sunset Yellow (SSY) is an aromatic heterocycle nano-sheet functionalized by hydrophilic sulphanate groups. SSY forms chromonic stacks and liquid crystal (LC) phases in aqueous solution. The DNA oligomer 5\ensuremath{'}-GCGCTTAAGCGC-3\ensuremath{'} is a self-complementary strand which forms duplexed B-form helices in aqueous solution, which, similarly, aggregate into chromonic stacks and form LC phases. Binary aqueous solutions of these two molecules were investigated using polarized optical microscopy, x-ray diffraction, and spectroscopy. At lower solute concentrations and/or higher temperatures these solutions form uniformly mixed single phases, including isotropic, chiral nematic, and hexagonal columnar LCs. At higher solute concentrations and/or lower temperatures, the uniform columnar solution separates into two columnar phases, one containing SSY with trace DNA and the other containing both SSY and DNA aggregates. The study of these solutions indicates that the mixed and unmixed phases are composed of single component SSY or DNA chromonic stacks, with the DNA stacks containing a small fraction of intercalated SSY, evidenced by structurally induced circular dichroism in the SSY absorption band. In the columnar monophase, the hexagonal lattice sites are occupied randomly by either DNA or SSY columns, with the column spacing varying continuously with the SSY-DNA mass ratio. The results demonstrate significant selectivity in the chromonic stacking of both molecules. The binding mode of these chromonic LCs may have applications to adaptive optics and nucleic acid chemistry.

Filamentous Viruses Grafted with Thermoresponsive Block Polymers: Liquid Crystal Behaviors of a Rodlike Colloidal Model with “True” Attractive Interactions

Understanding how attractive interactions among rigid polymers or rodlike particles influence their liquid crystal (LC) phase behavior is of fundamental and practical importance. This question has not been fully answered yet, mainly due to the shortage of model systems with “true” pairwise attractions on a single particle level while with excellent colloidal stability. Herein, we report on a well-defined rodlike system that fulfills such criteria, through covalently grafting the free end of the thermoresponsive PNIPAM block of poly(ethylene glycol)-block-poly(N-isopropylacrylamide) (PEG-b-PNIPAM) onto the classic rodlike model system—the fd or M13 virus—which is the hallmark in understanding the LC behaviors of rigid polymer or rodlike particles. Increasing temperature induces dehydration and collapse of the PNIPAM chains onto the virus surface and therefore introduces attractions among the viruses, while the outer hydrophilic PEG block offers steric stabilization to prevent interparticle aggregation, gel...

Synthesis, Self-Assembly, and Drug-Release Properties of New Amphipathic Liquid Crystal Polycarbonates.

New amphiphilic liquid crystal (LC) polycarbonate block copolymers containing side-chain cholesteryl units were synthesized. Their structure, thermal stability, and LC phase behavior were characterized with Fourier transform infrared (FT-IR) spectrum, 1H NMR, gel permeation chromatographic (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarizing optical microscope (POM), and XRD methods. The results demonstrated that the LC copolymers showed a double molecular arrangement of a smectic A phase at room temperature. With the elevating of LC unit content in such LC copolymers, the corresponding properties including decomposition temperature (Td), glass temperature (Tg), and isotropic temperature (Ti) increased. The LC copolymers showed pH-responsive self-assembly behavior under the weakly acidic condition, and with more side-chain LC units, the self-assembly process was faster, and the formed particle size was smaller. It indicated that the self-assembly driving force was derived from the orientational ability of LC. The particle size and morphologies of self-assembled microspheres loaded with doxorubicin (DOX), together with drug release tracking, were evaluated by dynamic light scattering (DLS), SEM, and UV–vis spectroscopy. The results showed that DOX could be quickly released in a weakly acidic environment due to the pH response of the self-assembled microspheres. This would offer a new strategy for drug delivery in clinic applications.

On the thermotropic and magnetotropic phase behavior of lipid liquid crystals containing magnetic nanoparticles.

The inclusion of superparamagnetic iron oxide nanoparticles (SPIONs) in lipid mesophases is a promising strategy for drug-delivery applications, combining the innate biocompatibility of lipid architectures with SPIONs' response to external magnetic fields. Moreover, the organization of SPIONs within the lipid scaffold can lead to locally enhanced SPIONs concentration and improved magnetic response, which is key to overcome the current limitations of hyperthermic treatments. Here we present a Small-Angle X-ray Scattering (SAXS) structural investigation of the thermotropic and magnetotropic behavior of glyceryl monooleate (GMO)/water mesophases, loaded with hydrophobic SPIONs. We prove that even very low amounts of SPIONs deeply alter the phase behavior and thermotropic properties of the mesophases, promoting a cubic to hexagonal phase transition, which is similarly induced upon application of an Alternating Magnetic Field (AMF). Moreover, in the hexagonal phase SPIONs spontaneously self-assemble within the lipid scaffold into a linear supraparticle. This phase behavior is interpreted in the framework of the Helfrich's theory, which shows that SPIONs affect the mesophase both from a viscoelastic and from a structural standpoint. Finally, the dispersion of these cubic phases into stable magnetic colloidal particles, which retain their liquid crystalline internal structure, is addressed as a promising route towards magneto-responsive drug-delivery systems (DDS).

