Tunable circularly polarized electroluminescence behaviors from chiral co-assembled conjugated liquid crystal polymers.

Chiral co-assembly strategy has proven effective in increasing the dissymmetry factor (gEL) of the emitting layers (EMLs) in circularly polarized organic light-emitting diodes (CP-OLEDs). Therefore, it is crucial to investigate the molecular structures that facilitate chiral co-assembly for further amplification of circularly polarized electroluminescence (CP-EL) signals. In this study, three types of achiral conjugated liquid crystal (LC) polymers (PFPh, PFNa and PFPy) and chiral binaphthyl-based polymer inducers (R/S-FO) were synthesized to construct corresponding chiral co-assemblies (R/S-FO)0.1-(PFPh/Na/Py)0.9 as EMLs for CP-OLEDs through strong intermolecular π-π stacking interactions. Interestingly, these resulting chiral co-assembled EMLs exhibited tunable CP-EL behaviors caused by the different conjugation linkers of LC polymers. Among them, the deep blue devices based on (R/S-FO)0.1-(PFNa)0.9 emitted the strongest CP-EL signals (|gEL| = 0.014, Lmax = 3039 cd m-2, CEmax = 1.16 cd A-1). It is attributed to the formation of ordered helical nanofibers facilitated by the excellent intermolecular compatibility due to the same naphthyl moieties in PFNa and R/S-FO. This study provides novel perspectives for developing high-performance CP-EL materials in chiral co-assembly systems.

Thin film resonant metasurface absorbers using patch-based arrays on liquid crystal polymer substrates for centimeter-wave applications.

This paper reports the design and development of thin-film resonant absorbers for narrowband and multiband operation in the frequency regions centered at 10 GHz. The structure of the resonant metasurface absorber (RMA) is based on a liquid crystal polymer (LCP) thin-film spacer with a copper patch array on the front surface and un-patterned copper film on the back surface of the LCP film. The design and simulation works were carried out using full-wave analysis of the RMA characteristics. The copper-based periodic patch array acts as a metasurface. The perfect RMA for a given LCP film thickness can be obtained through impedance optimization by adjustment of the dimensions of the lattice periods. The electric and magnetic field distributions were studied. The resonant film absorber based on a 100 µm thick LCP film has an electrical thickness of λ / 300 at 10 GHz. The experimental work was conducted using a narrowband RMA prototype consisting of 11 × 11 cells. The measured result of the resonant absorption is at 10.1 GHz, which is in close agreement with the design frequency of 10 GHz. For multiband functionality, double- and quad-band film resonant absorbers have been designed based on a coplanar supercell utilizing the superposition of the resonance effect. The LCP film-based absorbers have the potential to be used in EM shielding and sensing applications in centimeter-wave applications.

Fabrication of Single-Ion Conductors Based on Liquid Crystal Polymer Network for Quasi-Solid-State Lithium Ion Batteries.

Single-ion conductive polymer electrolytes can improve the safety of lithium ion batteries (LIBs) by increasing the lithium transference number (tLi+) and avoiding the growth of lithium dendrites. Meanwhile, the self-assembled ordered structure of liquid crystal polymer networks (LCNs) can provide specific channels for the ordered transport of Li ions. Herein, single-ion conductive nematic and cholesteric LCN electrolyte membranes (denoted as NLCN-Li and CLCN-Li) were successfully prepared. NLCN-Li was then coated on commercial Celgard 2325 while CLCN-Li was coated on poly(vinylidene fluoride-hexafluoropropylene) film, coupled with plasticizer, to make NLCN-Li/Cel and CLCN-Li/Pv quasi-solid-state electrolyte membranes, respectively. Their electrochemical properties were evaluated, and it was found that they possessed benign thermal stability and electrolyte/electrode compatibility, high tLi+ up to 0.98 and high electrochemical stability window up to 5.2 V. A small amount (0.5M) of extra Li salt added to the plasticizer could improve the ion conductivity from 1.79 × 10-5 to 5.04 × 10-4 S cm-1, while the tLi+ remained 0.85. The assembled LFP|Li batteries also exhibited excellent cycling and rate performances. The orderliness of the LCN layer played an important role in the distribution and movement of Li ions, thereby affecting the Li deposition and growth of Li dendrites. As the first report of nematic and cholesteric LCN single-ion conductors, this work sheds light on the design and fabrication of ordered quasi-solid-state electrolytes for high-performance and safe LIBs.

