Nematic-isotropic Phase Transition Research Articles

Simulating loading–unloading hysteretic behaviors of nematic-genesis polydomain nematic elastomers

Nematic elastomers (NEs) are lightly cross-linked elastomers with nematic mesogens integrated in their polymer networks. Combination of large deformation capability with nematic-isotropic phase transition enables NEs to be the most promising soft materials for impact attenuation, actuation and soft robotics. In this paper, we focus on nematic-genesis polydomain NEs (N-PNEs) where mesogens are cross-linked at nematic states. N-PNEs are capable of absorbing and dissipating energy and easy to synthesize. We present a Voronoi diagram-baseed finite element model for specimen-scale N-PNEs, and investigate the cyclic tensile and compressive behaviors of N-PNEs at different strain rates. Our simulations reveal a smooth polydomain-monodomain transition during loading, accompanied by a full recovery of polydomain texture after the load is removed, indicating a memory effect of initial disordered mesogen alignment. The predicted behaviors align well with experimental observations, which validates our model. Furthermore, we assess the energy absorption and dissipation capabilities of N-PNEs compared to monodomain NEs, identifying conditions where N-PNEs exhibit superior performance. This study not only enhances our understanding of polydomain-monodomain transitions in N-PNEs, but also lays the groundwork for the development of N-PNE-based energy absorbers

Topological defects as nucleation points of the nematic-isotropic phase transition in liquid crystal shells.

The transition from a nematic to an isotropic state in a self-closing spherical liquid crystal shell with tangential alignment is a stimulating phenomenon to investigate, as the topology dictates that the shell exhibits local isotropic points at all temperatures in the nematic phase range, in the form of topological defects. The defects may thus be expected to act as nucleation points for the phase transition upon heating beyond the bulk nematic stability range. Here we study this peculiar transition, theoretically and experimentally, for shells with two different configurations of four +1/2 defects, finding that the defects act as the primary nucleation points if they are co-localized in each other's vicinity. If the defects are instead spread out across the shell, they again act as nucleation points, albeit not necessarily the primary ones. Beyond adding to our understanding of how the orientational order-disorder transition can take place in the shell geometry, our results have practical relevance for, e.g., the use of curved liquid crystals in sensing applications or for liquid crystal elastomer actuators in shell shape, undergoing a shape change as a result of the nematic-isotropic transition.

Barocaloric effect in a Gay-Berne liquid crystal.

A coarse-grained molecular Monte Carlo simulation of the barocaloric effect in a model Gay-Berne liquid crystal is presented, following the so-called indirect approach wherein the caloric response is obtained from thermodynamic arguments applied to the simulated equilibrium relation between pressure, density, and temperature. From simulation, the magnitude of the effect across the isotropic-nematic and nematic-smectic phase transitions is estimated, together with the heat exchanged outside these transitions, in order to assess its potential for novel cooling and heat pumping applications. Under adiabatic conditions, pressure-induced phase transitions are predicted to result in a temperature variation of a few degrees Kelvin. As a by-product of the simulation, an approximate partial phase diagram of the Gay-Berne fluid under study is also obtained.

Thermoreversible Gel-Dispersed Liquid Crystals.

A simple model is introduced to describe phase behaviours of binary mixtures of a thermoreversible gel and a low-molecular-weight liquid crystal (LC). We predict novel phase diagrams on the temperature-concentration plane, including sol-gel transition, nematic-isotropic phase transition, and phase separation. At high temperatures, the phase separation between the isotropic sol and gel phases appears. As the temperature decreases, we have the phase separation between nematic sol and isotropic gel phases, in which the nematic domains are dispersed in the isotropic gel phase. We suggest that thermoreversible gelation of reactive molecules mixed with LCs will become one of the new classes of polymer-dispersed liquid crystals.

Flexible and elastic thermal regulator for multimode intelligent temperature control

AbstractAs nonlinear thermal devices, thermal regulators can intelligently respond to temperature and control heat flow through changes in heat transfer capacities, which allows them to reduce energy consumption without external intervention. However, current thermal regulators generally based on high‐quality crystalline‐structure transitions are intrinsically rigid, which may cause structural damage and functional failure under mechanical strain; moreover, they are difficult to integrate into emerging soft electronic platforms. In this study, we develop a flexible, elastic thermal regulator based on the reversible thermally induced deformation of a liquid crystal elastomer/liquid metal (LCE/LM) composite foam. By adjusting the crosslinking densities, the LCE foam exhibits a high actuation strain of 121% with flexibility below the nematic–isotropic phase transition temperature (TNI) and hyperelasticity above TNI. The incorporation of LM results in a high thermal resistance switching ratio of 3.8 over a wide working temperature window of 60°C with good cycling stability. This feature originates from the synergistic effect of fragmentation and recombination of the internal LM network and lengthening and shortening of the bond line thickness. Furthermore, we fabricate a “grid window” utilizing photic‐thermal integrated thermal control, achieving a superior heat supply of 13.7°C at a light intensity of 180 mW/cm2 and a thermal protection of 43.4°C at 1200 mW/cm2. The proposed method meets the mechanical softness requirements of thermal regulator materials with multimode intelligent temperature control.