Influence of anchoring in the phase behaviour of discotic liquid crystals.

Molecular dynamics simulations were performed for a Gay-Berne discotic fluid confined in a slab geometry for two different anchorings: homeotropic (face-on) and planar (edge-on), and for two different confinement lengths. Our results show that the behaviour of the more confined system in the temperature region of the isotropic-nematic transition is critically influenced by the presence of the walls: the growth of the solid-liquid crystal interface spans over the entire width of the cell, and the character of the transition is changed from first order to continuous. For all the confined systems studied, we observe a higher nematic-columnar transition temperature and a smaller nematic phase region in the phase diagram, as compared with the behaviour of the infinite system.

Self-organisation of semi-flexible rod-like particles.

We report on a comprehensive computer simulation study of the liquid-crystal phase behaviour of purely repulsive, semi-flexible rod-like particles. For the four aspect ratios we consider, the particles form five distinct phases depending on their packing fraction and bending flexibility: the isotropic, nematic, smectic A, smectic B, and crystal phase. Upon increasing the particle bending flexibility, the various phase transitions shift to larger packing fractions. Increasing the aspect ratio achieves the opposite effect. We find two different ways in which the layer thickness of the particles in the smectic A phase may respond to an increase in concentration. The layer thickness may either decrease or increase depending on the aspect ratio and flexibility. For the smectic B and the crystalline phases, increasing the concentration always decreases the layer thickness. Finally, we find that the layer spacing jumps to a larger value on transitioning from the smectic A phase to the smectic B phase.

Probabilistic and thermodynamic approach on phase behavior of nematic liquid crystals: A comparative study

ABSTRACTThe systems chosen for the present investigation, p-n-alkylbenzoic acid (nBAC; n = 6, 7) exhibits nematic-isotropic transition. A comparative study based on quantum probabilistic and statistical thermodynamics has been carried out with respect to translational and orientational motions. The evaluation of net atomic charges and dipole moment at each atomic centre has been carried out through the complete neglect differential overlap (CNDO/2) method. The modified Rayleigh-Schrodinger perturbation theory along with multicentered-multipole expansion method has been employed to evaluate the long-range intermolecular interactions, while the ‘6-exp’ potential function has been assumed for short-range interactions. The total interaction energy values obtained through these computations have been used as input to calculate the probability of occurrence of a particular configuration using the Maxwell-Boltzmann formula. Further, thermodynamic parameters such as Helmholtz free energy, and entropy at room temperature (300 K), and nematic-isotropic transition temperatures have been computed. An attempt has been made to understand the structure-phase behaviour relationship at molecular level.

Phase Behavior and Physical Properties of New Biobased Ionic Liquid Crystals.

Protic ionic liquids (PILs) have emerged as promising compounds and attracted the interest of the industry and the academy community, due to their easy preparation and unique properties. In the context of green chemistry, the use of biocompounds, such as fatty acids, for their synthesis could disclose a possible alternative way to produce ILs with a low or nontoxic effect and, consequently, expanding their applicability in biobased processes or in the development of bioproducts. This work addressed efforts to a better comprehension of the complex solid-[liquid crystal]-liquid thermodynamic equilibrium of 20 new PILs synthesized by using fatty acids commonly found in vegetable oils, as well as their rheological profile and self-assembling ability. The work revealed that their phase equilibrium and physical properties are significantly impacted by the structure of the ions used for their synthesis. The use of unsaturated fatty acids and bis(2-hydroxyethyl)ammonium for the synthesis of these biobased ILs led to a drastic decreasing of their melting temperatures. Also, the longest alkyl chain fatty acids promoted higher self-assembling and more stable mesophases. Besides their sustainable appeal, the marked high viscosity, non-Newtonian profile, and very low critical micellar concentration values of the PIL crystals here disclosed make them interesting renewable compounds with potential applications as emulsifiers, stabilizers, thickeners, or biolubricants.

Density functional theory and simulations of colloidal triangular prisms.

