Liquid Crystal Mixture Research Articles

Characterization and Application of Dual-Frequency Liquid-Crystal Mixtures in mm-Wave Reflectarray Cells to Improve Their Temporal Response

Liquid Crystal-based mm-wave spatially fed antennas with electronic reconfiguration are a promising solution at the higher frequencies required in next generation networks. However, one of the main drawbacks of the technology in these bands stems from the high reconfigurability times they present. Through this work, a relevant step towards overcoming the temporal problem by using Dual Frequency Liquid Crystals (DFLC) is presented. This paper details, for the first time, both the electromagnetic and temporal characterization of four commercially available DFLC mixtures in W-band, enabling their use in designing faster devices. To evaluate the experimental characterization, a reflectarray surface (made of 50x50 cells) specifically designed to achieve fast switching times with a sufficient phase range has been manufactured and measured. For this cell, a preliminary addressing technique based on overdriving has been used, exhibiting reconfigurability (rise and decay) times of 20 ms, one order of magnitude faster than the current state of the art of LC-based mm-wave planar devices. The measured results match the simulations, and reveal that a precisely designed biasing technique using overdrive must be used for DFLC-cells to achieve time reduction. Additionally, the benefits of this technology compared with other LC acceleration strategies in mm-wave are discussed.

Synthesis of Microparticles with Diverse Thermally Responsive Shapes Originated from the Same Janus Liquid Crystalline Microdroplets.

Liquid crystalline elastomer (LCE)-based microparticles that can change shapes in response to external stimuli are of great interest for potential applications such as artificial cells, micro-actuators, micro-valves, and smart drug carriers. Here, the synthesis of LCE microparticles with diverse temperature-dependent anisotropic shapes originated from the same Janus microdroplets is reported. The Janus microdroplets, suspended in an aqueous solution of surfactants, are transformed from microdroplets consisting of a mixture of liquid crystal (LC) monomers, oligomers, silicone oil, and an organic solvent, after the removal of the organic solvent. The molecular alignment of the LC part at the interface, whether planar, homeotropic, or hybrid, is dependent on the choice of the surfactants but not affected by the silicone oil. After polymerization and solvent extraction of the unreacted components, LCE microparticles of various shapes are obtained depending on the concentration and composition of the surfactants, the weight ratio of the LC part to the silicone oil part, and the choice of the extraction solvent. The microparticles that undergo different synthetic pathways show distinct thermally responsive shapes, much like how stem cells differentiate in different environmental conditions.

Sensitive liquid crystal composites for optical sensors

The paper presents a comparative analysis of liquid crystal cholesteric-nematic mixtures for their use as sensitive elements of gas sensors. Liquid crystal mixtures based on nematic mixture E7 and cholesteric impurity CB15 were considered. In order to determine the optimal mixture, a study of the spectral characteristics of the mixtures was carried out, and the main transmission peaks were determined for different concentrations of the optically active impurity. The temperature characteristics were measured to determine the threshold values for the transition of the mixtures to the isotropic state and stable temperature areas. As a result of the conducted research, we can state that as a sensitive element of optical sensors, it is advisable to use liquid crystal mixtures with impurity concentrations of CB15 of 38% and 44%. Their main transmission peaks are in the visible region of the spectrum of 500-600 nm. The temperature characteristics are slightly better in the 38% mixture, but we can claim a slightly higher sensitivity to organic substances in the 44% mixture. Further research of mixtures can be carried out during the direct development of optical sensors.

