Liquid Crystal Structures Research Articles

Single-step synthesis of shaped polymeric particles using initiated chemical vapor deposition in liquid crystals.

We elucidate a previously unknown synthesis pathway that leads to polymeric nanospheres, orientation-controlled microgels, or microspheroids via single-step polymerization of divinylbenzene (DVB) using initiated chemical vapor deposition (iCVD) in liquid crystals (LC). iCVD supplies vapor-phase reactants continuously, avoiding the critical limitation of reactant-induced disruption of LC structure that has plagued past LC-templated polymerization processes. LC is leveraged as a real-time display of the polymerization conditions and particle emergence, captured using an in situ long-focal range microscope. Detailed image analysis unravels key LC-guided mechanisms during polymerization. pDVB forms nanospheres due to poor solubilization by nematic LC. The nanospheres partition to the LC-solid interface and further assemble into microgel clusters whose orientation is guided by the LC molecular alignment. On further polymerization, microgel clusters transition to microspheroids that resemble liquid drops. We identify key energetic factors that guide trajectories along the synthesis pathway, providing the fundamental basis of a framework for engineering particle synthesis with shape control.

Liquid Crystal Ordering in Densely Packed Colloidal Suspensions of Highly Anisotropic Monolayer Nanosheets

Monolayer nanosheets of zirconium phosphate in aqueous suspension exhibit short-range repulsion and long-range attraction, producing, at overall volume fractions larger than about half a percent, phase separation into higher-concentration liquid crystal and lower-concentration isotropic regions. At high concentrations, this phase separation takes the form of an emulsion of condensed, liquid-crystalline droplets, which anneal to form lens-shaped tactoids. These tactoids provide an opportunity to study the liquid crystal ordering of inorganic nanosheets in the limit of large shape anisotropy (diameter/thickness~400) and high packing fraction (volume fraction ≳ 70%). The internal liquid crystal structure of the tactoids remains nematic even under conditions that would usually favor ordering into lamellar smectics. Local lamellar ordering is suggested by short-range, smectic-like layer correlations, but a full transition into a smectic phase appears to be inhibited by the nanosheet edges, which act as a perturbative population of dislocation loops in the system of layers. Under conditions of thermal equilibrium, the nanoplates organize positionally to enable bend deformation of the director, a hallmark of the nematic phase and its principal distinction from the smectic, where bend must be expelled.

Imaging with a twist: Three-dimensional insights of the chiral nematic phase of cellulose nanocrystals via SHG microscopy.

Cellulose nanocrystals (CNCs) are bio-based nanoparticles that, under the right conditions, self-align into chiral nematic liquid crystals with a helical pitch. In this work, we exploit the inherent confocal effect of second-harmonic generation (SHG) microscopy to acquire highly resolved three-dimensional (3D) images of the chiral nematic phase of CNCs in a label-free manner. An in-depth analysis revealed a direct link between the observed variations in SHG intensity and the pitch. The highly contrasted 3D images provided unprecedented detail into liquid crystal's native structure. Local alignment, morphology, as well as the presence of defects are readily revealed, and a provisional framework relating the SHG response to the orientational distribution of CNC nanorods within the liquid crystal structure is presented. This paper illustrates the numerous benefits of using SHG microscopy for visualizing CNC chiral nematic systems directly in the suspension-liquid phase and paves the road for using SHG microscopy to characterize other types of aligned CNC structures, in wet and dry states.

