Nematic Phase Research Articles

Reaction-Induced Liquid Crystalline Polybenzoxazine BearingAromatic Amide Side Branches.

In this study, a nematic phase structure is incorporated into polybenzoxazine to increase its thermal conductivity. A simple route for the synthesis of a thermally conductive polybenzoxazine containing liquid crystalline (LC) structure by grafting oligomeric p-sulfophenylene-terephthalamide (PSTA) is offered. Benzoxazine monomer of pHBA-da is synthesized via Mannich reaction of p-hydroxy benzoic acid, p-formaldehyde, and dodecyl amine. After ring-opening polymerization, the oligomer benzoxazine of OBZ─COOH is obtained. The OBZ─COOH/PSTA mixture is prepared by mixing PSTA with OBZ─COOH. Afterward, the grafted copolymer is named OBZ─PSTA copolymer. The liquid crystalline behavior of OBZ─COOH/PSTA is studied by polarized optical microscopy and small angle X-ray scattering analysis. The results show that the OBZ─PSTA forms the LC structure during isothermal and non-isothermal curing. The LC structure displays a floral textured nematic phase. The phase formation is induced by an amidation reaction. Due to the grafts of LC PSTA, the thermal conductivity of OBZ─PSTA is 0.296W m-1 K-1 , which is 26% greater than OBZ─COOH. The glass transition temperature (Tg ) of OBZ─PSTA is 241°C. The 5% (Td5 ) and 10% weight loss temperatures (Td10 ) of OBZ─PSTA are 346 and 362°C, respectively.

Electric field effects on N–Sm-A–Sm-C phase transitions

A liquid crystalline system formed by rod-shaped molecules that have a small transverse dipole moment is analyzed in the presence of an external electric field normal to the smectic layers. The approach focuses on the phase transition diagram displaying the N–Sm–A-Sm-C phases, when both negative and positive dielectric anisotropies are considered. The analysis is carried out within the framework of an extended mean field theory, which shows the emergence of a re-entrant Sm-C phase in the strong field regime, accompanied by a suppression of the translational ordering of the Sm-A phase, in the case of a negative anisotropy. A different scenario is observed in the case of positive anisotropy, as the electric field tends to suppress the Sm-C phase because the molecular alignment is driven by the field along its direction. In this case, the emergence of a residual nematic phase is also observed, which replaces the isotropic phase and is characterized by a low-value orientational order parameter.

Elastic properties of liquid crystals

The paper presents elastic properties of liquid crystals, especially their nematic phase. Anoutline of a development of theories describing these properties is given. The model describing liquidcrystal as continuous medium is formulated. The curvature theory of elasticity of nematic liquidcrystals based on Zocher – Oseen – Frank’s approach is discussed in details. In this way, essentialelastic properties of nematics as well their relative material parameters are described.Keywords: liquid crystals, nematics, elastic properties, deformations, continuous medium

Effect of graphene nanoparticles on the isotropic to nematic phase transition

ABSTRACT A model combining with Flory-Huggins theory of isotropic mixing and Landau theory is developed to describe the effect of graphene nanoparticles on the isotropic to nematic phase transition. The temperature and concentration of graphene nanoparticles dependence on the orientational order parameter, transition temperature and thermodynamic quantities near the isotropic to nematic phase transition are discussed. The orientational order parameter, transition temperature and enthalpy near the isotropic to nematic phase transition increase with the increase of graphene nanoparticles.

Stripes polymorphism and water-like anomaly in hard core-soft corona dumbbells

In this paper, we investigate the phase diagram of a dumbbell model composed of two hard-core soft-corona beads through NpT simulations. We chose this particular system due to its ability to exhibit a diverse range of stripe patterns. By analyzing the thermodynamic and structural changes along compression isotherms, we explore the transition between these distinct patterns. In addition to the stripe and Low-Density-Triangular solid phases obtained, we observed a Nematic Anisotropic phase characterized by a polymer-like pattern at high temperatures and intermediate pressures. Furthermore, we demonstrate the significant role played by the new characteristic length scale, which arises from the anisotropic geometry of the dumbbell structure, in the transition between the stripe patterns. Notably, not only do the structural properties exhibit intriguing behavior, but the diffusion and density in the nematic fluid phase also display a water-like anomalous increase under compression. These findings can be valuable in guiding the design of materials based on nanoparticles, with the aim of achieving specific mesopatterns.