Nanopolyhedra form a versatile toolbox to investigate the effect of particle shape on self-assembly. Here we consider rod-like triangular prisms to gauge the effect of the cross section of the rods on liquid crystal phase behavior. We also take this opportunity to implement and test a previously proposed version of fundamental measure density functional theory (0D-FMT). Additionally, we perform Monte Carlocomputer simulations and we employ a simpler Onsager theory with a Parsons-Lee correction. Surprisingly and disappointingly, 0D-FMT does not perform better than the Tarazona and Rosenfeld's version of fundamental measure theory (TR-FMT). Both versions of FMT perform somewhat better than the Parsons-Lee theory. In addition, we find that the stability regime of the smectic phase is larger for triangular prisms than for spherocylinders and square prisms.

Phase behavior and characterization of heptamethyltrisiloxane-based de Vries smectic liquid crystal by electro-optics, x rays, and dielectric spectroscopy.

A heptamethyltrisiloxane liquid crystal (LC) exhibiting I-SmA^{*}-SmC^{*} phases has been characterized by calorimetry, polarizing microscopy, x-ray diffraction, electro-optics, and dielectric spectroscopy. Observations of a large electroclinic effect, a large increase in the birefringence (Δn) with electric field, a low shrinkage in the layer thickness (∼1.75%) at 20 °C below the SmA^{*}-SmC^{*} transition, and low values of the reduction factor (∼0.40) suggest that the SmA^{*} phase in this material is of the de Vries type. The reduction factor is a measure of the layer shrinkage in the SmC^{*} phase and it should be zero for an ideal de Vries. Moreover, a decrease in the magnitude of Δn with decreasing temperature indicates the presence of the temperature-dependent tilt angle in the SmA^{*} phase. The electro-optic behavior is explained by the generalized Langevin-Debye model as given by Shen etal. [Y. Shen et al., Phys. Rev. E 88, 062504 (2013)10.1103/PhysRevE.88.062504]. The soft-mode dielectric relaxation strength shows a critical behavior when the system goes from the SmA^{*} to the SmC^{*} phase.

Strain-induced alignment and phase behavior of blue phase liquid crystals confined to thin films.

We report on the influence of surface confinement on the phase behavior and strain-induced alignment of thin films of blue phase liquid crystals (BPs). Confining surfaces comprised of bare glass, dimethyloctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride (DMOAP)-functionalized glass, or polyvinyl alcohol (PVA)-coated glass were used with or without mechanically rubbing to influence the azimuthal anchoring of the BPs. These experiments reveal that confinement can change the phase behavior of the BP films. For example, in experiments performed with rubbed-PVA surfaces, we measured the elastic strain of the BPs to change the isotropic-BPII phase boundary, suppressing formation of BPII for film thicknesses incommensurate with the BPII lattice. In addition, we observed strain-induced alignment of the BPs to exhibit a complex dependence on both the surface chemistry and azimuthal alignment of the BPs. For example, when using bare glass surfaces causing azimuthally degenerate and planar anchoring, BPI oriented with (110) planes of the unit cell parallel to the contacting surfaces for thicknesses below 3 μm but transitioned to an orientation with (200) planes aligned parallel to the contacting surfaces for thicknesses above 4 μm. In contrast, BPI aligned with (110) planes parallel to confining surfaces for all other thicknesses and surface treatments, including bare glass with uniform azimuthal alignment. Complementary simulations based on minimization of the total free energy (Landau-de Gennes formalism) confirmed a thickness-dependent reorientation due to strain of BPI unit cells within a window of surface anchoring energies and in the absence of uniform azimuthal alignment. In contrast to BPI, BPII did not exhibit thickness-dependent orientations but did exhibit orientations that were dependent on the surface chemistry, a result that was also captured in simulations by varying the anchoring energies. Overall, the results in this paper reveal that the orientations assumed by BPs in thin films reflect a complex interplay of surface interactions and elastic energies associated with strain of the BP lattice. The results also provide new principles and methods to control the structure and properties of BP thin films, which may find use in BP-templated material synthesis, and BP-based optical and electronic devices.

Lyotropic Liquid Crystal Formed in Aqueous Lecithin Solutions with IPM and AEO20 Additives

Abstract The phase behavior and rheological properties of a lyotropic liquid crystal formed in the lecithin/AEO20/IPM/H2O system were investigated by means of phase diagram, polarized optical microscopy and rheology techniques at 37°C. After adding polyoxyethylene-20-oleyl ether (AEO20) and isopropyl myristate (IPM) to lecithin solutions, an isotropic liquid phase and an anisotropic liquid crystal phase were found. By analyzing the shear viscosity (η γ=0.1) and yield stress (σ 0), with increase in water content, the η γ=0.1 and σ 0 increase firstly and then decrease; with increasing IPM content, a decrease in the η γ=0.1 and σ 0 is observed. Notably, at the relatively higher water content area, the water content has little effect on the η γ=0.1 and critical stress. When the lecithin/AEO20 mass ratio is 1:2, the liquid crystal phase displays a stronger shear resistance and more stable network structure.