Cholesteric Phase Research Articles

Design and rheological behaviour of lactic acid based cholesteric liquid crystalline materials with hydroquinone unit in the molecular core

In order to contribute to molecular structure – physical property relationship for chiral self-assembling materials, two chiral compounds derived from the lactic acid have been designed. Mesogenic core of materials consists of two benzoate units and one hydroquinone unit connected by the ester linkage groups and two flexible alkyl chains. Different lengths of the chiral alkyl chain were tested, while the length of the achiral alkyl was kept same for all materials. The mesomorphic properties were established by polarizing optical microscopy and differential scanning calorimetry. Both materials possess reasonably broad and stable cholesteric (N*) phase down to room temperature. The rheological characterisation was performed in the N* phase on the compound with shorter chiral alkyl chain using a rotational rheometer in a plate/plate geometry with and without external electric field applied perpendicularly to the flow direction. The results reveal a shear thinning behaviour, even without electric field applied. The N* phase exhibits a slight electrorheological effect, at low shear rates, that continuously decrease with the increase of the shear rate, due to the competition of the flow and electric fields. The mesomorphic behaviour of the designed materials was compared to structurally similar materials. Quite broad temperature range of the N* phase down to room temperature makes studied lactic acid derivatives as suitable chiral dopants for design of new multicomponent mixtures targeted for various applications in photonics and optoelectronics.

Structural Colors from Amyloid-Based Liquid Crystals.

The helical periodicity and layered structure in cholesteric liquid crystals (CLCs) may be tuned to generate structural color according to the Bragg's law of diffraction. A wide range of natural-based materials such as condensed DNA, collagen, chitin, cellulose, and chiral biopolymers exhibit cholesteric phases with left-handed helixes and ensued structural colors. Here, the possibility of using amyloid CLCs is reported to prepare films with iridescent color reflection and opposite handedness. Right-handed CLCs assembled by left-handed amyloid fibrils are dried into layered structures with variable pitch controlled by the addition of glucose. Circularly polarized light with the same handedness of amyloid CLCs helix is reflected in the Bragg regime. Varying the drying speed leads to the switching between films with a rainbow-like color gradient and large area uniform color. It is confirmed that the origin of the colors derives from the layered structures of the amyloid CLCs, given the negligeable birefringence of the films, calculated from optical rotatory dispersion. These findings provide a facile approach to constructing biosourced cholesteric materials and introduce an original class of proteinaceous materials for the generation of structural colors from right-handed circularly polarized light.

The effect of shape, polydispersity, charge, and fraction of crystallite bundles on the cholesteric pitch of cellulose nanocrystal suspensions

Using Onsager–Straley’s second-virial theory, we investigate the cholesteric pitch of cellulose nanocrystal (CNC) suspensions. We model the CNCs as hard chiral bundles of microfibrils and examine the effect of the shape of these chiral bundles, characterized by aspect ratio and chirality, on the cholesteric pitch. Additionally, we explore the impact of length polydispersity and surface charge on the cholesteric phase of CNCs. Furthermore, we consider binary mixtures of twisted bundles and achiral primary crystallites to provide a more realistic representation of CNC suspensions. Our findings reveal that the degree of bundle twisting significantly affects the helical twisting of the cholesteric phase. We also observe that the average particle length and length polydispersity have substantial effects on strongly twisted bundles but minimal effects on weakly twisted ones. Finally, our study indicates that as the range of electrostatic interactions increases, the transfer of chirality from the microscopic to macroscopic length scales becomes masked, resulting in an increase in the cholesteric pitch. In the case of binary mixtures, the bundles act as chiral dopants, and an increasing fraction of bundles progressively enhances the helical twisting of the cholesteric phase.