Anisotropic particle multiphase equilibria in nonuniform fields.

We report a method to predict equilibrium concentration profiles of hard ellipses in nonuniform fields, including multiphase equilibria of fluid, nematic, and crystal phases. Our model is based on a balance of osmotic pressure and field mediated forces by employing the local density approximation. Implementation of this model requires development of accurate equations of state for each phase as a function of hard ellipse aspect ratio in the range k = 1-9. The predicted density profiles display overall good agreement with Monte Carlo simulations for hard ellipse aspect ratios k = 2, 4, and 6 in gravitational and electric fields with fluid-nematic, fluid-crystal, and fluid-nematic-crystal multiphase equilibria. The profiles of local order parameters for positional and orientational order display good agreement with values expected for bulk homogeneous hard ellipses in the same density ranges. Small discrepancies between predictions and simulations are observed at crystal-nematic and crystal-fluid interfaces due to limitations of the local density approximation, finite system sizes, and uniform periodic boundary conditions. The ability of the model to capture multiphase equilibria of hard ellipses in nonuniform fields as a function of particle aspect ratio provides a basis to control anisotropic particle microstructure on interfacial energy landscapes in diverse materials and applications.

To Be or Not To Be Polar: The Ferroelectric and Antiferroelectric Nematic Phases.

We report two new series of compounds that show the ferroelectric nematic, NF, phase in which the terminal chain length is varied. The longer the terminal chain, the weaker the dipole-dipole interactions of the molecules are along the director and thus the lower the temperature at which the axially polar NF phase is formed. For homologues of intermediate chain lengths, between the non-polar and ferroelectric nematic phases, a wide temperature range nematic phase emerges with antiferroelectric character. The size of the antiparallel ferroelectric domains critically increases upon transition to the NF phase. In dielectric studies, both collective ("ferroelectric") and non-collective fluctuations are present, and the "ferroelectric" mode softens weakly at the N-NX phase transition because the polar order in this phase is weak. The transition to the NF phase is characterized by a much stronger lowering of the mode relaxation frequency and an increase in its strength, and a typical critical behavior is observed.

Trainable Bilingual Synaptic Functions in Bio-enabled Synaptic Transistors.

The signal transmission of the nervous system is regulated by neurotransmitters. Depending on the type of neurotransmitter released by presynaptic neurons, neuron cells can either be excited or inhibited. Maintaining a balance between excitatory and inhibitory synaptic responses is crucial for the nervous system's versatility, elasticity, and ability to perform parallel computing. On the way to mimic the brain's versatility and plasticity traits, creating a preprogrammed balance between excitatory and inhibitory responses is required. Despite substantial efforts to investigate the balancing of the nervous system, a complex circuit configuration has been suggested to simulate the interaction between excitatory and inhibitory synapses. As a meaningful approach, an optoelectronic synapse for balancing the excitatory and inhibitory responses assisted by light mediation is proposed here by deploying humidity-sensitive chiral nematic phases of known polysaccharide cellulose nanocrystals. The environment-induced pitch tuning changes the polarization of the helicoidal organization, affording different hysteresis effects with the subsequent excitatory and inhibitory nonvolatile behavior in the bio-electrolyte-gated transistors. By applying voltage pulses combined with stimulation of chiral light, the artificial optoelectronic synapse tunes not only synaptic functions but also learning pathways and color recognition. These multifunctional bio-based synaptic field-effect transistors exhibit potential for enhanced parallel neuromorphic computing and robot vision technology.

