Isotropic Phase Transition Temperature Research Articles

Broad temperature range ferrielectric liquid crystal: Temperature dependencies of dielectric and electro-optical properties

Broad temperature range ferrielectric liquid crystal mixture FerriLCM-1 was previously developed in 2022 (Pozhidaev et al. 2022). In that work dielectric and electro-optical properties of the mixture were studied at room temperature. Electrically induced birefringence index reached 0.01 at a wavelength of 532 nm with response times of 300 μs. In this paper we continue the FerriLCM-1 properties investigation in a wide temperature range from the room ones till the isotropic phase transition temperature. It is found that one of the critical electric fields is almost temperature independent, while the Kerr coefficient of quadratic electro-optical effect in deformed helix ferroelectric (DHF) mode grows with temperature increase. This leads to an increase in the depth of phase modulation. Another critical electric field decreases smoothly with temperature rising. At 47–50 °C two critical electric fields merge, while temperature dependencies of all other dielectric and electro-optical parameters of the mixture are continuous and smooth functions. At about 50 °C the maximum electrically induced birefringence in DHF-mode is ΔneffE=0.022 under the applied electric field E=0.4 V/μm and with 80 μs response time. FerriLCM-1 mixture operating in the DHF-mode exhibits a giant Kerr coefficient of 1700 nm/V2 (or even up to 2900 nm/V2 at λ=400nm) at the temperature of 85 °C combined with a 50 μs response time. This is the highest value of Kkerr coefficient among liquid crystals. All these properties make ferrielectric liquid crystal mixture FerriLCM-1 suitable for solving various problems of phase modulation of light and use in low-voltage devices.

Enhanced Orientation of Liquid Crystals Inside Micropores of Metal-Organic Frameworks Having Thermoresponsivity.

With the aim of controlling the orientation of liquid crystals (LCs) toward realizing external stimuli-responsive materials with tunable functionalities, we synthesized a composite of LCs and metal-organic frameworks (MOFs) by filling LCs into the pores of MOFs (LC@MOFs) for the first time. The included LCs interact with the MOFs through coordination bonds between the cyano groups of the LCs and the metal ions of the MOFs, enabling the orientation of the LC molecules inside the pores of the MOFs and the realization of birefringence of LC@MOFs. The three-dimensional nanometer interstice frameworks maintained the LC orientation even at temperatures much higher than the isotropic phase transition temperature of bulk LCs. Furthermore, the orientational state changed upon heating or cooling, inducing temperature-dependent birefringence. This study provides a new approach to the development of stimuli-responsive optical materials and stimuli-responsive MOFs.

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.

Amphiphilic Liquid Crystalline Polymer Micelles That Exhibit a Phase Transition at Body Temperature

Liquid crystalline polymers (LCPs), which exhibit unique structures and properties intermediate between those of liquids and solids, are widely utilized as functional and advanced materials for fabricating optical devices and high-performance fibers. This utility stems from their ability to abruptly change their organized structures and mobilities at their liquid crystalline-isotropic phase transition temperatures, similar to the properties of biological membranes. Despite these numerous potential applications of LCPs, no study on their use in medical applications such as drug delivery has been reported. In the present study, we synthesized amphiphilic side-chain LCPs (LCP-g-OEGs, where OEG is oligo(ethylene glycol)) for medical applications, where the LCP-g-OEGs undergo a nematic-isotropic phase transition at body temperature. The LCP-g-OEGs formed micelles with a diameter of approximately 130 nm in aqueous media. The micelles were stable and did not dissociate in aqueous media even when the temperature exceeded the nematic-isotropic phase transition temperature (TNI). Although the release of a dye as a model drug from micelles was suppressed at temperatures lower than TNI, their dye release was drastically enhanced at temperatures higher than TNI. The LCP-g-OEG micelles regulated dye release reversibly in accordance with stepwise changes in temperature, without undergoing dissociation, differing from the behavior of standard temperature-responsive micelles. The temperature-responsive dye release behavior is induced by dramatic changes in their well-organized and dynamic structures as a result of the nematic-isotropic phase transition. These results demonstrate that the LCP-g-OEG micelles have a lot of medical applications as reversibly stimuli-responsive drug carriers.

