Phase Behavior Of Liquid Crystals Research Articles

Self-Assembly of Ionic Superdiscs in Nanopores.

Discotic ionic liquid crystals (DILCs) consist of self-assembled superdiscs of cations and anions that spontaneously stack in linear columns with high one-dimensional ionic and electronic charge mobility, making them prominent model systems for functional soft matter. Compared to classical nonionic discotic liquid crystals, many liquid crystalline structures with a combination of electronic and ionic conductivity have been reported, which are of interest for separation membranes, artificial ion/proton conducting membranes, and optoelectronics. Unfortunately, a homogeneous alignment of the DILCs on the macroscale is often not achievable, which significantly limits the applicability of DILCs. Infiltration into nanoporous solid scaffolds can, in principle, overcome this drawback. However, due to the experimental challenges to scrutinize liquid crystalline order in extreme spatial confinement, little is known about the structures of DILCs in nanopores. Here, we present temperature-dependent high-resolution optical birefringence measurement and 3D reciprocal space mapping based on synchrotron X-ray scattering to investigate the thermotropic phase behavior of dopamine-based ionic liquid crystals confined in cylindrical channels of 180 nm diameter in macroscopic anodic aluminum oxide membranes. As a function of the membranes' hydrophilicity and thus the molecular anchoring to the pore walls (edge-on or face-on) and the variation of the hydrophilic-hydrophobic balance between the aromatic cores and the alkyl side chain motifs of the superdiscs by tailored chemical synthesis, we find a particularly rich phase behavior, which is not present in the bulk state. It is governed by a complex interplay of liquid crystalline elastic energies (bending and splay deformations), polar interactions, and pure geometric confinement and includes textural transitions between radial and axial alignment of the columns with respect to the long nanochannel axis. Furthermore, confinement-induced continuous order formation is observed in contrast to discontinuous first-order phase transitions, which can be quantitatively described by Landau-de Gennes free energy models for liquid crystalline order transitions in confinement. Our observations suggest that the infiltration of DILCs into nanoporous solids allows tailoring their nanoscale texture and ion channel formation and thus their electrical and optical functionalities over an even wider range than in the bulk state in a homogeneous manner on the centimeter scale as controlled by the monolithic nanoporous scaffolds.

Biaxial nematic order in fundamental measure theory.

Liquid crystals consisting of biaxial particles can exhibit a much richer phase behavior than their uniaxial counterparts. Usually, one has to rely on simulation results to understand the phase diagram of these systems since very few analytical results exist. In this work, we apply fundamental measure theory, which allows us to derive free energy functionals for hard particles from first principles and with high accuracy, to systems of hard cylinders, cones, and spherotriangles. We provide a general recipe for incorporating biaxial liquid crystal order parameters into fundamental measure theory and use this framework to obtain the phase boundaries for the emergence of orientational order in the considered systems. Our results provide insights into the phase behavior of biaxial nematic liquid crystals and, in particular, into methods for their analytical investigation.

Lyotropic liquid crystal phases of monoolein in protic ionic liquids.

Monoolein-based liquid crystal phases are established media that are researched for various biological applications, including drug delivery. While water is the most common solvent for self-assembly, some ionic liquids (ILs) can support lipidic self-assembly. However, currently, there is limited knowledge of IL-lipid phase behavior in ILs. In this study, the lyotropic liquid crystal phase behavior of monoolein was investigated in six protic ILs known to support amphiphile self-assembly, namely ethylammonium nitrate, ethanolammonium nitrate, ethylammonium formate, ethanolammonium formate, ethylammonium acetate, and ethanolammonium acetate. These ILs were selected to identify specific ion effects on monoolein self-assembly, specifically increasing the alkyl chain length of the cation or anion, the presence of a hydroxyl group in the cation, and varying the anion. The lyotropic liquid crystal phases with 20-80 wt. % of monoolein were characterized over a temperature range from 25 to 65 °C using synchrotron small angle x-ray scattering and cross-polarized optical microscopy. These results were used to construct partial phase diagrams of monoolein in each of the six protic ILs, with inverse hexagonal, bicontinuous cubic, and lamellar phases observed. Protic ILs containing the ethylammonium cation led to monoolein forming lamellar and bicontinuous cubic phases, while those containing the ethanolammonium cation formed inverse hexagonal and bicontinuous cubic phases. Protic ILs containing formate and acetate anions favored bicontinuous cubic phases across a broader range of protic IL concentrations than those containing the nitrate anion.