Thermomechanical Coupling in Polydomain Liquid Crystal Elastomers

Abstract Liquid crystal elastomers (LCEs) are made of liquid crystal molecules integrated with rubber-like polymer networks. An LCE exhibits both the thermotropic property of liquid crystals and the large deformation of elastomers. It can be monodomain or polydomain in the nematic phase and transforms to an isotropic phase at elevated temperature. These features have enabled various new applications of LCEs in robotics and other fields. However, despite substantial research and development in recent years, thermomechanical coupling in polydomain LCEs remains poorly studied, such as their temperature-dependent mechanical response and stretch-influenced isotropic-nematic phase transition. This knowledge gap severely limits the fundamental understanding of the structure-property relationship, as well as future developments of LCEs with precisely controlled material behaviors. Here, we construct a theoretical model to investigate the thermomechanical coupling in polydomain LCEs. The model includes a quasi-convex elastic energy of the polymer network and a free energy of mesogens. We study the working conditions where a polydomain LCE is subjected to various prescribed planar stretches and temperatures. The quasi-convex elastic energy enables a “mechanical phase diagram” that describes the macroscopic effective mechanical response of the material, and the free energy of mesogens governs their first-order nematic-isotropic phase transition. The evolution of the mechanical phase diagram and the order parameter with temperature is predicted and discussed. Unique temperature-dependent mechanical behaviors of the polydomain LCE that have never been reported before are shown in their stress-stretch curves. These results are hoped to motivate future fundamental studies and new applications of thermomechanical LCEs.

Room temperature tri-alkynyl benzene based discotic nematic mesophase enabling high-efficiency deep blue OLEDs

In the hunt to develop room-temperature nematic discotic materials, we engineered a molecular structure that employs a tri-alkynyl benzene core incompatible with π-π stacking, providing flexibility to the system. Micro-segregation was prohibited due to the direct attachment of the flexible alkoxy chain to the central benzene ring, leading to a discotic nematic phase. The nematic phase was found stable down to room temperature and, on further cooling, transformed into a glassy state. Detailed analysis of differential scanning calorimetry plots, polarized optical microscopic textures, and temperature-dependent X-ray diffraction patterns confirmed the glassy nematic phase at low temperatures. The tri-alkynyl benzene moiety imparts high solid and solution-state blue emission properties to mesogens 1a and 1b. On stimulating the compounds electrically as a solid-state emitter in organic light-emitting diodes, they showed emission in the deep blue (CIEy < 0.08) region at 100 cd m−2 luminance and pure blue (CIEy < 0.11) region at maximum luminance using CBP host. Amongst all the configurations used, the device based on 0.5 wt% 1a displayed the best performance with a maximum external quantum efficiency of 4.1% with a turn-on voltage of 3.5 V and CIExy coordinates of (0.16,0.07).

Haze-Suppressed Wideband Light Shutter from Near Ultraviolet to Infrared Rays Utilizing Electrophoretic Carbon Black Particles.

Carbon black (CB) particles that can absorb from near ultraviolet to infrared rays are well dispersed into an isotropic dielectric liquid and their optical properties can be kept even under exposure to sunlight over a long time. The shutter which controls the position of CB particles by electrophoretic force can be applied to switchable light shutters for windows in buildings and automobiles for the purpose of energy savings. Here, a wideband light shutter with three terminal electrodes is proposed, exhibiting excellent dark (transmittance ≈1.4%) and transparent state (transmittance >60%). The device operates at a low field intensity of about 1Vµm-1 to obtain transparent state and its wide temperature range operation from -50 to 120°C is confirmed while conventional liquid crystal-based shutter cannot perform such levels due to a limited temperature range in the nematic phase. In addition, haze is minimized in a transparent state by adopting an insulation layer over electrodes and a solution is found to keep a transparent state without applying power. It is believed that the proposed broadband shutter with fast response time could open a new chapter in switchable windows owing to its low power consumption and working in a wide temperature range.

Entanglement in the quantum phases of an unfrustrated Rydberg atom array

Recent experimental advances have stimulated interest in the use of large, two-dimensional arrays of Rydberg atoms as a platform for quantum information processing and to study exotic many-body quantum states. However, the native long-range interactions between the atoms complicate experimental analysis and precise theoretical understanding of these systems. Here we use new tensor network algorithms capable of including all long-range interactions to study the ground state phase diagram of Rydberg atoms in a geometrically unfrustrated square lattice array. We find a greatly altered phase diagram from earlier numerical and experimental studies, revealed by studying the phases on the bulk lattice and their analogs in experiment-sized finite arrays. We further describe a previously unknown region with a nematic phase stabilized by short-range entanglement and an order from disorder mechanism. Broadly our results yield a conceptual guide for future experiments, while our techniques provide a blueprint for converging numerical studies in other lattices.