Solvatochromism, electric dipole moments, optical properties and electronic structure of biphenylcarbonitrile liquid crystals

The UV–Vis. absorbance and fluorescence spectra of 4HC (4′-heptyl-4-biphenyl carbonitrile) and 4OB (4′-Octyl-4-biphenylcarbonitrile) liquid crystals were measured in 23 solvents with different polarities. As dependent on changing of solvents, while the change in absorbance spectrum of liquid crystals have less, change in fluorescence spectrum have more. Molecular interactions were quantitavely investigated by using Linear solvation energy relationships. Optical forbidden energy gap has been determined with using Tauc plot. The refractive index has been calculated with semi-empirical methods. The relationships between refractive index and Eg has been commented in n-hexane, acetic acid, water and 1,4-dioxane. The electric dipole moment has been calculated by using the Bilot-Kawski, Lippert-Mataga, Bakshiev, Kawski-Chamma-Viallet and Reichardt methods. Solvatochromic shifts showed to having large dipole moments of 4OB and 4HC LCs. Their molecular orbital energies, electric dipole moments, MEP, SAS, and reactivity properties of 4HC and 4OB LCs has been found by quantum chemical calculations. It was observed that the dipole moment of 4HC was higher than 4OB.

Twist disclinations mediated transformations in confined nematic liquid crystals

We studied numerically structural transformations in different confined nematic liquid crystals (LC) mediated by chargeless (twist) disclinations. Firstly, we focus on the role of twist disclinations in Moiré-type geometrical setup where LC is confined in a plane-parallel cell. We impose an azimuthal rotation to initially parallel wedge disclinations where the total topological charge of the system equals to zero. Two qualitatively different scenarii are observed depending on the cell thickness. In thin enough cells the disclinations touch in the mid-plane which enables continuous transformation into a final structure consisting of two twist disclinations confined to the limiting substrates. On the other hand, in thinner cells an additional chargeless loop is formed in the mid-plane. In this case, on rotating the initially parallel disclinations periodic structural reentrant behavior is observed. In cylindrical geometry we considered transformations between the initial metastable escaped radial structure with point defects (ERPD) into escaped radial (ER) or planar polar structure with line defects (PPLD). In both cases two nearby ring-like point defects within the ERPD structure collide and temporarily form a chargeless twist disclination loop. The latter in the ERPD-ER transformation shrinks and enables continuous transformation into the final thermodynamically stable structure. On the contrary, in the ERPD-PPLD transformation the twist loop, whose local structure matches PPLD configuration, increases and converts the system continuously into the global PPLD configuration. Detailed understanding of chargeless defect mediated transformations is beneficial for development of future switching devices based on continuous nematic structural transformations between LC structures exhibiting significantly different optical features.

Organic-Inorganic Hybrid Silica Film with a TGBA* Structure.

Twisted grain boundary (TGB) phases exhibit highly frustrated and complex liquid crystal structures, and have attracted enormous interest because of their unique internal structure, textures and properties. However, among the few real concerns related to these interesting structures, applying them to prepare polymer-stabilized colored liquid crystal films has been challenging. Herein, the organic-inorganic hybrid silica (OIHS) films with a TGBA* structure were prepared using two organosilanes and one chiral additive under an acidic condition. The structural color of the films can be adjusted by varying the polycondensation temperature and the concentration of the chiral additive. A structurally colored pattern was prepared by the inject printing, which was suitably applied for decoration and anti-counterfeiting.

Modelling nematic liquid crystal in fractal dimensions

In this paper we present a fractal Berreman's model which account for azimuthal surface anchoring of nematic liquid crystals which play a leading role nowadays in biomedical field and pharmaceutical controlled release dosage forms. The model is based on the concept of "product-like fractal measure" in anisotropic media which permits to describe liquid crystals formation in terms of fractal dimensions. It was observed that fractal dimensions affect both the polar azimuthal angle and the Franck excess elastic energy density of the distortion. For fractal dimensions close to unity, our analysis reveals the emergence of fluctuations and large deformations in the dynamical variables of the theory which suggest the presence of non-linear elastic instabilities or emergence of defect structures in liquid crystals. These fluctuations fade away for fractal dimensions much less than unity. We have evaluated the elastic energy per unit of area which is found to depend on the square of the fractal dimension. This leads to a decrease of the saturation voltage which is necessary to reduce the elastic energy of liquid crystals films in order to minimize the elastic energy. This reduction may describe nematic liquid crystals free from deformations, singularities or weak anchoring surfaces.