Photoisomerization dynamics of a light-sensitive chiral dopant in a nematic medium

ABSTRACT Azobenzene-based chiral dopants in cholesteric liquid crystals are of interest since the properties they induce in the liquid crystal could be tuned photochemically. Here, we use a substituted binaphthyl with a halogenated azobenzene as a chiral dopant to induce a photoswitchable cholesteric phase in the nematic 4-n-pentyl-4’-cyanobiphenyl. The azobenzene group chemically attached to the chiral dopant undergoes isomerisation from trans to cis upon irradiation with green light (wavelength 535 nm), and from cis to trans upon irradiation with blue light (wavelength 450 nm). The transition between the two isomers causes helicity inversion of the cholesteric, with a left-handed trans isomer and a right-handed cis isomer. We report on the kinetics of photoisomerisation of both processes (trans-to-cis and cis-to-trans) in the nematic host by following the pitch evolution over time. We show that the kinetic mechanism corresponds to a two-step process: a first-order isomerisation followed by a second-order autocatalytic isomerisation. This mechanism differs from the typical first-order kinetics for cis-to-trans or trans-to-cis isomerisation in azobenzenes. The autocatalytic process is attributed to interactions between the chiral dopant and the nematic host.

Short helix pitch ferroelectric liquid crystals induced in nematic matrix by chiral non-mesogenic dopants

We report the development of chiral smectic C (SmC*) ferroelectric liquid crystals (FLCs) obtained by mixing of a nematic liquid crystal (NLC) as a host and chiral non-mesogenic dopants. The NLC is a binary eutectic mixture of phenyl- and biphenyl-pyrimidines, while chiral dopants belong to homologous series of secondary dilactates with terphenyldicarboxylate core. The induction in the mixtures not only the cholesteric phase, but also the wide temperature range ferroelectric SmC* phase with the helix pitch p0≈100 nm and the spontaneous polarization Ps about 70 nC/cm2 has been confirmed by dielectric, optical, and electro-optical measurements. The developed FLC mixtures are highly efficient for the deformed helix ferroelectric liquid crystal electro-optical mode because the mixtures combine mechanical stability (or mechanical shock resistance) of NLCs and kilohertz switching frequency (due to short helix pitch) of FLCs. These FLCs can be used to create various photonic devices, such as generators of vortex light fields and field-sequential color displays.

Bio‐Inspired Cholesteric Phase Cellulose Composite with Thermochromic and Circularly Polarized Structural Color for Multilevel Encryption

AbstractThe escalating need for enhanced cryptographic security necessitates the development of advanced materials designed for the secure storage and transmission of information. Drawing inspiration from the unique color‐altering and polarizing capabilities of beetles, this work develops a transparent, thermochromic, and circularly polarized cholesteric phase cellulose composite (CPCC). This is achieved by integrating self‐assembled hydroxypropyl cellulose with cholesteric liquid crystal (CLC) structure in tandem with a crosslinked poly(N‐isopropyl acrylamide) (PNIPAM) network. The crosslinking density impacts the response degree of thermochromism, which can be regulated by modifying the UV exposure time during PNIPAM production. The CLC structure in CPCC uniquely results in reflected right circularly polarized light. When coupled with waveplates, this mechanism inverts the rotation direction of the reflected light, creating orthogonal structural colors of different brightness levels under left and right circularly polarized light. The excellent transparency of CPCC facilitates seamless integration with the environment, offering optimal camouflage. Sophisticated techniques, such as color coding and Morse coding, can further be incorporated within the CPCC to increase encryption security and the complexity of decryption. Collectively, the CPCC's transparency, thermochromism, and chirality present significant potential in the design and development of materials for high‐security information encryption, contributing valuable insights to the field.

A PSCLC Pattern Prepared Based on Handedness Inversion for Anti-counterfeiting.

Handedness inversion has been widely studied in supramolecular chemistry and material sciences. Herein, a photoisomerizable chiral dopant was synthesized, which could induce the formation of a cholesteric phase with right-handedness. The Bragg reflection band of the cholesteric liquid crystal (CLC) mixture shifted to the long wavelength with extending 365 nm UV light irradiation time. Based on this photochromic property, a colourful polymer-stabilized CLC (PSCLC) film was prepared using a grayscale mask. A handedness reversible CLC mixture was prepared using a mixture of this chiral dopant and S5011. With extending the UV light irradiation time, the handedness of the CLC mixture changed from right- to left-handedness. A patterned PSCLC film was prepared using this CLC mixture. Complementary images were observed under right- and left-handedness circularly polarized lights. The results shown here not only give us a better understanding the competition between photopolymerization and photoisomerization, but also lay the foundations for decoration and anti-counterfeiting.