Multilayer UWB bandpass filter using liquid crystal polymer technology.

This proposed design presents a novel bandpass filter employing a Marchand balun to attain ultra-wideband (UWB) performance extending from 3.1 to 10.7 GHz with 6.8 GHz central frequency and 110% FBW. The UWB bandpass filter's fractional bandwidth can be tailored owing to the diverse input/output impedances of the planar Marchand balun. This adaptability is accomplished by connecting two planar Marchand baluns consecutively, leveraging the concepts of transversal filter ideas and multilayer LCP technology resulting in 0.3 dB and 12 dB insertion and return losses respectively. In-depth guidelines for the formulation and synthesis of the UWB bandpass filter are incorporated.

Preparation and Properties of Multi-Responsive Liquid Crystalline Poly(urethane-acrylate)s and Its Composite Membranes.

In this work, a kind of side chain liquid crystalline poly(urethane-acrylate)s was synthesized by free polymerization based on self-made liquid crystalline monomers, and a series of liquid crystalline polyurethane/shape memory polyurethane composite membranes were prepared by electrospinning. The synthesized liquid crystalline poly(urethane-acrylate)s have excellent thermal stability. Due to the regular arrangement of azobenzene on the side chains, polymers can rapidly undergo a photoinduced transition from trans-isomerism to cis-isomerism in THF solution and restore reversible configurational changes under visible light. The composite membranes prepared by electrospinning can also undergo photoinduced deformation within 6 s, and the deformation slowly returns under visible light. Meanwhile, the composites have shape memory, and after deformation caused by stretching, the membranes can quickly recover their original shape under thermal stimulation. These results indicate that the composites have triple response performances of photoinduced deformation, photo-, and thermal recovery.

Fully Aromatic Thermotropic Copolyesters Based on Vanillic, Hydroxybenzoic, and Hydroxybiphenylcarboxylic Acids.

Several series of new polymers were synthesized in this study: binary copolyesters of vanillic (VA) and 4'-hydroxybiphenyl-4-carboxylic (HBCA) acids, as well as ternary copolyesters additionally containing 4-hydroxybenzoic acid (HBA) and obtained via three different ways (in solution, in melt, and in solid state). The high values of logarithmic intrinsic viscosities and the insolubility of several samples proved their high molecular weights. It was found that the use of vanillic acid leads to the production of copolyesters with a relatively high glass transition temperature (~130 °C). Thermogravimetric analysis revealed that the onset of weight loss temperatures of ternary copolyesters occurred at 330-350 °C, and the temperature of 5% mass loss was in the range of 390-410 °C. Two-stage thermal destruction was observed for all aromatic copolyesters of vanillic acid: decomposition began with VA units at 420-480 °C, and then the decomposition of more heat-resistant units took place above 520 °C. The copolyesters were thermotropic and exhibited a typical nematic type of liquid crystalline order. The mechanical characteristics of the copolyesters were similar to those of semi-aromatic copolyesters, but they were much lower than the typical values for fully aromatic thermotropic polymers. Thus, vanillic acid is a mesogenic monomer suitable for the synthesis of thermotropic fully aromatic and semi-aromatic copolyesters, but the processing temperature must not exceed 280 °C.

Amplified Circularly Polarized Luminescence Behavior in Chiral Co-assembled Liquid Crystal Polymer Films via the Strategic Manipulation of Chiral Inducers.