Faraday waves on a nematic liquid crystal, and its coupling with Marangoni convection about the thermal phase transition.

Using a linear hydrodynamic theory, we demonstrate that Faraday waves occur in liquid crystalline fluids. The use of already experimentally known material parameters of a N-(4-methoxybenzylidene)-4-butylaniline liquid crystal allows us to confirm and realize the predictions of this theory. It provides the critical wave number and necessary driving acceleration at instability wave onset. Additionally, these observables experience an abrupt change originated by Marangoni convection due to the temperature gradient at the isotropic-nematic phase transition temperature. Correspondingly, the Marangoni number versus temperature also shows a sharp change in the transition temperature.

Ordering properties of anisotropic hard bodies in one-dimensional channels.

The phase behavior and structural properties of hard anisotropic particles (prisms and dumbbells) are examined in one-dimensional channels using the Parsons-Lee (PL) theory, and the transfer-matrix and neighbor-distribution methods. The particles are allowed to move freely along the channel, while their orientations are constrained such that one particle can occupy only two or three different lengths along the channel. In this confinement setting, hard prisms behave as an additive mixture, while hard dumbbells behave as a non-additive one. We prove that all methods provide exact results for the phase properties of hard prisms, while only the neighbor-distribution and transfer-matrix methods are exact for hard dumbbells. This shows that non-additive effects are incorrectly included into the PL theory, which is a successful theory of the isotropic-nematic phase transition of rod-like particles in higher dimensions. In the one-dimensional channel, the orientational ordering develops continuously with increasing density, i.e., the system is isotropic only at zero density, while it becomes perfectly ordered at the close-packing density. We show that there is no orientational correlation in the hard prism system, while the hard dumbbells are orientationally correlated with diverging correlation length at close packing. On the other hand, positional correlations are present for all the systems, the associated correlation length diverging at close packing.

Equation of State of Charged Rod Dispersions.

We study the accuracy of the theory of Stroobants, Lekkerkerker, and Odijk [Macromolecules 1986, 19, 2232-2238], called SLO theory, to describe the thermodynamic properties of an isotropic fluid of charged rods. By incorporation of the effective diameter of the rods according to SLO theory into scaled particle theory (SPT), we obtain an expression for the rod concentration-dependent free volume fraction and the osmotic pressure of a collection of charged hard spherocylinders. The results are compared to Monte Carlo simulations. We find close agreement between the simulation results and the SLO-SPT predictions for not too large values of the Debye length and for high rod charge densities. The deviations increase with rod density, particularly at concentrations above which isotropic-nematic phase transitions are expected.

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.

Thermotropic liquid crystal doped with silica, silica grafted with aniline (ANI@SiO2) and polyaniline (PANI@SiO2)

ABSTRACT Nanoparticles dispersed in liquid crystals exhibit novel and intriguing properties, which make them suitable materials for displays and photonic applications. This paper reports on the impact of non-modified silica (SiO2), silica grafted with aniline (ANI@SiO2) and silica grafted with polyaniline (PANI@SiO2) nanoparticles on the physical parameters of 7CB liquid crystal. A slight change in the nematic-isotropic phase transition temperature was observed. The results from dielectric experiments revealed an increase in free ion concentration in the doped samples. By fitting a suitable equivalent electric circuit model to the experimental data, we demonstrate changes in the electro-physical parameters of the liquid crystal in the bulk and at the liquid crystal-metal electrode interface. Therefore, we were able to calculate the ion mobility and the diffusion constant. It was also demonstrated that the doping of 7CB with the above-mentioned nanoparticles increases the response time, thresholds, and viscosity.

Surface acoustic wave investigation of magnetic nanoparticle size and concentration effect on liquid crystal behavior.

The effect of spherical magnetic nanoparticles with different size (5, 10, 15, and 20 nm) and volume concentration (10-3, 5 × 10-4, and 10-4) on liquid crystal 4-cyano-4'-hexylbiphenyl (6CB) behavior was investigated using surface acoustic wave (SAW). The attenuation response of SAW propagating along with the substrate/liquid crystal interface was used to study the structural changes induced by an applied magnetic field. The obtained results showed the shift of the threshold magnetic field with an increase in the volume concentration of nanoparticles toward lower fields and also the decrease in the isotropic-nematic phase transition temperature depending on the nanoparticle size and the nanoparticle volume fraction. Results confirmed again that the bulk viscosity coefficients should dominate the SAW attenuation and that the SAW investigation in the presented configuration is applicable to monitoring of the role of magnetic dopants in structural changes under external fields. Some theoretical background of the presented SAW investigation is introduced as well. Obtained results are discussed within the context of previous ones.