Curvature-directed anchoring and defect structure of colloidal smectic liquid crystals in confinement

Abstract Rod-like objects at high packing fractions can exhibit liquid crystalline ordering. By controlling how the rods align near a boundary, i.e. the anchoring, the defects of a liquid crystal can be selected and tuned. For smectic phases, the rods break rotational and translational symmetry by forming lamellae. Smectic defects thereby include both discontinuities in the rod orientational order (disclinations), as well as in the positional order (dislocations). In this work, we use experiments and simulations to uncover the geometrical conditions necessary for a boundary to set the anchoring of a confined, particle-resolved, smectic liquid crystal. We confine a colloidal smectic within elliptical wells of varying size and shape for a smooth variation of the boundary curvature. We find that the anchoring depends upon the local boundary curvature, with an anchoring transition observed at a critical radius of curvature approximately twice the rod length. Surprisingly, the critical radius of curvature for an anchoring transition holds across a wide range of rod lengths and packing fractions. The anchoring controls the defect structure. By analyzing topological charges and networks composed of maximum density (rod centers) and minimum density (rod ends), we quantify disclinations and dislocations formed with varying confinement geometry. Circular confinements, characterized by planar anchoring, promote disclinations, whereas elliptical confinements, featuring antipodal regions of homeotropic anchoring, promote long-range smectic order and dislocations. Our findings demonstrate how geometrical constraints can control the anchoring and defect structures of liquid crystals—a principle that is applicable from molecular to colloidal length scales.

MODELS OF FALSE AND CORRECT DETECTION OF INFORMATION LEAKAGE SIGNALS FROM MONITOR SCREENS BY A SPECIALIZED TECHNICAL MEANS OF ENEMY INTELLIGENCE

The calculation expressions for the probability of false detection of a leakage signal, taking into account the discrete representation of time in the models of detection of side radiation signals from static images on the monitor screen on liquid crystal structures by a specialised technical means of enemy intelligence, which implements an asymptotically optimal joint algorithm for detecting side radiation signals and estimating the duration of the image on the monitor screen, are refined. For this purpose, a large independent array of noise was generated in the Mathcad software environment, and the process of false signal detection by a specialised enemy intelligence vehicle was modelled in several Excel workbooks under conditions of a priori uncertainty about the duration of a static image on the monitor screen.

The Correlations between Microstructures and Color Properties of Nanocrystalline Cellulose: A Concise Review.

Cellulose nanocrystals (CNCs) are a green resource which can produce photonic crystal films with structural colors in evaporation-induced self-assembly; CNC photonic crystal films present unique structural colors that cannot be matched by other colored materials. Recently, the mechanisms of CNC photonic crystal films with a unique liquid crystal structure were investigated to obtain homogenous, stable, and even flexible films at a large scale. To clarify the mechanism of colorful CNC photonic crystal films, we briefly summarize the recent advances from the correlations among the preparation methods, microstructures, and color properties. We first discuss the preparation process of CNCs, aiming to realize the green application of resources. Then, the behavior of CNCs in the formation of liquid crystal phases is studied, considering the influence of the CNCs' size and shape, surface properties, and the types and concentrations of solvents. Finally, the film formation process of CNCs and the control of structural colors during the film formation are summarized, as well as the mechanisms of CNC photonic crystal films with full color. In summary, considering the above factors, obtaining reliable commercial CNC photonic crystal films requires a comprehensive consideration of the subsequent preparation processes starting from the preparation of CNCs.

Bifocal lenses with adjustable intensities enabled by bilayer liquid crystal structures.