Liquid crystalline substances doped with carbon nanotubes as a sensitive medium of the CO2 sensor

The creation of highly sensitive optical CO2 sensors in air is an urgent problem, as it allows monitoring of the content of CO2 both indoors and in ambient air, where its level is usually 600…1000 ppm. As a sensitive element of the CO2 sensor, it is proposed to use a liquid crystal substance (cholesteric-nematic mixture based on 5CB with cholesteric impurities), supplemented with multi-layered carbon nanotubes. The spectral characteristics of the liquid crystal mixture in the range of 400…600 nm were studied. The content of carbon nanotubes ranged from 0.1 to 0.5 wt.%. It was established that with an increase in concentration in the range of 10…100 mg/m3, the transmission minimum shifts to the long-wave region of the spectrum. The maximum spectral sensitivity in this range is 6 nm ⁄ mg ⁄ m3. The researched material can be used as a sensitive element of an optical CO2 sensor. Further research should be conducted in the direction of investigating the interaction of such a composite with other gases, as well as finding opportunities to improve the properties of the composite. Perhaps the use of multi-walled carbon nanotubes.

Chirality transfer to harness mesophase transitions in liquid crystal mixtures containing an oxadiazole derivative

ABSTRACT Chiral liquid crystal mixtures are an important field of research in the development of these materials. The main advantage of chiral liquid crystal mixtures is their ability to produce an optically active three-dimensional structure. Moreover, 1,3,4-oxadiazoles have been widely used as electron-transporting/hole-blocking materials or emitting layers in electroluminescent diodes and nonlinear optical materials owing to their interesting properties. Here, we investigate the phase transitions in a mixture of a chiral oxadiazole derivative liquid crystal, EOS-12, and a traditional nematic liquid crystal, E7. EOS-12 is miscible with the E7 matrix at all concentrations. The mesomorphic properties of these mixtures were studied using differential scanning calorimetry (DSC), polarised optical microscopy (POM) and digital colourimetry analysis. In addition, the cholesteric pitch is measured using the Grandjean-Cano technique and photophysical studies were performed in solutions and films. Mixtures show polymorphism depending on the concentration and temperature: nematic, chiral nematic, TGBA*, and smectic phases. A temperature-concentration phase diagram was established using POM. Stabilisation of the SmA phase is observed with a greater temperature range than the constituents of the mixture. According to these results, the properties of the mixture can be used to create various material functionalities, depending on the composition of the mixture.

Colourful patterns prepared using a cholesteric liquid crystal mixture with both thermochromic and photochromic properties

ABSTRACT Colourful polymer-stabilised cholesteric liquid crystal (PSCLC) film attracted much attention for their applications in decoration and anti-counterfeiting. Herein, a chiral dopant was synthesised using trans-p-hexoxycinnamic acid. With the addition of this chiral dopant in a reactive LC mixture, both thermochromic and photochromic phenomena were found. The Bragg reflection band of the CLC mixture shifted to long wavelength with extending 365-nm UV light irradiation time or increasing temperature. The structural colour can cover the visible range. The photochromic property of the CLC mixture was driven by the photoisomerisation of the chiral dopant. Colourful PSCLC patterns were prepared based on the thermochromic and/or photochromic properties and using masks. The results shown here not only give us a better understanding the competition between photopolymerisation and photoisomerisation, but also lay a foundation for the preparation of the decorations.

Phase behavior of nematic-nanoparticle mixtures

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

Liquid Crystal-Templated Porous Microparticles via Photopolymerization of Temperature-Induced Droplets in a Binary Liquid Mixture.

Porous polymeric microspheres are an emerging class of materials, offering stimuli-responsive cargo uptake and release. Herein, we describe a new approach to fabricate porous microspheres based on temperature-induced droplet formation and light-induced polymerization. Microparticles were prepared by exploiting the partial miscibility of a thermotropic liquid crystal (LC) mixture composed of 4-cyano-4'-pentylbiphenyl (5CB, unreactive mesogens) with 2-methyl-1,4-phenylene bis4-[3-(acryloyloxy)propoxy] benzoate (RM257, reactive mesogens) in methanol (MeOH). Isotropic 5CB/RM257-rich droplets were generated by cooling below the binodal curve (20 °C), and the isotropic-to-nematic transition occurred after cooling below 0 °C. The resulting 5CB/RM257-rich droplets with radial configuration were subsequently polymerized under UV light, resulting in nematic microparticles. Upon heating the mixture, the 5CB mesogens underwent a nematic-isotropic transition and eventually became homogeneous with MeOH, while the polymerized RM257 preserved its radial configuration. Repeated cycles of cooling and heating resulted in swelling and shrinking of the porous microparticles. The use of a reversible materials templating approach to obtain porous microparticles provides new insights into binary liquid manipulation and potential for microparticle production.