One of the most important factors for the future application of circularly polarized luminescence (CPL) materials is their high dissymmetry factors (gem), and more and more studies are working tirelessly to focus on increasing the gem value. Herein, we chose an achiral liquid crystal polymer (LC-P) and two chiral binaphthyl-based inducers (R/S-3 and R/S-6) with different substitution positions (3,3' positions for R/S-3 and 6,6' positions for R/S-6) to construct chiral co-assemblies and explored their induced amplification CPL behaviors. Interestingly, after the thermal annealing treatment, this kind of chiral co-assembly (R/S-3)0.05-(LC-P)0.95 can emit a superior CPL signal (|gem| = 0.31 and λem = 424 nm), which achieves about 13-fold signal amplification in the spin-coated film, compared to (R/S-6)0.1-(LC-P)0.9 (|gem| = 0.023 and λem = 424 nm). This is because (R/S-3)0.05-(LC-P)0.95 could further co-assemble to form a more ordered arrangement LC state and generate regular helix nanofibers than that of (R/S-6)0.1-(LC-P)0.9. This work provides an efficient method for synthesizing high-quality CPL-active materials through the strategic manipulation of the structure of chiral binaphthyl-based inducers in chiral co-assembled LCP systems.

Achieving High-Performance Lithium-Sulfur Batteries by Modulating Li+ Desolvation Barrier with Liquid Crystal Polymers.

Lithium-sulfur (Li-S) batteries offer high theoretical capacity but are hindered by poor rate capability and cycling stability due to sluggish Li2S precipitation kinetics. Here a sulfonate-group-rich liquid crystal polymer (poly-2,2'-disulfonyl-4,4'-benzidine terephthalamide, PBDT) is designed and fabricated to accelerate Li2S precipitation by promoting the desolvation of Li+ from electrolyte. PBDT-modified separators are employed to assemble Li-S batteries, which deliver a remarkable rate capacity (761 mAh g-1 at 4 C) and cycling stability (500 cycles with an average decay rate of 0.088% per cycle at 0.5 C). A PBDT-based pouch cell even delivers an exceptional capacity of ≈1400 mAh g-1 and an areal capacity of ≈11 mAh cm-2 under lean-electrolyte and high-sulfur-loading condition, demonstrating promise for practical applications. Results of Raman spectra, molecular dynamic (MD) and density functional theory (DFT) calculations reveal that the abundant anionic sulfonate groups of PBDT aid in Li+ desolvation by attenuating Li+-solvent interactions and lowering the desolvation energy barrier. Plus, the polysulfide adsorption/catalysis is also excluded via electrostatic repulsion. This work elucidates the critical impact of Li+ desolvation on Li-S batteries and provides a new design direction for advanced Li-S batteries.

Circularly Polarized Luminescence of Cholesteric Liquid Crystal Polymer Networks with a Europium(III) Complex as an Emitter.

A coordination complex, Eu(C12C12dbm)3(phen), with strong emission and a high quantum yield (QY ∼ 51.9%) was synthesized. The EuIII complex, as a fluorescent emitter, was embedded in cholesteric liquid crystal polymer networks (CLCNs). A series of free-standing EuIII-CLCN films were obtained, generating a typical sharp emission band corresponding to the EuIII complex. Tunable handedness of circularly polarized luminescence (CPL) with high |glum| values (up to 0.63) was observed. A series of CPL-active CLCN-coated PET films were also prepared (|glum| values up to 0.63), which can be used for large-area preparations. Moreover, by stacking an emitter-embedded PMMA layer and a CLCN layer, a composite system was built, and a large |glum| value (∼1.42) was achieved. Fluorescence patterns were prepared, and distinct images of CLCN films were recognized under both daylight and UV light. This work not only demonstrated that coordination compounds could be incorporated with CLCN films to prepare CPL-active materials with high |glum| values but also provided a new perspective for emissive CLCN materials used for anticounterfeiting and encryption.