A Photomechanical Film in which Liquid Crystal Design Shifts the Absorption into the Visible Light Range.

Liquid crystalline polymer networks (LCN) with azobenzene monomers bend reversibly under UV-light irradiation, combining photomechanical and photothermal effects. However, the harmful nature of UV-light limits their use in biology and soft robotics. Although visible light-absorbing tetra-ortho-fluoro-substituted azobenzenes exist, liquid crystalline monomers have never been prepared. Previously, such azobenzenes were added as photoactive additives (up to 10%) to otherwise passive liquid crystalline polymer networks. In this work, a molecular design of a liquid crystalline, polymerizable azobenzene switchable by visible light is presented. The monomer assembles in a highly fluid nematic phase, but polymerizes in a layered smectic C phase. The films are produced solely from the monomer without additional liquid crystalline components and are actuated with visible light. Bending experiments in air and under water differentiate photomechanical and photothermal effects. Remarkably, a 60µm splay aligned film maintains its deformation for hours, slowly reverting over days. Monomer liquid crystallinity is characterized using differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS), and polarized optical microscopy (POM); polymer films are analyzed using WAXS and DSC on a homogeneously aligned film. The synthetic procedure is high yielding and polymer film fabrication is scalable, which enables the use of safe and efficient photomechanical LCNs in soft robotics, engineering and biology.

Charge-driven liquid-crystalline behavior of ligand-functionalized nanorods in apolar solvent.

Concentrated colloidal suspensions of nanorods often exhibit liquid-crystalline (LC) behavior. The transition to a nematic LC phase, with long-range orientational order of the particles, is usually well-captured by Onsager's theory for hard rods, at least qualitatively. The theory shows how the volume fraction at the transition decreases with increasing aspect ratio of the rods. It also explains that the long-range electrostatic repulsive interaction occurring between rods stabilized by their surface charge can significantly increase their effective diameter, resulting in a decrease in the volume fraction at the transition, as compared to sterically stabilized rods. Here, we report on a system of ligand-stabilized LaPO4 nanorods, of aspect ratio ≈11, dispersed in apolar medium exhibiting the counter-intuitive observation that the onset of nematic self-assembly occurs at an extremely low volume fraction of ≈0.25%, which is lower than observed (≈3%) with the same particles when charged-stabilized in polar solvent. Furthermore, the nanorod volume fraction at the transition increases with increasing concentration of ligands, in a similar way as in polar media where increasing the ionic strength leads to surface charge screening. This peculiar system was investigated by dynamic light scattering, Fourier-transform infrared spectroscopy, zetametry, electron microscopy, polarized light microscopy, photoluminescence measurements, and X-ray scattering. Based on these experimental data, we formulate several tentative scenarios that might explain this unexpected phase behavior. However, at this stage, its full understanding remains a pending theoretical challenge. Nevertheless, this study shows that dispersing anisotropic nanoparticles in an apolar solvent may sometimes lead to spontaneous ordering events that defy our intuitive ideas about colloidal systems.

Non-linear optical chiral nematic bandgap

ABSTRACTWe construct a joint Lagrangian to describe the interaction between a non-magnetic chiral or twisted nematic phase and an electromagnetic wave. Using the well-known Oseen transformation, we rewrite the Lagrangian to transform the director angle of the liquid crystal in an ignorable coordinate which allows to decouple the electric components from the director angle to get the non-linear dynamical equation governing the electromagnetic fields within the liquid crystal phase. We propose a trial solution to get an approximated solution of the fields which allow us to get an intensity dependent band structure that we analyse.

Effect of Surface Functionality on the Rheological and Self-Assembly Properties of Chitin and Chitosan Nanocrystals and Use in Biopolymer Films.