Effects of ionic liquids as catalysts on liquid crystal aromatic polyester based on thin‐film polymerization technique

AbstractLiquid crystal aromatic polyesters (LCAPs) have been used in wide applications, such as chip packaging and airship skin. The traditional polymerization of LCAP is catalyzed by inorganic salts, for example, sodium acetate. Herein, we reported three kinds of ionic liquids (ILs) as catalysts to promote LCAP polymerization for the first time. The effects of ILs on the polymerization behaviors are investigated by in situ observing the liquid crystal (LC) phase behaviors based on the thin‐film polymerization technique. The evolution of LC phase over time was detailly investigated by analyzing the emergence, fusion, and growth of LC phase. The temperature from 170 to 210°C and the catalyst concentration in range from 0 to 0.5 wt% are compared, showing that temperature at 210°C and catalyst concentration at 0.5 wt% are the best polymerization conditions for all ILs catalysts. In comparison with trimethylsulfonium iodide and piperidine acetate, 1‐ethyl‐3‐methylimidazolium acetate has the best catalytic effect for the polymerization of LCAP in all experimental conditions. The successful polymerization was confirmed by FT‐IR spectra, showing the increased intensity of vibration peak at 1735 cm−1 attributed to the generation of ester groups while the decreased intensities of vibration peaks at 1759 and 1370 cm−1.

Effect of quantum dots on the phase behavior and order of 8CB liquid crystal

We experimentally investigate the impact of surface functionalized hydrophobic core-shell CdSe/ZnS quantum dots on the phase behavior and order of the host liquid crystal compound 4-cyano-4'-octylbiphenyl (8CB) by means of polarized optical microscopy, polarized micro-Raman spectroscopy and X-ray diffraction. The orientational order of the nanocomposite system is probed by means of birefringence measurements as a function of temperature and mass fraction of the quantum dots. The dispersion quality of the dopant in the samples, partial-aggregation phenomena and/or nanoparticle organization give rise to non-monotonic variation of the probed thermodynamic quantities. A critical dopant mass fraction above which the nematic phase becomes paranematic is evidenced. A phenomenological model accounts for phase separation effects and a qualitative interpretation of the experimental results. The impact of nanoparticles on the macroscopic nematic order is discussed in the frame of a random anisotropy Lebwohl-Lasher model.

Prediction of the liquid-crystal phase behavior of hard right triangles from fourth-virial density-functional theories.

We have used an extended scaled-particle theory that incorporates four-body correlations through the fourth-order virial coefficient to analyze the orientational properties of a fluid of hard right isosceles triangles. This fluid has been analyzed by computer simulation studies, with clear indications of strong octatic correlations present in the liquid-crystal phase, although the more symmetric order tetratic phase would seem to be the most plausible candidate. Standard theories based on the second virial coefficient are unable to reproduce this behavior. Our extended theory predicts that octatic correlations, associated to a symmetry under global rotations of the oriented fluid by 45^{∘}, are highly enhanced, but not enough to give rise to a thermodynamically stable phase with strict octatic symmetry. We discuss different scenarios to improve the theoretical understanding of the elusive octatic phase in this intriguing fluid.

Phase behavior of nematic-nanoparticle mixtures

We study the effects of nanoparticles (NPs) on thermotropic nematic liquid crystals (LCs) in relatively dilute NP–LC mixtures. We are interested in the fundamental generic mechanisms that quantitatively and qualitatively affect the phase behavior of LCs. A simple molecular field analysis shows that a phase transition will likely occur upon entry into the ordered phase. Moreover, the interaction between nematogenic NPs and LCs could force a sergeant–soldier-like behavior, in which only the phase behavior of one component is affected despite the symmetric appearance of the coupling term. When NPs are anisotropic, their influence on LC phase behavior can be qualitatively different depending on the anchoring, even in the absence of the disorder. We illustrate numerically that a random-field-type disorder might impose either short-range, quasi-long-range, or even long-range order, which might survive.