Cover Image, Volume 140, Issue 25

This cover image was created by Chun-Yen Liu and co-authors. Asymmetrically constructed cholesteric liquid crystal elastomers show direction-controllable thermal rolling actuation. The background shows a POM texture of the prepared liquid crystal mixture. In this manuscript, we demonstrate a novel design of cylindrical liquid crystal elastomers which were fabricated by Michael addition, and the synthesized CLCE prepolymers were then uniaxially stretched with a twisted angle and fixed with UV polymerization. The synthesized asymmetrically constructed CLCEs reveal that the gravity center shifts from the geometric center, showing thermal rolling actuation. DOI: 10.1002/app.53970

Tailoring the physical parameters of ferroelectric liquid crystal mixture with cadmium selenide quantum dots

ABSTRACT Present studies demonstrate the dispersion effect of cadmium selenide quantum dots on ferroelectric liquid crystal mixture properties. Varying concentrations of cadmium selenide quantum dots (0.05 wt.%, 0.10 wt.% and 0.50 wt.%) have been taken to investigate its influence on the physical parameters of ferroelectric liquid crystal mixture KCFLC 10R. Phase transition, textural, electro-optical and photoluminescence studies have been performed in planar aligned cells. The presence of QDs disturbs the geometrical symmetry and molecular tilt of ferroelectric liquid crystal molecules which results in the modification of physical parameters of ferroelectric liquid crystal. It has been observed that doped samples have shown decrement in spontaneous polarisation and rotational viscosity. However, there is an improvement in the response time of the doped samples. The reduction in the spontaneous polarisation with voltage signifies that doped samples can operate at low voltage (~6 V) as compared to ferroelectric liquid crystal mixture (~12 V). Photoluminescence studies reveal that all the samples absorb UV light ~340 nm and produce visible emission at ~ 400 nm which can behave as UV light storage and high contrast display. This would be beneficial for luminescent displays as well as UV to visible light conversion applications.

Impact of red emissive ZnCdTeS quantum dots on the electro-optic switching, dielectric and electrochemical features of nematic liquid crystal: Towards tunable optoelectronic systems

In the present study, the concentration-dependent dielectric, electro-optical, and electrochemical properties of ZnCdTeS quantum dots (QDs) doped E7 nematic liquid crystal (NLC) mixtures were investigated. The dielectric permittivity components (ε‖ and ϵꓕ) and dielectric anisotropy (Δϵ = ε‖ ˗ ϵꓕ) of NLC samples containing varied concentrations of ZnCdTeS QDs (i. e. 0.10, 0.25, 0.50, 0.75, and 1 wt%) were measured at various temperatures. In the nematic phase, the results demonstrated that ε‖ increases much more than ϵꓕ upon an increase in the concentration of ZnCdTeS QDs. Δϵ enhanced as the concentration of QDs increased, reaching a maximum at 0.50 wt%, then decreased with further addition. Dielectric measurements revealed the formation of self-aligned QD arrays along the nematic director, which act similarly to multiple parallel capacitors in the NLC system. Moreover, electro-optical studies illustrated the significant effect of QDs doping on lowering the threshold voltage and response time. Interestingly, the optical switching-off time of NLC containing 0.50 wt% of the QDs decreased by ∼50% compared to that of the pure E7 sample. The reduced screening effect resulting from the QDs ion-capturing mechanism, enhanced effective intermolecular interactions, and increased dielectric anisotropy in the NLC system are the major factors responsible for the improved electro-optical characteristics. The impedance behavior of NLC cells was studied in the frequency range of 0.1 Hz–100 kHz. It indicated that the addition of ZnCdTeS QDs results in a remarkable increase of 96% in the electrical conductivity of the NLC system. Furthermore, the QDs doping significantly improved the NLC device's charge capacitance. Such studies would undoubtedly be beneficial for designing next-generation tunable optoelectronic systems since QDs can be utilized for tuning the dielectric anisotropy, electro-optical characteristics, charge capacitance, and conductivity of NLCs.