Toward In Silico Design of Highly Tunable Liquid Crystal Elastomers

In this work, a two-component acrylate liquid crystal elastomer, with varying composition and templating phase, is synthesized in the laboratory and investigated in parallel using atomistic molecular dynamics simulations. The anisotropic nature of both the mono- and bifunctional acrylates used in this study enables a large tunability in the compositional range while still retaining liquid crystalline properties in the final elastomer. The use of simulations allows important evaluation and comparison of physical properties such as glass transition temperature, nematic to isotropic phase transition temperature, and order parameter. The dependence of physical properties (glass transition, nematic to isotropic transition, order parameter, coefficient of thermal expansion, and mechanical properties) is established as a function of chemical composition, showing a high degree of tunability. Interestingly, the templating phase (nematic or isotropic) is also shown to impact the subsequent elastomer properties, with excellent agreement shown here between experiments and simulations. The in silico approach to polymerization, coupled with excellent comparison with the experimental system, represents a new methodology for the targeted design of liquid crystal elastomers with specific physical properties.

Carbon Nanotubes Blended Nematic Liquid Crystal for Display and Electro-Optical Applications

In this paper, we investigate a commercial nematic liquid crystal (LC) mixture namely E7 dispersed with small concentrations of multi-walled carbon nanotubes (MWCNTs). The dielectric and electro-optical characterizations have been carried out in the homogeneously and vertically aligned LC cells. The electro-optical response of LC molecules has been enhanced by 60% after the addition of MWCNTs, which is attributed to the reduced rotational viscosity in the composites. MWCNTs act like barricades for ionic impurities by reducing them up to ∼34.3% within the dispersion limit of 0.05 wt%. The nematic–isotropic phase transition temperature (TNI) of the E7 LC has also been shifted towards the higher temperature, resulting in a more ordered nematic phase. The enhanced birefringence and orientational order parameter in the LC-MWCNTs are attributed to π-π electron stacking between the LC molecules and the MWCNTs. The outlined merits of the LC-MWCNTs composites evince their suitability for ultrafast nematic-based electro-optical devices.

Thermal- and photo-responsive liquid crystalline elastomers fabricated using tung oil-based azobenzene

Azobenzene-based liquid crystalline elastomers with dynamic ester bonds exhibit high thermal- and photo-responsive properties. However, there are a few studies that focus on photo-induced and thermal-induced behaviors separately. Herein, novel thermal- and photo-responsive LCEs containing dynamic ester bonds were prepared from 4,4’-diglycidyloxy-azobenzene, sebacic acid and tung oil-based azobenzene, which acted as a side chain. The dynamic transesterification reactions on the network structure were confirmed through stress relaxation. The photo-induced and thermal-induced behaviors were also investigated. The monodomain LCEs film was obtained by uniaxial stretching at a temperature above the smectic–isotropic phase transition temperature (Ti ∼82 °C). Due to the breakage and formation of dynamic ester bonds and the order-disorder smectic phase transition caused by heat and the trans-cis isomerization of azobenzene mesogens, the thermal-induced stress of the monodomain LCEs film reached ∼3 MPa. The LCEs film also exhibited thermal-induced shape-memory properties. Investigation of its photo-responsive behavior further demonstrated that the monodomain LCEs film generated stress of ∼1.1 MPa while exhibited photo-induced deformation due to the trans-cis isomerization of azobenzene mesogens upon irradiation with 365 nm UV light. Finally, we observed that the monodomain LCEs film could undergo quickly photo-induced deformation and could be processed into a photo-driven gripper.

Reprogrammable 3D Liquid‐Crystalline Actuators with Precisely Controllable Stepwise Actuation

Liquid‐crystalline elastomers (LCEs) are considered ideal soft actuator materials for a wide range of applications, especially the thriving soft robotics. However, 3D LCE actuators capable of precisely controllable stepwise actuation, which can enhance functionality and versatility of LCE robots for multifarious complicated applications, are still in urgent need for the reported LCE actuators mainly exploit the one‐step actuation upon the liquid‐crystallin (LC)‐isotropic phase transition temperature (Ti). Herein, a catalyst‐free LC‐vitrimer actuator with supercritical behavior is designed, which can perform precisely controllable stepwise actuation with extraordinary shape stability over a broad temperature range of about 70 °C. Moreover, supercritical behavior enables the actuator to be used in nematic phase, imparting the actuator with some extra advantages, such as higher mechanical strength and actuation stability, over the one used above Ti. Furthermore, the LCE can be reprogrammable into arbitrary 3D actuators, which can further be integrated into single‐material actuators with complex stepwise actuation, offering a generalized strategy of LCE actuators for sophisticated practical soft robots.