Effect of Phenoxyethanol and Sodium benzoate on the liquid crystal phase behavior of mixed surfactant system

Surfactants in a mixed concentrated (∼30 wt% and higher)-surfactant system self-assemble to form a variety of liquid crystal (lc) types depending the lc curvature determined by the surfactant chemistries and their relative compositions. Preservatives, fragrances and other minor additives present in an industrial formulation can either incorporate into the lc and/or influence the aqueous phase ionic strength to alter the spatial arrangements of the surfactants and the lc curvature. These mechanisms could additively or competitively determine the lc curvature and thereby the lc types formed. We report on the mechanisms for preservatives Phenoxyethanol (PE) and Sodium benzoate (NaB) governing the lc phase behavior for a mixed concentrated-surfactant system: 16 wt% zwitterionic Cocoamidopropyl betaine (CAPB), and 7 wt% each of anionic Sodium Lauroyl isethionate (SLI), Sodium Methyl Lauroyl Taurate (SMLT), and 6 wt% Lauric acid. The lc type(s), the lc dimensions including inter-lc distances were derived from SAXS and polarized microscopy images. The predominant lc phase without preservatives was H1lc, while anionic SLI and SLMT present in excess were insoluble to form dispersed crystals. The addition of PE molecules resulted in their incorporation in the lc surfactant film to cause a transition to micelles, and Lα lc due to incorporation-induced flattening of the film. NaB molecules prevented micelles formation and preserved the H1lc by serving as a hydrotropic agent. The NOESY spectra for the lc systems with PE or NaB at 0–3 wt% confirmed incorporation of PE in surfactant film as opposed to NaB. For both PE and NaB present in a lc system, the dominance of hydrotropic nature of NaB causing film bending rather than the film flattening effect of PE at low (∼1 wt%) PE levels resulted in H1lc as the predominant phase, and reduced dominance of film bending effect at a high PE level (≥ 2 wt%) led to the formation of Lα lc.

Anisotropic Nanomaterial Liquid Crystals: From Fiber Spinning to Additive Manufacturing.

There have long been synergistic relationships among the discovery of new anisotropic materials, advancements in liquid crystal science, and the production of manufactured goods with exciting new properties. Ongoing progress in understanding the phase behavior and shear response of lyotropic liquid crystals comprised of one-dimensional and two-dimensional nanomaterials, coupled with advancements in extrusion-based manufacturing methods, promises to enable the scalable production of solid materials with outstanding properties and controlled order across multiple length scales. This Perspective highlights progress in using anisotropic nanomaterial liquid crystals in two extrusion-based manufacturing methods: solution spinning and direct ink writing. It also describes current challenges and opportunities at the interface of nanotechnology, liquid crystalline science, and manufacturing. The intent is to inspire additional transdisciplinary research that will enable nanotechnology to fulfill its potential for producing advanced materials with precisely controlled morphologies and properties.

Tuning of optical properties and phase behavior of Nanomaterial-stabilized blue phase liquid crystals

HypothesisNanoparticles of various shapes and sizes can affect the optical properties and blue phase (BP) stabilization of BP liquid crystals (BPLCs). This is because nanoparticles, which are more compatible with the LC host, can be dispersed in both the double twist cylinder (DTC) and disclination defects in BPLCs. ExperimentsThis study presents the first systematic study of the use of CdSe nanoparticles having various sizes and shapes (spheres, tetrapods and nanoplatelets) to stabilize BPLCs. Unlike previous studies using commercial nanoparticles (NPs), we custom-synthesized NPs with the same core and nearly identical long chain hydrocarbon ligand materials. Two LC hosts were used to investigate the NP effect on BPLCs. FindingsThe size and shape of nanomaterials greatly influence the interaction with LCs, and the dispersion of NPs in the LC medium affects the position of the BP reflection band and the stabilization of BPs. Spherical NPs were found to be more compatible with the LC medium than tetrapod shape and platelet shape NPs, resulting in a wider temperature range of BP and a redshift of the reflection band of BP. In addition, the inclusion of spherical NPs tuned the optical properties of BPLCs to a significant extent, whereas BPLCs with nanoplatelets displayed a limited influence on the optical properties and temperature window of BPs due to poor compatibility with LC hosts. The tunable optical behavior of BPLC as a function of the type and concentration of NPs has not been reported.