Photo- and Humidity-Responsive Liquid Crystal Copolymer Actuators Fabricated via Vapor-Assisted Alignment.

Deformable liquid crystal polymers (LCPs) driven by more than one external stimulus have received extensive attention in fields ranging from multifunctional soft robots to bionic actuators. Combining responsive liquid crystal with nonmesogenic responsive groups within polymer offers a versatile way to obtain multiresponsive LCPs. However, the incorporation of nonmesogenic responsive groups causes interruption in the assembly of mesogens and brings a challenge to the alignment of LCPs. Herein, a new method is put forward to facilitate uniform mesogen alignment by exerting water vapor in the film preparation process. Using this method, vapor-assisted alignment, the homeotropic alignment of azobenzene mesogens is achieved in a copolymer containing nonmesogenic poly(ethylene glycol) (PEG). The obtained copolymer films present photodeformation brought by azobenzene isomerization and humidity-responsive deformation resulting from the asymmetric swelling of film surfaces. The dual-responsive smart "blinds" and bionic flower actuators are fabricated to demonstrate the integration of the two different stimuli. This work is anticipated to provide a feasible alignment method for multiresponsive LCPs, showing the potential applications in soft robots, sensors, and biomimetic devices.

Dynamic Shape Change of Liquid Crystal Polymer Based on An Order-Order Phase Transition.

Liquid crystal actuators conventionally undergo shape changes across an order-disorder phase transition between liquid crystal (LC) and isotropic phases. In this study, we introduce an innovative Liquid Crystal Polymer (LCP) actuator harnessing an order-order LC phase transition mechanism. The LCP film is easily stretchable within the LC phase, facilitated by the π-π stacking of phenyl groups serving as robust physical crosslinking points, and thereby transforms to a stable monodomain structure. The resultant monodomain LCP actuator shows a distinctive reversible dynamic shape change, exhibiting extension followed by contraction along the LC director on cooling. The extension is propelled by the reversible smectic C to smectic A phase transition, and the contraction is attributed to the re-entry to the smectic C phase from smectic A phase. Thermal annealing temperature determines this peculiar dynamic shape change, which occurs during both heating and cooling processes. This pivotal attribute finds manifestation in gripper and flower-shaped actuators, adeptly executing grabbing and releasing as well as blooming and closure motions within a single thermal stimulation. In essence, our study introduces an innovative approach to the realm of LCP actuators, ushering in a new avenue for the design and fabrication of versatile and dynamically responsive LCP actuators.

Mechanical Actuation via Homeomorphic Transformations of Topological Solitons within Polymer Coatings.

Topological solitons are currently under investigation for their exotic properties, especially in nonlinear physics, optics, and material sciences. However, challenges of robust generation and limited stability over time have hindered their practical uses. To address this issue, an approach is developed to form structured arrays of solitons in films of polymerizable liquid crystals. Their complex molecular architecture is preserved by in situ photopolymerization forming a stable liquid crystal network. Most excitingly, their properties are advanced to include responsiveness functions. When thermally actuated, these topological solitons mediate the reconfiguration of surface topographies. Complex shape changes occur depending on the intrinsic complex spatial distribution of the director, which may even lead to full shape inversion and topographical changes as high as ≈40% of the initial thickness. Conversely, the shape changes provide information on the initial director profile, which is consistent with the mathematical model. The soliton-containing polymer coatings are applicable in multiple domains, ranging from tunable optics to haptics, and from shape-coupled sensing systems to temperature-coupled heat management.

Universal Strategy for Inorganic Nanoparticle Incorporation into Mesoporous Liquid Crystal Polymer Particles.