Large Range Thermochromism in Liquid Crystalline Elastomers Prepared with Intra‐Mesogenic Supramolecular Bonds

AbstractLiquid crystalline elastomers (LCEs) that retain the cholesteric phase (CLCEs) are soft, polymeric materials that retain periodic structure and exhibit a selective reflection. While prior studies have examined thermochromism in CLCEs, the association of temperature change and reflection wavelength shift has been limited to 1.4 nm °C−1. Here, CLCEs with intra‐mesogenic supramolecular bonds are prepared to enhance tunability as well triple the rate (e.g., 4.8 nm °C−1). Specifically, these materials incorporate liquid crystalline monomers based on dimerized oxy‐benzoic acid (OBA) derivatives. Increasing the concentration of the OBA comonomers increases the magnitude of red‐shifting thermochromism of the selective reflection. At and above a threshold concentration, the selective reflection in the CLCEs can disappear upon heating, analogous to on‐off “switching.” Further, the introduction of the supramolecular bonds within the CLCE enable mechanical programming and enhanced one‐time tunable thermochromism via a one‐way shape memory process. Accordingly, this research could enable functional use in low temperature sensitive optical elements, fail‐safe thermal indicators for food packaging, and smart window coatings.

Uniaxial - biaxial lyotropic cholesteric phase transition of lyotropic liquid crystals

ABSTRACT A Landau model is proposed to describe the uniaxial – biaxial lyotropic cholesteric phase transition of lyotropic liquid crystals (LLC). The model free energy is based on a mixture of rod-shaped and disc-shaped micelles. The possibility of the existence of two biaxial lyotropic cholesteric phases and two uniaxial lyotropic cholesteric phases of LLC is discussed. The phase transitions between two biaxial lyotropic cholesteric phases and two uniaxial lyotropic cholesteric phases are explored. Qualitative comparisons between theoretical predictions and recent experimental results are discussed.

Pre-Smectic Ordering and the Unwinding Helix in Monte Carlo Simulations of Cholesteric Liquid-Crystals.

In this paper, molecular chirality is studied for liquid-crystal fluids represented by hard rods with the addition of an attractive chiral dispersion term. Chiral forces between molecular pairs are assumed to be long-ranged and are described in terms of the pseudotensor of Goossens [W. J. A. Goossens, Mol. Cryst. Liq. Cryst. 1971, 12, 237-244]. Following Varga and Jackson [S. Varga and G. Jackson, Chem. Phys. Lett. 2003, 377, 6-12], this is combined with a hard-spherocylinder core. We investigate the relationship between molecular chirality and the helical pitch of the system, which occurs in the absence of full three-dimensional periodic boundary conditions. The dependence of the wavenumber of this pitch on the thermodynamic variables, temperature, and density is measured. We also explore the use of a novel surface boundary interaction model. As a result of this approach, we are able to lower the temperature of the system without the occurrence of nematic droplets, which would interfere with the formation of a uniaxial pitch. Regarding the theoretical predictions of Wensink and Jackson [H. H. Wensink and G. Jackson, J. Chem. Phys. 2009, 130, 234911], on the one hand, we have qualitative agreement with the observed non-monotonic density dependence of the wavenumber. Initially increasing with density, the wavenumber reaches a maximum, before falling as the density moves toward the point of phase transition from cholesteric to smectic. However, further analysis for shorter rods, in the presence of novel boundary conditions, reveals some disagreement with the theory, at least in this case; the unwinding of the cholesteric helix in the cholesteric phase occurs simultaneously with subtle increases in smectic ordering. These pre-smectic fluctuations have not been accounted for so far in theories on cholesterics but turn out to play a key role in controlling the pitch of cholesteric phases of rod-shaped mesogens with a small to moderate aspect ratio.

Recyclable Cholesteric Phase Liquid Crystal Device for Detecting Storage Temperature Failure.

The planar state of a cholesteric liquid crystal (CLC) often exhibits oily streak defects, which negatively impact the characteristics of precision optics, including transmission and selective reflection. In this paper, we introduced polymerizable monomers into liquid crystals and examined the effects of monomer concentration, polymerization light intensity, and chiral dopant concentration on oily streak defects in CLC. With the proposed method of heating cholesteric liquid crystals to the isotropic phase followed by rapid cooling, the oil streak defects presented in the liquid crystal can be successfully eliminated. Furthermore, a stable focal conic state can be obtained by a slow cooling process. Two stable states with different optical properties can be obtained based on the cholesteric liquid crystal at different cooling rates, which makes it possible to detect whether the stored procedure of temperature-sensitive material is qualified. These findings have widespread applications in devices that require a planar state without oily streak defects and temperature-sensitive detection devices.