English

This paper reports details of phase transitions of a new generation “Tertiary Liquid Crystal System” (TLCS). This TLCS was made with a mixture of 5CB, 6CB, and 7CB liquid crystals. The TLCS was run in DSC to find changes taking place in its heat flow as a function of time and temperature analyzed with Logger Pro. The sample of TLCS was run from -40 °C to 80 °C with a 20 °C/min ramp rate in DSC. It was observed that the TLCS shows two phase transitions on heating and one transition on cooling. All these transitions were found to shift when compared to their single members. The unique behavior of TLCS is that it never shows crystallization in cooling, even though the sample was cooled to -40 °C. This indicated an increase in its Nematic range, making it more useful in the Liquid Crystal Display (LCD) field.

Composite of DNA-Stabilized Multiwalled Carbon Nanotube and Nematic Liquid Crystal for Display Performance Optimization

We have prepared composites of a nematic liquid crystal (NLC) mixture to improve display performance by doping multiwalled carbon nanotubes (MWCNTs) and single-stranded-DNA-wrapped MWCNTs. Polarized optical microscopy images indicated the uniformity of the composite. Infrared absorption spectra showed there existed an interaction between MWCNTs and 4-pentyl-4′-cyanobiphenyl (5CB, a practical solvent-type monomer NLC) due to π–π stacking and charge transfer, indicating the anchoring of 5CB molecules on the MWCNT surface. The electro-optical property proved the incorporation of MWCNTs and DNA-wrapped MWCNTs reduced the threshold voltage and response time, thus following the changed splay elastic constant and rotational viscosity coefficient of LC, reflecting that DNA can improve the stability of MWCNTs in 5CB. Moreover, dielectric measurement showed the enhanced value to dielectric anisotropy and shift in relaxation frequency, including the changes of dielectric permittivity and loss, revealing the electrically “inertness” MWCNTs at high frequencies and the DNA-induced broadened frequency range of low dielectric loss. Then electrical conductivity tests further proved the cooperative orientation of MWCNTs with 5CB under the applied voltage and the contribution of MWCNTs’ high conducting along the long axis. This study revealed that MWCNT doping could improve the physical properties of NLCs, and DNA wrapping could pave a promising way toward stabilized MWCNT/NLC composites for display performance optimization.

Optical and flexoelectric biosensing based on a hybrid-aligned liquid crystal of anomalously small bend elastic constant

Liquid crystal (LC)-based biosensors rely on the response of the LC molecules to perturbation generated by analytes at the interface, leading to the susceptible change in molecular alignment or orientation. The sensitivity of these biosensors is primarily dependent on the LC's material properties and surface anchoring strength. By incorporation of an unconventional mesogenic compound (CB7CB) coupled with the hybrid-alignment cell configuration, this work presents a binary nematic LC for label-free biosensing, manifesting a novel sensing technology that takes advantage of CB7CB-induced flexoelectricity in the transducer. Herein, we prepared LC mixtures by blending a typical rod-like nematic LC (E7) with the bent-core mesogen CB7CB in various weight ratios and studied the effect of the CB7CB content on E7/CB7CB-based biosensing performance in vertically aligned and hybrid-aligned nematic (HAN) cells. Owing to the anomalously small bend elastic constant K33 in CB7CB, the mixture designated CB45 with the highest CB7CB weight percentage (45 wt% in this study) was best applicable to biosensing in HAN cells. When observed under a polarizing optical microscope, CB45 in the HAN geometry showed the capability of detection of as low as 10−10 g/mL for the protein standard bovine serum albumin (BSA). Moreover, the quantitation of the assay was fulfilled by both dielectric and light transmission measurements of the hybrid-aligned cholesteric CB45/R5011. The limit of detection of 7 × 10−10 g/mL was achieved by spectrometric analysis. To the best of our knowledge, this work is the first to demonstrate flexoelectric biosensing on the basis of flexoelectric polarization associated with giant flexoelectricity in CB7CB partially constituting the LC transducer.