Microwave-Assisted Synthesis of Mushrooms Like MWCNT/SiO2@ZnO Nanocomposite: Influence on Nematic Liquid Crystal E7 and Highly Effective Photocatalytic Activity in Degradation of Methyl Blue

Mostly-uniform spherical mushrooms like MWCNT/SiO2@ZnO nanocomposite was synthesized under microwave power and characterized using TEM, XRD, EDX, TG/DTA and FT-IR techniques. The modified chemical process was used in three steps for the synthesis of the nanocomposite. Having a nano-capillary structure of MWCNT as nano-core, chemically and physically inert silica cover are a vital backbone for ZnO, which is a semiconductor. Because of the excellent chemical and physical properties of MWCNT/SiO2@ZnO nanocomposite, it has shown unique catalytic properties in the photocatalytic degradation of methyl blue. Approximately all of the methyl blue was degraded in water in 10 min. under sun-light and after 60 min., rarely left from dye in the water. The thermal and electrical behavior of mushrooms like nanocomposite doped E7 was investigated. According to the obtained results, the nematic to isotropic phase transition temperature of sample enhanced with nanocomposite dispersion and threshold voltage of mushroom like nanocomposite doped Nematic Liquid Crystal E7 decreased was founded.

Electrical properties of the octyl cyanobiphenyl nematic liquid crystal dispersed with graphene oxide

Graphene oxide (GO) with different concentrations was dispersed to pristine octyl cyanobiphenyl nematic liquid crystal. The characteristics of the used GO were investigated with X-Ray diffraction (XRD), scanning electron microscopy (SEM) and UV–Vis spectroscopy. Also the bandgap values of GO were calculated. The impact of doping concentration on the thermal and electrical properties of prepared samples was investigated. The phase transition temperatures of samples were studied by differential scanning calorimeter. The isotropic phase transition temperature has decreased by the addition of graphene oxide ratio in samples. The electrical properties of the samples have been examined by measuring dielectric permittivity, capacitance and impedance of samples with an impedance analyzer. Also, electrical behaviors of pure and GO-dispersed samples under bias voltage were studied. The relaxation frequencies of specimens were obtained. The dielectric anisotropy and relaxation frequency also increased due to the presence of graphene oxide flakes. The dielectric permittivity $${\varepsilon }^{^{\prime}}$$ of GO-dispersed samples enhanced under the bias voltage was revealed.

Influence of carbon quantum dots on electro–optical performance of nematic liquid crystal

A simple synthesis of carbon quantum dots (CQDs) from green sources has attracted increasing attention nowadays. Here we report the synthesis of water-soluble fluorescent carbon quantum dots from mandarin juice by hydrothermal method. When excited at 364 nm, CQDs give maximum fluorescence at 462 nm. As verified from Transmission Electron Microscopy, obtained CQDs were very small, with an average diameter of 2.37 ± 0.42 nm. These very small-sized nanoparticles were dispersed to nematic liquid crystal mixture E7. As is known, particle size is a significant parameter for nanoparticle dispersed liquid crystal applications. The threshold voltage of pure and CQDs doped liquid crystals was derived from dielectric spectroscopy measurements, and it was observed that the threshold voltage increased with the increasing CQDs doping concentration. The nematic to the isotropic phase transition temperature of samples was investigated with DSC thermograms and POM. The phase transition temperatures gradually decreasing with increasing CQDs doping concentration were revealed.

Textural and electro-optical study of a room temperature nematic liquid crystal 4̍-pentyl-4-biphenylcarbonitrile doped with metal oxide nanowires in planar and in-plane switching cell configurations

ABSTRACT This work shows the doping effect of metal oxide nanowires (alumina nanowires) on the textural and electro-optical characteristics of nematic liquid crystal (5CB) in planar and in-plane switching (IPS) cell configurations. Results indicate the increase in nematic to isotropic phase transition temperature after doping in both planar and IPS cells. A decrease in threshold voltage in addition to increase in contrast ratio, birefringence, and band gap energy was observed after doping with alumina nanowires in both types of cells. Overall analysis shows that IPS cell configuration has more improved threshold voltage and contrast ratio in addition to decrease in birefringence and transmission intensity, as compared to planar cell configuration. No effect of cell configuration was observed on energy band gap and found same value for both planar and IPS cell configurations, as energy band gap is a material specific property.