13C Nuclear Magnetic Resonance Investigations of Molecular Mesogens with a Terminal Phenyl Ring Linked via a Spacer: Odd-Even Effect.

A set of mesogens considered as model molecules to the technologically important twist-bend (NTB) nematogens are investigated. They consist of a three-ring core connected to a phenyl ring via a flexible spacer and displayed enantiotropic nematic and smectic C mesophases. In such systems, odd or even number of atoms present in the spacer could influence the orientation of the terminal phenyl ring and thus have a bearing on designing the NTB phase, considered as intermediate between the nematic and the cholesteric phases. One-dimensional (1D) and two-dimensional (2D) 13C NMR spectra have been recorded in the liquid crystalline phases and the alignment-induced chemical shifts (AIS) and the 13C-1H dipolar couplings obtained. The order parameters of the phenyl rings reveal features relatable to the odd/even number of atoms of the flexible spacer and the type of linkage. The AIS plots of the phenyl rings of the even spacer-based mesogen showed the usual behavior for all of the phenyl rings with a decrease in AIS with increasing temperature. However, for the odd-spacer mesogens, unusual behaviors are noted for the terminal phenyl ring. Thus, two of the mesogens showed an increase of AIS in the smectic C phase that continued till the middle of the nematic phase temperature range, followed by a decrease. The other two odd-spacer mesogens also showed different behaviors. These observations indicate that the terminal phenyl ring is oriented at an angle with respect to the long molecular axis for the odd-spacer mesogens that changes as a function of temperature. The angles have been found to depend on the nature of the atom/group connecting the spacer to the terminal ring and the spacer length. Thus, the present study provides critical information on the design of the odd dimers that are recognized to generate fascinating NTB mesophases.

Fabrication of mesogenic epoxy microsphere-filled negative-dielectric-anisotropy cholesteric liquid crystals for bistable devices

Bistable devices, which can operate in two field-free stable states, are highly desirable for developing smart optical devices with true energy conservation. Cholesteric liquid crystals (CLCs) have been demonstrated as promising candidates for fabricating smart windows and light modulators with bistable characteristics. However, not all CLCs can be fabricated into bistable devices. It is meaningful to develop new technologies to process the CLCs that only have one stable field-free state into bistable devices. In this work, mesogenic epoxy microspheres are prepared by thermal curing between a liquid crystalline epoxide and a thiol monomer in a negative-dielectric-anisotropy CLC solvent to obtain mesogenic epoxy microsphere-filled CLCs. The mesogenic epoxy microspheres are expected to provide anchoring energy to increase the energy barrier between focal-conic and planar textures. The pristine CLC host is only stable in the planar texture, and its focal-conic texture and low-transmittance state cannot be maintained for a long time in the absence of electric fields with a low frequency. On the contrary, for mesogenic epoxy microsphere-filled CLCs, both the planar texture/large-transmittance state and the focal-conic texture/low-transmittance state of the cholesteric phase can be stable for a long time without continuous power input. Moreover, the mesogenic epoxy microsphere-filled CLCs is also developed into bistable smart windows with low energy consumption. This work could provide a simple and interesting strategy for fabricating the bistable CLC devices promising for applications in energy-saving fields.

Achieving a full color palette with thickness, temperature, and humidity in cholesteric hydroxypropyl cellulose

Hydroxypropyl cellulose (HPC) is a sustainable, cost-efficient, and bio-compatible cellulose derivative that forms cholesteric liquid crystalline phases in highlyconcentrated water solutions that reflects colour in the visible range. While there have been studies exploiting HPC’s structural coloration and transferring the cholesteric order of the solutions into solid form via cross-linking, there is still lack of understanding on the thermotropic mechanisms that enable the transfer of the structural ordering of the pure HPC at higher temperatures. In this work, we demonstrate the balance between the temperature, humidity, and film thickness to achieve a full color palette of pure HPC. We reveal that at the early stages of the evaporation, formation of a dense skin over the lyotropic phase facilitates the thermal expansion of the HPC during the heat treatment. Increasing the thickness, applying higher drying temperatures, and exposing the samples to higher humidity during the evaporation all result with increased pitch values that cause a red-shift in coloration in the solid state. Our analysis of the HPC samples dried in controlled temperature and humidity conditions at a fixed thickness provided an understanding of the dominance of the thermal expansion which drives the final structural organization in the solid cholesteric phase. When the thickness of the films was varied against fixed temperature and humidity conditions, the color shift from red to violet follows the thickness gradient of the sample due to the change in the drying time required to reach the solid form.