P‐12.12: Development and Application of High Birefringence Liquid Crystal Materials

The development of new liquid crystal optoelectronic devices, including laser phase modulation, microwave and terahertz devices, requires liquid crystal materials with high birefringence. In this paper, three new molecular design strategies are proposed, including the introduction of olefin chain, lateral fluorine substitution and new ring core. Four new series of isothiocyanate liquid crystal compounds with high birefringence, low melting point and wide nematic temperature range were synthesized. Based on these new liquid crystal compounds, a liquid crystal mixture with nematic temperature range of ‐40~146 ºC and birefringence of 0.42 was developed. At 19 GHz, the new liquid crystal mixture shows excellent dielectric properties, with dielectric anisotropy of 1.28 and dielectric loss of 0.0087. The new liquid crystal mixture also has very low viscoelastic coefficient. The results at 1550nm and 60 ºC show that the response speed can reach 3.6 milliseconds with 2π phase modulation in the reflection mode.

Fluorination Improves the Electro-Optical Properties of Benzoxazole-Terminated Liquid Crystals in High Birefringence Liquid Crystal Mixtures: Experimental and Theoretical Investigations.

Aromatic heterocyclic liquid crystal (LC) materials have received much attention from LC chemists for their high birefringence and large dielectric anisotropy, yet few have reported their properties in LC mixtures. In this work, a series of fluorinated benzoxazole liquid crystal compounds were synthesized to evaluate their electro-optical properties in high birefringence LC mixtures, with the expectation of further establishing the theoretical basis and experimental evidence for their applications in LC photonics. Firstly, the effects of the lateral fluorine substituent positions on the molecular synthetic yield, mesomorphic and solubility properties were comparatively investigated. Afterwards, we focused on the fluorination effects on the core electro-optical properties, including birefringence, dielectric anisotropy and further investigation of the viscoelastic coefficient of high birefringence LC mixtures. Research results showed that the benzoxazole liquid crystal compounds possess low melting points, wide nematic phase intervals and good solubility by appropriate lateral fluorine substitution, which is beneficial to further improve the electro-optical properties of high birefringence LC mixtures. Meanwhile, the theoretical and experimental results corroborate each other to well reveal the structure-property relationship. This study demonstrates that fluorination would promote promising applications of benzoxazole-terminated liquid crystals in emerging LC optical devices.

Modulation of electro-optical properties of polymer-dispersed liquid crystals by multi-walled carbon nanotube/polymer nanocomposite fibres

ABSTRACT In this article, polymer-dispersed liquid crystal (PDLC) films were prepared from a mixture of prepolymer, liquid crystal and reticular nanofibre films containing multi-walled carbon nanotubes (MWCNT) by the polymerisation-induced phase separation (PIPS) method. By comparing the microstructure and electro-optical profiles of different contents of liquid crystals as well as monomer types, it was demonstrated that the pore size pairs of the polymer network can modify the electro-optical properties of PDLC. Different types of loaded multi-walled carbon nanotube reticular nanofibre films were introduced into the liquid crystal mixture specimens and the altered polymer network and electro-optical properties of these specimens were analysed using SEM, POM, TEM, and electro-optical curves. It was found that the electro-optical properties of PDLC were greatly improved and the resistance to ageing was also greatly enhanced by mesh nanofibre films doped with a certain amount of multi-walled carbon nanotubes. Therefore, the development of PDLC doped with loaded MWCNT reticular nanofibre films with faster response times and better electro-optical properties will greatly improve the promising technological applications of PDLC-based devices for optical windows, displays, energy storage and flexible devices.