Spectroscopic, dielectric and nonlinear current–voltage characterization of a hydrogen-bonded liquid crystalline compound influenced via graphitic nanoflakes: An equilibrium between the experimental and theoretical studies

Herein, we investigate a hydrogen-bonded liquid crystal compound, namely 4-(Heptyloxy) benzoic acid (7OBA), and its composites by dispersing Graphene and reduced graphene oxide (rGO) flakes into an optimized concentration. The pristine 7OBA and its composites are characterized by different instrumental techniques like polarized optical microscopy, differential scanning calorimetry (DSC), dielectric, UV-visible, and Fourier-transform infrared (FTIR) spectroscopy. DSC thermograms of the 7OBA composites evince the down-shift in the smectic C−nematic and nematic−isotropic phase transition temperatures. The polarized optical micrographs (POMs) of composites reveal the homogeneous distribution of graphene and rGO flakes in the 7OBA compound without any aggregation. The π-π* transitions in phenyl ring of 7OBA compound and π-π* transitions in CC bonds of graphitic materials are superimposed to each other providing an enhanced UV absorbance nearly at 255 nm for the composites. The presence of graphene and rGO enhances the tan δ and electrical conductivity of the composites, whereas dielectric anisotropy, Δϵ, reduces as a function of temperature in comparison to the pristine 7OBA compound. The sign inversion of Δϵ has been observed for the 7OBA/rGO composite which has been explained via dipole−dipole interactions. The I−V behavior of the pristine 7OBA compound yields the ohmic I−V curve with a non-zero current at 0 V attributing to the pseudocapacitance effect, whereas, after the dispersion of graphene and rGO flakes, nonlinear diode like I−V curves having a hundred times larger conduction current were obtained. Furthermore, the molecular interactions have been analyzed by the FTIR which confirms the formation of hydrogen bonding in the 7OBA/rGO composite. At last, these experimental findings are compared with the simulated results by DFT. The experimental and theoretical simulations are commensurable to each other. The studied composites have shown their vital applications in nonlinear electronics.

Liquid-crystalline behavior and ferroelectric property of viologen-based ionic liquid crystals

Viologen-based ionic liquid crystals (VILCs) bearing viologen cations and various counter anions (Br−1, CsO−, PF6−1, CF3COO−, TsO−, and BF4−1) were prepared using cholesterol, bromobutanoyl chloride, bipyridine and different anionic salts. The chemical structures and the SmC⁎ phase were identified, and the effect of different anions on both liquid crystalline behavior and ferroelectric property was investigated. Melting temperatures of these VILCs with different anions were similar, but SmC*-isotropic phase transition temperatures were elevated in sequence of TsO−, CsO−, CF3COO−, PF6−, Br− and BF4−. They showed different polarization values changed from −9.1 to 9 nC/cm2 as the electric field changed from −10 V to 10 V. The ferroelectric parameters ±Ec, ±Pr, and ±Ps changed a little due to the different counter anions. The VILC with BF4− anion showed the optimal ferroelectric properties in these VILCs series. Unlike conventional ferroelectric liquid crystals, the VILCs displayed asymmetry in the hysteresis loops due to formation of double electrical layers in the ordered SmC⁎ phase.

A cholesteric liquid crystal device having stable uniform lying helix structure

A cholesteric liquid crystal device having the uniform lying helix (ULH) structure shows stable and reversible characteristics and it has been demonstrated for the analogue modulation in 10 micro-second response time at room temperature. The device comprises a polymer-free chiral nematic liquid crystal mixture and the photoalignment layer is irradiated by the UV light to cause a preferred orientation of the liquid crystal. The ULH structure is obtained by cooling the liquid crystal mixture from the isotropic phase transition temperature in the presence of electric field. On the electrical and thermal cycling, no noticeable hysteresis has been observed. In addition, the tilt angle and response time have been measured in good agreement with Meyer's theory on the flexoelectric effect in liquid crystals.

Electro-Optical and Dielectric Responses of ZnO Nanoparticles Doped Nematic Liquid Crystal in In-Plane Switching (IPS) Mode

In present work, electro-optical and dielectric characteristics of ZnO nanoparticles (NPs) doped nematic liquid crystal mixture are studied in In-Plane Switching (IPS) mode. Effect of doping of ZnO nanoparticles on phase transition behaviour, threshold and operating voltage were studied. Polarising Optical Microscope (POM) study confirms a reduction in nematic to isotropic (N-I) phase transition temperature after doping of ZnO NPs. A decrease in threshold and operating voltages with better contrast ratio was observed. Further, a significant change in dielectric behaviour of NLC was also perceived in doped sample.