Testing different supervised machine learning architectures for the classification of liquid crystals

ABSTRACTDifferent convolutional neural network (CNN) and inception network architectures were trained for the classification of isotropic, nematic, cholesteric and smectic liquid crystal phase textures to test the prediction accuracy for each one of these models. Varying the number of layers and inception blocks, as well as the regularisation, and application to different phase transitions and classification tasks, it is shown that in general the architecture of an inception network with two blocks leads to the best classification results. Regularisation, such as image flipping, and dropout layers additionally somewhat increase the classification accuracy. Even for simple tasks like the isotropic-nematic transition, which is of importance for applications in the automatic readout of sensors, convolutional neural networks need more than one layer. Care must be taken to not apply architectures of too large complexity, as this will again reduce the classification accuracy due to overfitting. Architecture complexity needs to be adjusted to the given classification task

Synthesis of Thiophene-Based Derivatives and the Effects of Their Molecular Structure on the Mesomorphic Behavior and Temperature Range of Liquid-Crystalline Blue Phases

The development of blue-phase liquid crystal (BPLC) materials with a wide temperature range is of great significance for practical applications in the optoelectronic field. In the study, bent-core derivatives with a 3-hexyl-2,5-disubstituted thiophene central ring in the λ-shaped molecular structure were designed and synthesized. Their mesomorphic behavior and effect on the blue-phase (BP) temperature range were investigated. Interestingly, a BP was achieved both during the heating and cooling processes by doping with a proper concentration of chiral compound into the thiophene bent-shaped molecule with high rigidity, while derivatives with fluorine atom substitution only exhibited cholesteric phase no matter how many chiral compounds were added. This result proved that BP is highly sensitive to the molecular structures of bent-shaped molecules. Moreover, the BP temperature range was broadened when adding these molecules into a BPLC host, which thus improved the BP temperature range from the initial value, no more than 4 °C, to as much as 24 °C. The experimental phenomena were reasonably explained through molecular simulation calculations. The study may provide some experimental basis and theoretical guidance for the design of novel bent-shaped molecules and BPLC material with a wide temperature range.

Bioinspired Photonic Materials from Cellulose: Fabrication, Optical Analysis, and Applications.

Polysaccharides are a class of biopolymers that are widely exploited in living organisms for a diversity of applications, ranging from structural reinforcement to energy storage. Among the numerous types of polysaccharides found in the natural world, cellulose is the most abundant and widespread, as it is found in virtually all plants. Cellulose is typically organized into nanoscale crystalline fibrils within the cell wall to give structural integrity to plant tissue. However, in several species, such fibrils are organized into helicoidal nanostructures with a periodicity comparable to visible light (i.e., in the range 250-450 nm), resulting in structural coloration. As such, when taking bioinspiration as a design principle, it is clear that helicoidal cellulose architectures are a promising approach to developing sustainable photonic materials. Different forms of cellulose-derived materials have been shown to produce structural color by exploiting self-assembly processes. For example, crystalline nanoparticles of cellulose can be extracted from natural sources, such as cotton or wood, by strong acid hydrolysis. Such "cellulose nanocrystals" (CNCs) have been shown to form colloidal suspensions in water that can spontaneously self-organize into a cholesteric liquid crystal phase, mimicking the natural helicoidal architecture. Upon drying, this nanoscale ordering can be retained into the solid state, enabling the specific reflection of visible light. Using this approach, colors from across the entire visible spectrum can be produced, alongside striking visual effects such as iridescence or a metallic shine. Similarly, polymeric cellulose derivatives can also organize into a cholesteric liquid crystal. In particular, edible hydroxypropyl cellulose (HPC) is known to produce colorful mesophases at high concentrations in water (ca. 60-70 wt %). This solution state behavior allows for interesting visual effects such as mechanochromism (enabling its use in low-cost colorimetric pressure or strain sensors), while trapping the structure into the solid state enables the production of structurally colored films, particles and 3D printed objects. In this article, we summarize the state-of-the-art for CNC and HPC-based photonic materials, encompassing the underlying self-assembly processes, strategies to design their photonic response, and current approaches to translate this burgeoning green technology toward commercial application in a wide range of sectors, from packaging to cosmetics and food. This overview is supported by a summary of the analytical techniques required to characterize these photonic materials and approaches to model their optical response. Finally, we present several unresolved scientific questions and outstanding technical challenges that the wider community should seek to address to develop these sustainable photonic materials.