In this paper, we propose bifocal lenses based on bilayer structures composed of a liquid crystal (LC) cell and LC polymer, and the relative intensity of two foci can be adjusted arbitrarily through applying an external voltage. Two LC layers have different light modulation functions: when circularly polarized light passes through the first layer, part of the outgoing light is converted with PB phase modulation and another part is not converted; followed by the second layer, PB modulation of these two parts would be simultaneously realized but with opposite signs; thus the transmitted left- and right-handed circularly polarized (LCP and RCP) light can be independently controlled. As proof-of-concept examples, longitudinal and transverse bifocal lenses are designed to split an incident LCP light into two convergent beams with orthogonal helicity, and the position of the two foci can be flexibly arranged. Benefitting from the electrically controlled polarization conversion efficiency (PCE) of the LC cell, the relative intensity of the two foci can be adjusted arbitrarily. Experimental results agree well with theoretical calculations. Besides, a broadband polarization and an edge imaging system based on the proposed bifocal LC lenses have also been demonstrated. This paper presents a simple method to design a functional multilayer LC device and the proposed bifocal lenses may have potentials in the optical interconnection, biological imaging, and optical computing.

Study on the influence of oils on the formation of liquid crystal structure of hydrogenated lecithin system

ABSTRACT Hydrogenated lecithin (HLC) is a liquid crystal emulsifier which can be oriented at the oil-water interface to form a long-range ordered and short-range disordered liquid crystal (LC) structure. In this study, the effects of oils commonly used in cosmetics (white oil, squalane, caprylic/capric triglyceride, Jojoba seed oil, shea butter) on the formation of LC structure for HLC system were investigated. The results showed that the numerous LCs was formed when the mass ratio of cetostearyl alcohol/HLC exceeded 8/2 in a single oil system. Among them, the liquid crystals formed by white oil and shea butter were more orderly. Meanwhile, the content of different oils also had a certain impact on the amount of liquid crystal. In this regard, the influence of compound oil system on liquid crystal was further studied by regulating the proportion and type of oils. It was found that the LC area was the largest and the LC structures were relatively regular when squalane/caprylic/capric triglyceride/shea butter was compounded. This study provided certain experimental basis and references for the development of LC emulsion formulations of hydrogenated lecithin system.

Stable hierarchical ionic liquid nanochannels for highly efficient CO2 adsorption, separation and conversion

Constructing stable nanochannels and nanoconfined environments for ionic liquids holds significant application value in gas separation, ion channels, and related fields. The functional polyionic liquid synthesized in this study exhibits a controllable assembly structure and demonstrates liquid crystal properties. Through heating and water treatment, the polyionic liquids crosslink to form multi-hierarchical nanopores, including sub-nanochannels with pore sizes similar to CO2, without the need for a catalyst. The specific surface area and pore size of the polyionic liquid network (PILC) were adjusted by regulating the self-assembly of polyionic liquids in water. The unique PILC, combining ionic liquid nanopores and liquid crystal structure properties, shows high CO2 adsorption performance and excellent CO2/N2 selectivities, surpassing commonly reported ionic liquid porous materials. Furthermore, PILC-2 exhibits good catalytic performance for CO2 cycloaddition, and its catalytic activity and selectivity did not significantly decrease after five cycles. This study successfully introduces hierarchical ionic liquid nanochannels into porous networks without involving any inorganic ordered nanomaterials. This provides a simple and effective approach for the highly selective adsorption and separation of CO2, as well as for the preparation of catalytic materials.

Electro-optical effect of unpolarized light modulation in homeoplanar structures of ferroelectric and ferrielectric liquid crystals.

A clearly expressed effect of unpolarized light electro-optical modulation by homeoplanar structures of a smectic C* ferroelectric liquid crystal (FLC) and a ferrielectric liquid crystal (FerriLC) was discovered and investigated for the first time to our knowledge. This effect of electrically controlled light scattering is insensitive to the applied voltage sign, as for polymer-dispersed nematic liquid crystals (PDLCs), but the electro-optical modulation frequency reaches the kilohertz range. Occurrence conditions and essential features of the effect, as well as its physical origin, are discussed.