Nematic-isotopic phase separations induced by hydrogen bonding between a rodlike polymer and solvent molecules

ABSTRACT We theoretically study nematic-isotropic phase transitions and phase separations in aqueous rodlike polymer solutions, such as rigid DNA (or rodlike polymer) in water. By taking into the hydrogen bonding between a rodlike polymer and solvent molecules, we predict novel phase diagrams, such as overhang-type coexistence curves with isotropic-nematic ( I + N ) phase separations and re-entrant I + N separations. We demonstrate that the hydrogen bonding between molecules of different components stabilises the nematic phase at lower polymer concentrations and temperatures.

Pair correlation functions and stability of nematic in a system of Gay-Berne ellipsoids doped with spherical colloids

Pair-structure of a binary mixture of soft-ellipsoids and spheres interacting via generalized Gay-Berne intermolecular potential using Percus–Yevick (PY) integral equation theory. The generalized Gay-Berne interaction model allows us to vary the diameter of the spheres in comparison to the width of the Gay-Berne ellipsoids. Three different cases of sphere size namely diameter of the spheres being smaller, equal and larger than the minor axis of the ellipsoids have been considered. We have analyzed the radial distribution functions and static structure factors of the mixtures and found that addition of spherical particles to a system of ellipsoids results in stronger pair-correlations between ellipsoidal particles. We observe that smaller spherical additives are more effective in enhancing the ellipsoidal pair-correlations in comparison to the bigger spheres at similar density.The static structure factors are not found to diverge in the low wavelength limit indicating a stable mixture for the set of parameters studied in this work. We have also used classical density functional theory of freezing to investigate the effect of spherical additives and their size on the isotropic-nematic phase transition. We found a stable nematic phase whose order parameter is found to increase with the increase in not only the density of spherical additives but also with increase in their size.

Nanotechnology for purifying nematic liquid crystals based on magnetic separation accompanied by phase transition

Free ions are generally unfavorable in liquid crystal (LC) displays, and LC purification technologies are critically important. The colloidal γ-Fe2O3 magnetic nanoparticles coated with oleic acid (γ-Fe2O3@OA MNPs) have a high ratio of surface to volume, which may adsorb more free ions and are uniform in the LC at room temperature. In this work, the precipitation and separation of the doped colloidal γ-Fe2O3@OA MNPs resulting from the magnetic field accompanied by an isotropic-nematic phase transition are more efficient than in the single case of the phase transition or the magnetic field. The residual ion concentrations have decreased distinctly using the low gradient magnetic field (∇ B ∼ 2 T/m) with the phase transition. In addition, when the doped colloidal γ-Fe2O3@OA MNPs are 0.4 % and 0.2 % by weight, the former concentrations of the residual ions and γ-Fe2O3@OA MNPs are lower than the latter. As a result, the commercial nematic LC can be purified by this approach based on nanotechnology in our study.

Shape memory behaviors of 3D printed liquid crystal elastomers

As soft active materials, shape-memory polymers (SMPs) and liquid crystal elastomers (LCEs) have attracted considerable research interest due to their potential applications in various areas. SMPs refer to polymeric materials that can return to their permanent shape in response to external stimuli, such as heat, light, and solvent. In this sense, LCEs can exhibit intrinsic shape-memory behaviors since LCEs can switch between two shapes with temperature change due to the order-disorder transition of liquid crystals. In this work, we fabricate both the polydomain and monodomain nematic LCEs through direct ink writing 3D printing. With increasing the temperature of the substrates, the printed LCEs change from the monodomain state to the polydomain state. For polydomain LCEs, a reversible shape change can occur upon constant loading, while the monodomain can switch the shape with temperature in the stress-free state. This two-way shape-memory behavior is caused by the nematic-isotropic phase transition. We further show that the printed LCEs exhibit a good one-way shape-memory effect due to glass transition. The shape recovery region increases with the programming temperature, which is a typical temperature memory effect. Finally, it is demonstrated that complex shape-memory performance can be designed by combining one-way and two-way shape-memory effects. Specifically, for the monodomain LCEs, with increasing temperature, the programmed shape first recovers, and a second shape change can further occur due to the nematic-isotropic transition.

Orientational phase transition in monolayers of multipolar straight rigid rods: The case of 2-thiophene molecule adsorption on the Au(111) surface.