Developing inorganic-organic composite polymers necessitates a new strategy for effectively controlling shape and optical properties while accommodating guest materials, as conventional polymers primarily act as  carriers that transport inorganic substances. Here, a universal approach is introduced utilizing mesoporous liquid crystal polymer particles (MLPs) to fabricate inorganic-organic composites. By leveraging the liquid crystal phase, morphology and optical properties are precisely controlled through the molecular-level arrangement of the host, here monomers. The controlled host material allows the synthesis of inorganic particles within the matrix or accommodation of presynthesized nano-inorganic particles, all while preserving the intrinsic properties of the host material. This composite material surpasses the functional capabilities of the polymer alone by sequentially integrating one or more inorganic materials, allowing for the incorporation of multiple functionalities within a single polymer particle. Furthermore, this approach effectively mitigates the drawbacks associated with guest materials resulting in a substantial enhancement of composite performance. The presented approach is anticipated to hold immense potential for various applications in optoelectronics, catalysis, and biosensing, addressing the evolving demands of the society.

Harnessing Smectic Ordering for Electric-Field-Driven Guided-Growth of Surface Topography in a Liquid Crystal Polymer.

The guided-growth strategy has been widely explored and proved its efficacy in fabricating surface micro/nanostructures in a variety of systems. However, soft materials like polymers are much less investigated partly due to the lack of strong internal driving mechanisms. Herein, the possibility of utilizing liquid crystal (LC) ordering of smectic liquid crystal polymers (LCPs) to induce guided growth of surface topography during the formation of electrohydrodynamic (EHD) patterns is demonstrated. In a two-stage growth, regular stripes are first found to selectively emerge from the homogeneously aligned region of an initially flat LCP film, and then extend neatly along the normal direction of the boundary line between homogeneous and homeotropic alignments. The stripes can maintain their directions for quite a distance before deviating. Coupled with the advanced tools for controlling LC alignment, intricate surface topographies can be produced in LCP films starting from relatively simple designs. The regularity of grown pattern is determined by the LC ordering of the polymer material, and influenced by conditions of EHD growth. The proposed approach provides new opportunities to employ LCPs in optical and electrical applications.

Synthesis and Properties of Room-Temperature Phosphorescent Liquid Crystal Copolymers with Linearly Polarized Luminescence Characteristic.

Room-temperature phosphorescent (RTP) liquid crystal materials have garnered considerable attention because of their significant applications in organic light emitting diodes, polarized light emitting materials, and so forth. How to efficiently synthesize pure organic RTP liquid crystals and regulate their performance is of great significance. In this article, we propose a simple and feasible method to synthesize RTP liquid crystals and manipulate their properties through copolymerization. We constructed RTP liquid crystal copolymers by copolymerizing a phosphorescent monomer bearing biphenyl mesogen with a phosphorescent monomer bearing a dibenzofuran chromophore. All the synthesized copolymers show a liquid crystal property because of the introduction of biphenyl mesogen. Meanwhile, by changing the composition of copolymers, it is possible to regulate their RTP performance, including luminescence color and lifetime. As the content of the PMDFM0C component in copolymers increases, the phosphorescence lifetime gradually increases. For poly(MDFM0C(0.46)-co-MBi18C(0.54)), the phosphorescence lifetime can reach 463.0 ms. Moreover, the phosphorescence color of the PMDFM0C component in copolymers changes with the copolymer composition, which can induce variable room-temperature phosphorescence. In addition, when oriented, liquid crystal copolymer films can emit linearly polarized fluorescence and linearly polarized phosphorescence. The linearly polarized phosphorescence dichroic ratio and polarization ratio values of the oriented poly(MDFM0C(0.46)-co-MBi18C(0.54)) film are 3.33 and 0.50, respectively.

Steerable and Agile Light-Fueled Rolling Locomotors by Curvature-Engineered Torsional Torque.