Construction of Nano-Janus emulsion by phase inversion composition

Nano-Janus emulsion possesses excellent solubilization capabilities of both aqueous and organic materials, various liquid–liquid interfaces, and precisely controllable morphology. Successful construction of nano Janus droplets at mild conditions of room temperature and low-energy input will expand the industrial application. Two immiscible liquids of silicone oil (SO) and oleic acid (OA) are used as internal phases, and water is added dropwise at mild temperature. The topology of the nano-sized complex droplets is characterized by cryo-TEM, SAXS, and FF-TEM. Micro structure of lamellar liquid crystal (Lα), which is the critical transition phase, is investigated to reveal the formation mechanism. Topology adjustment including size range, volume ratio, and interface curvature is investigated. Complex nano droplets with snowman shape are successfully constructed in batch-scale at mild temperature of 30 °C and water-dripping rate of 1.0 mL/h. Formation of a four-component Lα phase is the critical point to the successful construction of the nano-Janus emulsion, which also creates additional freedom for structural regulation. The size of the complex droplets is freely alternated in the range of 50–500 nm and the morphology of one lobe is controlled from “crescent” to “half-moon”, and “moon with a hole”.

Liquid crystal-based reconfigurable antenna for 5G millimeter-wave

This paper proposed a frequency reconfigurable antenna that utilizes a multilayer structure of liquid crystal (LC) material. This antenna design incorporates a three-layer stacked structure to create an LC-injected cavity. The inverted microstrip line structure is designed to be in contact with the LC, serving as both a radiating element and a bias electrode. A parasitic patch is placed at the top of the antenna to enhance bandwidth. To prevent interference with DC and RF sources, a bias tee is integrated into the microstrip line input. Experimental results demonstrate that the proposed antenna exhibits excellent impedance matching and stable radiation patterns within the operational frequency range. By comparing the simulated performance of the existing LC antenna with our proposed design, the bandwidth is tripled at a center frequency of 30.3 GHz. In addition, the effective area of the proposed reconfigurable antenna (154 mm2) is 24.6% of the area of the previous reconfigurable antenna (625 mm2).

On the Feasibility of an LCD-Based Real-Time Converter for Ionizing Radiation Imaging.

Here we present the cascade converter (CC), which provides real-time imaging of ionizing radiation (IoR) distribution. It was designed and manufactured with the simplest architecture, utilizing liquid crystal display (LCD) technology. Based on two merged substrates with transparent electrodes, armed with functional layers, with the cell filled with nematic liquid crystal, a display-like, IoR-stimulated CC was achieved. The CC comprises low-absorbing polymer substrates (made of polyethylene terephthalate-PET) armed with a transparent ITO electrode covered with a thin semipermeable membrane of polymer (biphenylperfluorocyclobutyl: BP-PFCB) doped with functional nanoparticles (NPs) of Lu2O3:Eu. This stack was covered with a photoconductive layer of α-Se and finally with a thin polyimide (PI) layer for liquid crystal alignment. The opposite substrate was made of LCD-type glass with ITO and polyimide aligning layers. Both substrates form a cell with a twisted structure of nematic liquid crystal (TN) driven with an effective electric field Eeff. An effective electric field driving TN structure is generated with a sum of (1) a bias voltage VBIAS applied to ITO transparent electrodes and (2) the photogenerated additional voltage VXray induced between ITO and α-Se layers with a NPs-doped BP-PFCB polymer layer in-between. The IoR (here, X-ray) conversion into real imaging of the IoR distribution was achieved in the following stages: (1) conversion of IoR distribution into non-ionizing red light emitted with functional NPs, (2) transformation of red light into an electric charge distributed in a layer of the photoconductive α-Se, which is what results in the generation of distributed voltage VXray, and (3) a voltage-mediated, distributed switching of the TN structure observed with the naked eye. The presented imaging device is characterized by a simple structure and a simple manufacturing process, with the potential for use as a portable element of IoR detection and as a dosimeter.

Preparation and Application of Decanoic Acid/Arginine Hydrogels to a Transdermal Formulation.