Synthesis and characterisation of novel aromatic ester swallow-tailed cholesteric liquid crystal polymers

ABSTRACT In this paper, two novel aromatic ester swallow-tailed liquid crystal monomers M1 and M2 and a straight chain cholesteric liquid crystal monomer M3 were designed and synthesised. Two series of liquid crystal polymers, P1 series and P2 series, were graft-copolymerised with M and polymethylhydrosiloxane (PHMS). All the synthesised liquid crystal monomers and polymers were characterised by IR and 1H NMR and confirmed to the predicted molecular structure. The liquid crystal and thermal properties of the synthesised compounds were tested by DSC, POM, TGA and optical rotation. The results show that the monomer M1 is a monotropic nematic liquid crystal, and the Schlieren texture appears during the cooling process. M2 is an enantiotropic nematic liquid crystal with filamentous and schlieren texture. M3 is a thermotropic enantiotropic cholesteric phase with oily streak and focal cone texture. Both polymers P1 and P2 show typical Grand-Jean texture, and with the increase of monomer M3 content, the polymer clearing point temperature Ti increases continuously, the liquid crystal mesophase range widens, and the specific rotation value increases.

Effect of Quantum Dots Dispersion on the Structural, Optical, and Thermal Properties of Liquid Crystal System

Liquid crystal-quantum dot (LC-QD) composites are promising new materials for a number of applications in displays, energy harvesting, and photonics. In the present work, quantum dispersion in the mixture of LCs of cholesteric and nematic phases is reported. The combination of two LCs, namely Cholesteryl Palmitate (cholesteric 97%) and 4′-Pentyl-4-biphenylcarbonitrile (nematic, 98%), were used in equal proportion while CdS quantum dots were added in this mixture. The thermal, optical, and structural properties of this new LC-QD composite system were analyzed using differential scanning calorimetry (DSC), ultra-violet visible (UV-VIS) spectroscopy, Fabry-Perot scattering studies (FPSS), and Fourier transform infrared (FTIR) spectroscopy. Structural studies indicate that the QDs are uniformly dispersed inside the LC matrix rather than on the surface area. It was observed that quantum dot dispersion increases the strength of the LC mixture. It also changes the phase behavior of the LC mixture affecting the overall performance of LC-QD composite systems. The present findings would be very helpful for the design of the display and photonic devices with an improved optical response.

Emergence of disordered branching patterns in confined chiral nematic liquid crystals

Spatial branching processes are ubiquitous in nature, yet the mechanisms that drive their growth may vary significantly from one system to another. In soft matter physics, chiral nematic liquid crystals provide a controlled setting to study the emergence and growth dynamic of disordered branching patterns. Via an appropriate forcing, a cholesteric phase may nucleate in a chiral nematic liquid crystal, which self-organizes into an extended branching pattern. It is known that branching events take place when the rounded tips of cholesteric fingers swell, become unstable, and split into two new cholesteric tips. The origin of this interfacial instability and the mechanisms that drive the large-scale spatial organization of these cholesteric patterns remain unclear. In this work, we investigate experimentally the spatial and temporal organization of thermally driven branching patterns in chiral nematic liquid crystal cells. We describe the observations through a mean-field model and find that chirality is responsible for the creation of fingers, regulates their interactions, and controls the tip-splitting process. Furthermore, we show that the complex dynamics of the cholesteric pattern behaves as a probabilistic process of branching and inhibition of chiral tips that drives the large-scale topological organization. Our theoretical findings are in good agreement with the experimental observations.