Difluorovinyl Liquid Crystal Diluters Improve the Electro-Optical Properties of High-∆n Liquid Crystal Mixture for AR Displays.

A liquid crystal (LC) mixture in liquid crystal on silicon (LCoS) is the core material for augmented reality (AR) displays. However, a LC mixture with high birefringence (Δn) and large dielectric anisotropy (Δε) possesses high viscosity (γ1), which results in a slow response time of LCoS devices for AR displays. This work proposes to apply difluorovinyl-based LC diluters to fine balance the low viscosity, high ∆n, and large ∆ε of the LC mixture for a fast response time. Through studying their effects on the key electro-optical properties of a high-∆n LC mixture, it is found that doping these diluter molecules to a high-∆n LC mixture can decrease the viscoelastic coefficient (γ1/K11), increase ∆ε and the figure of merit, maintain a wide nematic phase temperature range, a high clearing point, and ∆n. It also means that these diluters could effectively regulate the relationship between ∆n, ∆ε, and γ1 in the LC mixtures to achieve a fine balance of various excellent properties and further improve the LC device's response time. The widespread applications of these liquid crystal diluters in emerging liquid crystal optical devices are foreseeable.

Temperature and frequency dependence on dielectric permittivity and electrical conductivity of recycled Liquid Crystals

The dielectric behavior and the electrical conductivity response of recycled nematic Liquid Crystals (LCs) were studied over a wide range of frequencies (0.1 to 106 Hz) and temperatures (100 to −20 °C) with a broadband dielectric spectroscopy technique. These LC mixtures were extracted from a total of 65700 End-Of-Life (EOL)-Liquid Crystals Displays (LCD) such as computers, tablets and TVs of various sizes, brands, and production years. After a stage of purification, the recycled LC blends seemed to possess similar physical properties as conventional nematic LCs. In this report, two types of anchoring of LC molecules, obtained with homeotropic or homogeneous alignment cells, were investigated. All dielectric data were analyzed with adapted models: Havriliak-Negami and Almond West formalisms for the frequency dependence of the data, as well as Arrhenius and Vogel-Fulcher-Tammann models for their temperature dependence. In this article, it is demonstrated that despite the wide variety of EOL-LCD devices used leading to a large number of LC molecules, the frequency and temperature evolution of the recorded spectra are comparable to those of commercial LC mixtures as reported in the literature. Therefore, their future reuse could be envisaged for display applications.

Photorefractive flexoelectric liquid crystal mixtures and their application to laser ultrasonics

A photorefractive effect of mixtures of flexoelectric liquid-crystal (flex LC) was investigated and applied to laser ultrasonics. Mixtures of flex LC, composed of smectic-C liquid crystals, photoconductive chiral compounds, and a sensitizer, are demonstrated to exhibit a large photorefractive effect. The experiments of a two-beam mixing with a photorefractive flexoelectric liquid crystal (PR-flex LC) show that a gain coefficient was measured as 1400 cm–1 and a response time was 960 microseconds, both with an applied electric field of 2.0 V/µm. The large gain and fast response are advantageous for remote ultrasound detection by using two-beam mixing with PR-flex LC. This remote sensing method can be used to probe the internal structure of an object or to measure the thickness of a plate object. The experimental results of acoustic time-of-flight in an aluminum (Al) plate are presented by using an adaptive two-beam interferometer with a PR-flex LC. A 3-D surface topology is shown by using laser ultrasonics with 2-D scanning of a test Al plate. With a fast response time in PR-flex LC, the system is not affected by vibrations in an industrial environment.