Cross-linkable, phosphobetaine-based, zwitterionic amphiphiles that form lyotropic bicontinuous cubic phases.

The design, synthesis, and lyotropic liquid crystal phase behaviour of six cross-linkable, phosphobetaine-based, zwitterionic amphiphiles are described. Two form a QII phase with aq. NH4Cl solution, giving 3D-nanoporous membrane materials that can be used for water desalination and are not susceptible to ion exchange like traditional ionic analogues.

Liquid-crystalline behaviors of single-walled carbon nanotube aqueous dispersions with different nanotube aspect ratios and surfactants

We investigate the liquid crystal (LC) phase behaviors of the sodium cholate stabilized single-walled carbon nanotube (SWCNT) aqueous dispersions with different SWCNT aspect ratios. The isotropic-to-nematic phase transition occurs at a lower concentration for the SWCNT dispersion with a larger aspect ratio, which is expected by the Onsager theory. The well-aligned film is successfully fabricated from the dispersion with the higher SWCNT aspect ratio by the simple blade coating. We also prepare the SWCNT dispersions with different surfactants, sodium deoxycholate, and sodium taurodeoxycholate, changing the surface condition of SWCNTs, which may affect the LC transition concentrations.

Novel branched liquid crystal oligomers containing azo and Schiff base groups

Three novel azo-Schiff base mesogens with different alkyl chain lengths and three series of novel branched liquid crystal oligomers with 4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid as the center and cholesterol as the chiral group were designed and synthesized. The test results showed that their liquid crystal phase behavior was closely related to the number of mesogenic units and the rigidity and flexibility of the structure. In the same series, as the value of n increased, the mesophase ranges were widened. When the value of n was the same in different series, as the degree of branching increased, the mesophase ranges were widened.

Dynamics in field-induced biaxial nematic liquid crystals of board-like particles

Biaxial nematic (NB) liquid crystals have been indicated as promising candidates for the design of next-generation displays with novel electro-optical properties and faster switching times. While at the molecular scale their existence is still under debate, experimental evidence, supported by theory and simulation, has unambiguously proved that suitable colloidal particles can indeed form NB fluids under specific conditions. While this discovery has sparked a widespread interest in the characterisation of the phase behaviour of NB liquid crystals, significantly less attention has been devoted to the study of their transport properties. To bridge this gap, by Dynamic Monte Carlo simulations we have investigated the equilibrium dynamics of field-induced NB phases comprising monodisperse hard cuboids. In particular, we calculated the long-time self-diffusion coefficients of cuboids over a wide range of anisotropies, spanning prolate to oblate geometries. Additionally, we have compared these diffusivities with those that, upon switching the external field off, are measured in the thermodynamically-stable isotropic or uniaxial nematic phases at the same density. Our results indicate that while prolate cuboids diffuse significantly faster in biaxial nematics than in less ordered fluids, we do not observe such an increase with oblate cuboids at high packing fractions. We show that these changes are most likely due to the field-induced freezing of the axes perpendicular to the nematic director, along with a substantial increase in the ordering of the resulting NB phase.

Branched schiff base liquid crystalline oligomers: synthesis and properties

ABSTRACT Three series of new branched liquid crystal oligomers with 4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid as the centre and cholesterol as the chiral group were designed and synthesised (Dn, Fn and Hn, n = 4,6,8). DSC and POM results showed that their liquid crystal phase behaviour was closely related to the number of mesogenic unit and the rigidity and flexibility of the structure. They were all cholesteric liquid crystals. In the same series, as the value of n increased, the mesophase ranges became narrower. When the value of n was the same in different series, as the degree of branching increased, the mesophase ranges became narrower.

Polymer induced liquid crystal phase behavior of cellulose nanocrystal dispersions.