Chitin nanocrystals (ChNCs) are unique to all other bio-derived nanomaterials in one aspect: the inherent presence of a nitrogen moiety. By tuning the chemical functionality of this nanomaterial, and thus its charge and hydrogen bonding capacity, one can heavily impact its macroscopic properties such as its rheological and self-assembly characteristics. In this study, two types of ChNCs are made using acid hydrolysis (AH-ChNCs) and oxidative (OX-ChNCs) pathways, unto which deacetylation using a solvent-free procedure is utilized to create chitosan nanocrystals (ChsNCs) of varying degree of deacetylation (DDA). These nanocrystals were then studied for their rheological behavior and liquid crystalline ordering. It was found that with both deacetylation and carboxylation of ChNCs, viscosity continually increased with increasing concentrations from 2 to 8 wt %, contrary to AH-ChNC dispersions in the same range. Interestingly, increasing the amine content of ChNCs was not proportional to the storage modulus, where a peak saturation of amines provided the most stiffness. Conversely, while the introduction of carboxylation increased the elastic modulus of OX-ChNCs by an order of magnitude from that of AH-ChNCs, it was decreased by increasing DDA. Deacetylation and carboxylation both inhibited the formation of a chiral nematic phase. Finally, these series of nanocrystals were incorporated into biodegradable pectin-alginate films as a physical reinforcement, which showed increased tensile strength and Young's modulus values for the films incorporated with ChsNCs. Overall, this study is the first to investigate how surface functionalization of chitin-derived nanocrystals can affect their rheological and liquid crystalline properties and how it augments pectin/alginate films as a physical reinforcement nanofiller.

Magnetic Field-Induced Spin Nematic Phase Up to Room Temperature in Epitaxial Antiferromagnetic FeTe Thin Films Grown by Molecular Beam Epitaxy.

Electronic nematicity, where strong correlations drive electrons to align in a way that lowers the crystal symmetry, is ubiquitous among unconventional superconductors. Understanding the interplay of such a nematic state with other electronic phases underpins the complex behavior of these materials and the potential for tuning their properties through external stimuli. Here, we report magnetic field-induced spin nematicity in a model system tetragonal FeTe, the parent compound of iron chalcogenide superconductors, which exhibits a bicollinear antiferromagnetic order. The studies were conducted on epitaxial FeTe thin films grown on SrTiO3(001) substrates by molecular beam epitaxy, where the bicollinear antiferromagnetic order was confirmed by in situ atomic resolution scanning tunneling microscopy imaging. A 2-fold anisotropy is observed in in-plane angle-dependent magnetoresistance measurements, indicative of magnetic field-induced nematicity. Such 2-fold anisotropy persists up to 300 K, well-above the bicollinear antiferromagnetic ordering temperature of 75 K, indicating a magnetic field-induced spin nematic phase up to room temperature in the antiferromagnet FeTe.

Chiral nematic and fluctuation-induced first-order phase transitions in AB-stacked kagome bilayers

Chiral nematic and fluctuation-induced first-order phase transitions in AB-stacked kagome bilayers

Proton-decoupled deuterium NMR study of an asymmetric liquid crystal dimer having two nematic phases.

Proton-decoupled deuterium NMR spectra were obtained for an asymmetric liquid crystal dimer 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'-yl)hexane (CB6OCB) containing a single -CD_{2}- group. The sample has two nematic liquid crystal phases: a twist-bend nematic, N_{TB}, at the lowest temperature followed by a uniaxial nematic, N_{U}, on increasing the temperature. Proton decoupling reduces the linewidths of the peaks in the deuterium spectrum from kHz to ∼100Hz, enabling quadrupolar splittings, Δν, to be obtained with enhanced precision as well as the dipolar coupling between deuterium nuclei within the CD_{2} group, hence enhancing the information content.

Theory of phase transitions in the assembly of biaxial molecules interacting via dispersion forces II: on phase transitions of flexible molecules

Previously, I investigated phase transitions in an assembly of biaxial molecules interacting via dispersion forces. Consequently, a uniaxial and two biaxial nematic phases, as well as a disco-nematic phase, were reported to appear in such an assembly of biaxial molecules. However, the investigation was performed at limited points in the space of anisotropy parameters ɛx and ɛy. In the present study, phase transitions at all points in the space of anisotropy parameters are investigated because understanding phase transitions in a system of flexible molecules, whose shape and/or anisotropy of molecular interaction change with temperature or density, is valuable and important.