We prepared a supramolecular hydrogel composed of decanoic acid and arginine (C10/Arg gel) and evaluated its application to a transdermal formulation. C10/Arg gel adjusted to pH 7 with 1 M NaOH aq or 1 M HCl aq provided a translucent hydrogel with a lamellar liquid crystal structure in the concentration region of decanoic acid ≥12% and arginine ≤9%. Rheological measurements showed that C10/Arg gel is a viscoelastic material with both solid and liquid properties, with elasticity being dominant over viscosity in the low shear stress region. The skin permeability of hydrocortisone (HC) and indomethacin (IM) from C10/Arg gels was investigated in vitro using hairless mouse skin and compared to control formulation drug suspensions (IM or HC) in water. The cumulative permeation amount of HC and IM from the C10/Arg gel at 10 h after application was approximately 16 and 11 times higher than that of the control, respectively. On the other hand, the flux of IM decreased with increasing arginine concentration, likely due to the acid-base interaction between Arg and IM in C10/Arg gel. Adequate drug skin permeation enhancement by C10/Arg gel requires optimizing the gel composition for each specific drug.

Multiple Phase Structures and Enhanced Dielectric Properties of Side-Chain Liquid Crystalline Polymer Containing Unique Biaxial Mesogen with Large Dipole Moment

To achieve all-organic polymer with high dielectric performances, we have designed a novel side-chain liquid crystalline polymer (P7) with strong polar mesogen of (Z)-4-(2-cyano-2-phenylvinyl)benzonitrile (CSCN) attached to polycyclooctene backbone. The bis-cyano-substituted CSCN is board-shaped and exhibits a large dipole moment (8.54 D) which tilts ∼34.2° away from its molecular long axis. Consequently, CSCN shows unique dual molecular anisotropy: one from biaxial shape anisotropy and the other from polarization anisotropy. The complex phase behaviors of P7 were investigated employing mainly the techniques of differential scanning calorimetry and X-ray diffraction. Four liquid crystal (LC) phases are identified as K0, K1, K2 and K3, which are SmA, highly-ordered biaxial SmA, B5-like and B7-like, respectively, with the thermal stability increased in sequence. The experimental results indicate that the different LC phases are arisen from the competition and balance between π-π stacking and dipole-dipole interaction. While the face-to-face π-π stacking is dominant in K0 and K1, optimizing the dipole-dipole interaction causes the CSCN mesogens within the smectic layer to tilt and rotate, resulting in K2 and K3. We further investigated the dielectric properties of P7 films using polarization-electric field loops test. The dielectric constant (εr) of P7 is found to be LC structure dependent, which is increased when the LC phase is varied from K0 to K3. With an average εr of 9.7 achieved in K3 and the low dielectric loss (tan δ = 0.001), P7 film offers a promising material in advanced applications like energy storage and electronic devices.

Study on the application and performance of liquid crystal emulsion system in sunscreen products

ABSTRACT Liquid crystal (LC) emulsion is a new emulsion system which has excellent application potential in the field of cosmetics. In this study, the LC emulsifier and traditional emulsifier were used to prepare the emulsions containing different types of sunscreen agents, respectively. The microstructure, sunscreen performance and rheological properties of the emulsions were studied systematically. The results showed that the formation of LC structure was not affected by sunscreen agents. LC structure can also enhance the sunscreen property of the emulsion as well as improve the sensory property. Further, we combined different sunscreen agents to prepare LC sunscreen emulsion. The sunscreen performance and repair effectiveness of emulsion were evaluated by human test. The results showed that LC sunscreen emulsion has an increased SPF value from 56 to 70 compared to non-LC sunscreen emulsion. Meanwhile, the LC structure also enhanced the moisturising properties of the emulsion, and the TEWL value of LC emulsion and non-LC emulsion was 67.4% and 96.5%, respectively. In addition, LC sunscreen emulsion has higher safety and better storage stability. In conclusion, this study provided the practical application of LC emulsion systems as well as the important guidance for developing excellent sunscreen emulsions.