Cellulose nanocrystals (CNCs) are a promising bio-based material that has attracted significant attention in the fabrication of functional hybrid materials. The rod-like shape and negative surface charge of CNCs enable their rich colloidal behavior, such as a liquid crystalline phase and hydrogel formation that can be mediated by different additives. This study investigates the effect of depletion-induced attraction in the presence of non-absorbing polyethylene glycol (PEG) of different molecular weights in CNC aqueous dispersions, where the polymer molecules deplete the space around particles, apply osmotic pressure and drive the phase transition. Polarized light microscopy (PLM), rheology, small angle X-ray scattering (SAXS) and atomic force microscopy (AFM) are used to characterize the phase behavior over a time period of one month. In our results, pure CNC dispersion shows three typical liquid crystal shear rheology regimes and cholesteric self-assembly behavior. Tactoid nucleation, growth and coalescence are observed microscopically, and eventually the dispersion presents macroscopic phase separation. PEG with lower molecular weight induces weak attractive depletion forces. Tactoid growth is limited, and the whole system turns into a fully nematic phase macroscopically. With PEG of higher molecular weight, attractive depletion force becomes predominant, thus CNC self-assembly is inhibited and nematic hydrogel formation is triggered. Overall, we demonstrate that depletion induced attraction forces by the addition of PEG enable precise tuning of CNC self-assembly and phase behavior with controllable mechanical strength and optical activity. These findings deepen our fundamental understanding of cellulose nanocrystals and advance their application in colloidal systems and nanomaterials.

Effect of Amorphous Crosslinker on Phase Behavior and Electro-Optic Response of Polymer-Stabilized Blue Phase Liquid Crystals.

Blue phase liquid crystals (BPLCs) composed of double-twisted cholesteric helices are promising materials for use in next-generation displays, optical components, and photonics applications. However, BPLCs are only observed in a narrow temperature range of 0.5–3 °C and must be stabilized with a polymer network. Here, we report on controlling the phase behavior of BPLCs by varying the concentration of an amorphous crosslinker (pentaerythritol triacrylate (PETA)). LC mixtures without amorphous crosslinker display narrow phase transition temperatures from isotropic to the blue phase-II (BP-II), blue phase-I (BP-I), and cholesteric phases, but the addition of PETA stabilizes the BP-I phase. A PETA content above 3 wt% prevents the formation of the simple cubic BP-II phase and induces a direct transition from the isotropic to the BP-I phase. PETA widens the temperature window of BP-I from ~6.8 °C for BPLC without PETA to ~15 °C for BPLC with 4 wt% PETA. The BPLCs with 3 and 4 wt% PETA are stabilized using polymer networks via in situ photopolymerization. Polymer-stabilized BPLC with 3 wt% PETA showed switching between reflective to transparent states with response times of 400–500 μs when an AC field was applied, whereas the application of a DC field induced a large color change from green to red.

Surface Properties and Liquid Crystal Properties of Alkyltetra(oxyethyl) β-d-Glucopyranoside.

Hydrophilic alkyl polyglycosides (APGs) and alkyl glycosides (AGs) with anomeric pure are a class of important substitutes for petroleum-based surfactants. Improving their water solubility should make such hydrophilic glycosurfactants have more excellent potential application value. To solve the inherent problem of poor water solubility of traditional alkyl β-d-glucopyranoside (5), a series of alkyltetra(oxyethyl) β-d-glucopyranosides (4a-4g, n = 7-18) were successfully synthesized by introducing tetra(oxyethylene) fragments to carry out the structural modification. The relationship between the related structure and the physicochemical properties was further investigated, including their hydrophilic-lipophilic balance (HLB), water-solubility, foaming performance, emulsification, hygroscopicity, surface activity, and thermotropic/lyotropic liquid crystal phase behavior. The results showed that the water solubility gradually decreased as the alkyl chain length increased due to the gradual decrease of their HLB number. Octadecyltetra(oxyethyl) β-d-glucopyranoside (4g, n = 18) was found to be insoluble in water at 25 °C. Taken together, long-chain alkyl glycosides had good foaming properties and excellent emulsifying properties. Among them, dodecyltetra(oxyethyl) β-d-glucopyranoside (4d, n = 12) had the best foaming performance. In the rapeseed oil/water system, cetyltetra(oxyethyl) β-d-glucopyranoside (4f, n = 16) had the best emulsifying ability. With the increase of the alkyl chain length, the critical micelle concentration (Ccmc), γcmc, Γmax, and hygroscopicity of this series of glycosides showed a downward trend. Differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) showed that the thermal stability increased with the increase of the alkyl chain length, and alkyltetra(oxyethyl) β-d-glucopyranosides (4d-4g, n = 12-18) had the corresponding melting points and clearing points. Alkyltetra(oxyethyl) β-d-glucopyranosides (4b-4g, n = 8-18) formed a smectic phase with a typical fan-shaped and focal conic texture during the cooling process. In the water contact experiments, it was found that glycosides (4b-4g, n = 8-18) at high concentrations transformed into various lyotropic liquid crystal including hexagonal phase, bicontinuous cubic phase, and lamellar phase phases. Therefore, such green nonionic glycosurfactants alkyltetra(oxyethyl) β-d-glucopyranosides should have potential practical application prospects.