Monte Carlo simulations and finite-size scaling theory have been carried out to study the critical behavior and universality for the isotropic-nematic (IN) phase transition in a system of straight rigid pentamers adsorbed on a triangular lattice with polarized nonhomogeneous intermolecular interactions. The model was inspired by the deposition of 2-thiophene molecules over the Au(111) surface, which was previously characterized by experimental techniques and density functional theory. A nematic phase, observed experimentally by the formation of a self-assembled monolayer of parallel molecules, is separated from the isotropic state by a continuous transition occurring at a finite density. The precise determination of the critical exponents indicates that the transition belongs to the three-state Potts universality class. The finite-size scaling analysis includes the study of mutability and diversity. These two quantities are derived from information theory and they have not previously been considered as part of the conventional treatment of critical phenomena for the determination of critical exponents. The results obtained here contribute to the understanding of formation processes of self-assembled monolayers, phase transitions, and critical phenomena from novel compression algorithms for studying mutual information in sequences of data.

Photopolymerization of 1D photonic structures induced by nematic-isotropic phase transition in liquid crystal.

In this paper, two types of polymer-stabilized periodic structures created by photopolymerization of a nematic liquid crystal confined in a cylindrical structure are presented. Both types of structures were induced by nematic-isotropic phase transition in liquid crystal doped with gold nanoparticles. The first type of structure was created by stabilizing periodic phase separation at the nematic-isotropic phase transition temperature. As a result, a periodic structure with two distinct molecular orientations of nematic liquid crystal was achieved. The period of this structure was equal to the period induced by nematic-isotropic phase separation. The second type of structure, also related to the phase transition, was created due to an induced periodic density change of gold nanoparticles in the sample volume. Through photopolymerization it was possible to preclude the dispersion of gold nanoparticles while preserving the periodicity. An increased concentration of gold nanoparticles caused periodic defects in molecular orientation of the liquid crystal. Both types of structures were stable at room temperature. Consequently, two types of 1D photonic structures stabilized by photopolymerization are presented.

Nematic-isotropic phase transitions in thin slabs of liquid crystals with topological defect arrays.

We study the nematic-to-isotropic phase transitions in thin slabs of nematic liquid crystals with photopatterned director fields of topological defect arrays at constant heating rates and show that the transition kinetics is significantly impacted by both the heating rate and the topological strengths of these defects. Specifically, with ±1/2 defect arrays, the isotropic domains emerge from the defect cores when the heating rate is high, while from random places when the heating rate is low. With ±1 defect arrays, the isotropic domains always emerge from the defect cores regardless of the heating rate. Furthermore, the isotropic domains show significant movements at slow heating rates, and the total area of the isotropic domains grows with the temperature T following a simple power law (T - T')γ, where the exponent γ is approximately 1 in most cases and is 2/3 for the ±1 defect arrays at low heating rates when the isotropic domains are pinned on the defect cores. We attribute this phenomenon to an interplay between the surface tension and bulk free energy.

All-Optical Tunability of Metalenses Permeated with Liquid Crystals.

Metasurfaces have been extensively engineered to produce a wide range of optical phenomena, allowing exceptional control over the propagation of light. However, they are generally designed as single-purpose devices without a modifiable postfabrication optical response, which can be a limitation to real-world applications. In this work, we report a nanostructured planar-fused silica metalens permeated with a nematic liquid crystal (NLC) and gold nanoparticle solution. The physical properties of embedded NLCs can be manipulated with the application of external stimuli, enabling reconfigurable optical metasurfaces. We report the all-optical, dynamic control of the metalens optical response resulting from thermoplasmonic-induced changes of the NLC solution associated with the nematic-isotropic phase transition. A continuous and reversible tuning of the metalens focal length is experimentally demonstrated, with a variation of 80 μm (0.16% of the 5 cm nominal focal length) along the optical axis. This is achieved without direct mechanical or electrical manipulation of the device. The reconfigurable properties are compared with corroborating numerical simulations of the focal length shift and exhibit close correspondence.

An investigation on nematic-isotropic phase transition, viscosity and diffusion coefficient of liquid crystalline elastomers at different temperatures using molecular dynamics simulation

The most considerable feature of liquid crystalline elastomers (LCEs) is nematic-isotropic phase transition which has severe effects on their properties such as crystallinity, viscosity, and diffusion coefficient. The aim of this work is to investigate the phase transition temperature of LCEs based on 4-bis-[4-(3-acryloyloxypropypropyloxy) benzoyloxy]-2-methylbenzene as monomer using a coarse-grained molecular dynamics simulation. In this regard, by assessing the crystallinity as a function of temperature, the most suitable ratio of crosslinker to other components including monomer and flexible spacer is 50 %; thereby, obtaining the highest nematic phase percentage around 60 %. At this condition, the nematic-isotropic phase transition temperature is predicted 360 K. Besides the crystallinity studies, the viscosity and diffusion coefficient against temperature show that the nematic-isotropic phase transition temperature has significant influence on the variations of structural and dynamic properties of LCEs.