Improvement in electro-optical and dielectric characteristics of ZnO nanoparticles dispersed in a nematic liquid crystal mixture

Reported herein is the effect of dispersion of a fixed amount of 0.5% (wt/wt) ZnO nanoparticles (NPs) in a nematic (E7) liquid crystal (LC) mixture. Dispersion of ZnO NPs results in a significant improvement in electro-optical and dielectric parameters of the nematic mixture. Comparative analysis of undoped and NP-dispersed samples shows a reduced threshold voltage with better transmittance without compromising dielectric permittivity characteristics. In addition, an increase in the contrast ratio, birefringence, alternating-current conductivity and band gap was observed after dispersion of ZnO NPs in LCs. A polarized optical microscopic study of the NP-dispersed sample substantiates a slight increase in nematic–isotropic phase transition temperature of LCs.

Thermal and electro-optic properties of graphene oxide-doped hexylcyanobiphenyl liquid crystal

Hexylcyanobiphenyl liquid crystal was doped with graphene oxide at ratios %0.25GO, %0.5GO, %1GO and %2GO, and the change in physical properties of pristine and the doped liquid crystals has been investigated. The phase transitions of prepared samples were studied by differential scanning calorimeter and polarized optical microscopy. The differential scanning calorimeter and polarized optical microscopy results are in good agreement when examining the nematic–isotropic liquid phase transition temperatures of the hexylcyanobiphenyl. The liquid crystal texture images obtained with polarized optical microscopy reveals that thermal stability of sample changed with graphene oxide concentration, i.e., increased with graphene oxide concentration. Impedance, capacitance, conductivity and real and imaginary dielectric constants of the pure and doped liquid crystals were obtained depending on frequency and voltage at the room temperature by using impedance analyzer. These electrical properties of the pure and the graphene oxide-doped samples showed an increase with increasing the graphene oxide ratio. The voltage-dependent light transmittance experiment revealed that threshold voltage of LC cells decreased for %0.25GO- and % 1GO-dispersed samples, but it was increased at %0.5GO- and %2GO-dispersed samples.

Molecular-weight dependence of phase structure and viscosity in a liquid crystalline polyester with strong π–π interaction

ABSTRACTIn this article, the molecular-weight dependence of the phase structure, rheological behaviour and thermal stability of a main-chain liquid crystalline polyester (PBDPS) with strong π–π interaction was investigated in details by differential scanning calorimetry, polarising optical microscopy, wide-angle X-ray diffraction, dynamic oscillatory rheological measurements and thermogravimetric analysis. While the molecular weight of PBDPS is 5.2k, it shows smectic B and smectic A phases prior to isotropic phase. With increasing molecular weight, smectic B phase of PBDPS gradually disappeared. Moreover, the smecitc B to smectic A (Tlc) and smectic A to isotropic (Ti) phase transition temperatures decreased as increased molecular weight. The rheology results suggested that fluid type of PBDPSs changed from Newtonian fluid to pseudo-plastic fluid as the molecular weight of PBDPS increased. In addition, the zero-shear viscosity (η0) of PBDPS showed a power law relationship () with molecular weight of PBDPS. All the PBDPSs showed good thermal stability with an initial decomposition temperature higher than 360°C.

Synergistic effect of non-covalent interaction in colloidal nematic liquid crystal doped with magnetic functionalized single-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs), CNT@Fe3O4, and Fe3O4 nanocomposites were doped to eutectic uniaxial nematic liquid crystal (NLC's) (E5CN7) to improve physiochemical properties such as phase transition temperature, activation energy (Ea), dielectric anisotropy, and electro-optical properties. The thermal study of nematic phase shows a decrease in the nematic to isotropic phase transition temperature as CNT is doped. However, higher doping concentration of CNTs leads to the further increase in transition temperature. The anchoring effect or π-π interaction plays a key role in N-I phase transition. The functionalization of SWCNTs with Fe3O4 diminishes the CNT aggregation while the magnetic susceptibility is increased. The functionalized CNT doping to NLC's decrease significantly the phase transition temperature compared to doping of non-functionalized CNTs. Attractive interaction between guest and host molecules by magnetic and geometry effect increased the enthalpy and entropy of phase transition in the SWCNT@Fe3O4 sample compared to non-functionalized CNT doped system. Also, the Ea values are decreased as SWCNT@Fe3O4 is doped to pure E5CN7. The difference of N-I phase transition temperature was observed in Fe3O4 and CNT@Fe3O4 compared to SWCNT doped systems. Finally, dielectric anisotropy was increased in the doped system compared to pure NLC.