Phase behaviour of n-CB liquid crystals confined to controlled pore glasses

In this review, we present the phase behaviour of liquid crystals (LCs) confined to Controlled-Pore Glasses (CPG) of various pore sizes. We consider either non-treated or silane-treated CPG pore surfaces, which impose parallel and homeotropic alignment to n-cyanobiphenyl (n-CB) LCs, respectively. The resulting nematic or smectic ordering depends on the characteristic void radii R and is well described in terms of the Landau-de Gennes free energy. Experimental data for different n-CB LCs, 5CB, 8CB, and 12CB, demonstrate phase transitions in orientation and translational degrees of freedom. In the bulk, 5CB and 8CB exhibit on cooling from the isotropic (I) phase the 1st order isotropic-nematic (I−N) phase transitions. In addition, 8CB also exhibits on further cooling a 2nd order nematic-smectic A (N−SmA) phase transition. 12CB, on the other hand, only has a 1st order isotropic-smectic A (I−SmA) phase transition. The bulk LCs exhibit a variety of different phase structures. When LCs are confined to porous media, their phase structures can be modified and even glass transition is possible.For LCs confined to CPG, the phase transition temperatures are shifted, depending on the pore size and the pore surface treatment. The Landau-de Gennes model predicts that the present phase transition shifts display inversely linear and inversely quadratic contributions in terms of the characteristic pore sizes. Furthermore, for strong enough confinement the phase transitions are replaced by gradual evolution of LCs order. These predictions are in line with nuclear magnetic resonance, small- angle X-ray scattering, and high-resolution calorimetry experimental observations.

Chemistry and Geometry of Counterions Used in Hydrophobic Ion Pairing Control Internal Liquid Crystal Phase Behavior and Thereby Drug Release.

The combination of Flash NanoPrecipitation and hydrophobic ion pairing (HIP) is a valuable approach for generating nanocarrier formulations of ionic water-soluble drugs with controllable release properties dictated by liquid crystalline structuring of the ion pairs. However, there are few examples of this in practice in the literature. This work aims to decipher the influence of the nature of the hydrophobic counterion used in HIP and its consequent impact on liquid crystalline structuring and drug release. The hypothesis of this study was that hydrophobic counterions with different head and tail groups used for FNP with HIP would give rise to different liquid crystalline structures, which in turn would result in different drug release behavior. A cationic, water-soluble antibiotic, polymixin B, was complexed with eight different hydrophobic counterions with varying head and tail groups and encapsulated into nanocarriers 100-400 nm in size prepared using FNP. Sixteen formulations were assessed for internal structure by synchrotron small-angle X-ray scattering, and drug release was measured in vitro in physiological conditions. The liquid crystalline phases formed depended on the counterion head group and tail geometry, drug:counterion charge ratio, and the ionic strength and pH of the release medium. Drug release occurred more rapidly when no liquid crystalline phases were present and more slowly when higher-ordered phases existed. Specific findings include that phosphonic acid counterions lead to the formation of lamellar structures that persisted at pH 2.0 but were not present at pH 7.3. In contrast, sulfonic acids lead to lamellar or hexagonal phases that persisted at both pH 7.3 and 2.0, while hydrophobic counterions without alkyl tails did not form internal structures. It was also clear that the lipophilicity of the counterion does not dictate drug release. These findings confirm that the liquid crystalline phase behavior of the drug:counterion complex dictates drug release and significantly improves our understanding of the types of controlled release formulations that are possible using FNP with HIP.