On-demand photo-steerable amphibious rolling motions are generated by the structural engineering of monolithic soft locomotors. Photo-morphogenesis of azobenzene-functionalized liquid crystal polymer networks (azo-LCNs) is designed from spiral ribbon to helicoid helices, employing a 270° super-twisted nematic molecular geometry with aspect ratio variations of azo-LCN strips. Unlike the intermittent and biased rolling of spiral ribbon azo-LCNs with center-of-mass shifting, the axial torsional torque of helicoid azo-LCNs enables continuous and straight rolling at high rotation rates (≈720 rpm). Furthermore, center-tapered helicoid structures with wide edges are introduced for effectively accelerating photo-motilities while maintaining directional controllability. Irrespective of surface conditions, the photo-induced rotational torque of center-tapered helicoid azo-LCNs can be transferred to interacting surfaces, as manifested by steep slope climbing and paddle-like swimming multimodal motilities. Finally, the authors demonstrate continuous curvilinear guidance of soft locomotors, bypassing obstacles and reaching desired destinations through real-time on-demand photo-steering.

Tribological and Mechanical Applications of Liquid-Crystal-Polymer-Modified Carbon-Fiber-Reinforced Polyamide-Polyurethane Composites.

An aromatic copolyester liquid crystal polymer (LCP) was introduced into carbon-fiber-reinforced polyamide-polyurethane (CF/PA-PU) composites through melt blending to improve the tribological properties of the composites. The effects of LCP on the mechanical, processing, and thermal properties of CF/PA-PU composites were compared to those of commonly-used graphite (Gr). The results showed that at 5 wt.% LCP content, the coefficient of friction (COF) was decreased by 16.06%, and the wear rate by 32.22% in the LCP/CF/PA-PU composite compared to the CF/PA-PU composite. Furthermore, using LCP instead of Gr showed significantly improved mechanical properties and reduced processing viscosity. The tensile strength of 5%LCP/CF/PA-PU composite could reach 99.08 MPa, while the equilibrium torque was reduced, being 26.85% higher and 18.37% lower than those of CF/PA-PU composite, respectively. The thermal stability of LCP/CF/PA-PU composites was also enhanced. The addition of 5 wt.% LCP to CF/PA-PU composite increased the initial decomposition temperature by 14.19% compared to CF/PA-PU. In sharp contrast, the addition of Gr increased equilibrium torque and actual processing temperature leading to processing difficulties and instability. This approach offers a novel strategy for tribological applications and tackles the problem of high viscosity in CF/PA-PU composites.

Geometry Controlled Oscillations in Liquid Crystal Polymer Films Triggered by Thermal Feedback.

Light-induced oscillatory behavior of liquid crystal polymer network (LCN) films has been demonstrated by several researchers in the past decade. Similarly, oscillations in LCN films under constant thermal stimulus have been reported recently, although the mechanism and the factors that govern the oscillatory behavior are not well understood. In this work, we study the dynamics of self-sustained oscillations exhibited by LCN films under a constant thermal stimulus through experiments and simulations. Geometrically asymmetric films such as a right triangle and an equilateral triangle are obtained from a twisted nematic square film. A multiphysics computational framework using the finite element method is developed to simulate the oscillatory behavior of the LCN films kept on a hot plate. The framework accounts for a coupling between heat transfer and mechanical deformations during the oscillations. Small temperature fluctuations (≈ 1 °C) coupled with gravity induced torque are shown to drive the oscillatory behavior at a specific plate temperature. We show for the first time that self-sustained oscillations can also be achieved in symmetric shapes, such as square films, by creating a thickness tapering between two opposite edges. The frequency of the oscillations is found to be in the range of 0.5 to 2.5 Hz for different geometries studied. The oscillation temperature depends on the mean thickness, size, and thickness profile of the films. As a possible application, we demonstrate a thermally actuated optical chopper using the oscillatory response of the films.

Non-volatile optical memory based on cooperative orientation switching: improvement of recording speed and contrast by utilizing out-of-plane orientation mode.

Herein, we report a novel strategy toward non-volatile optical memory with high-contrast, high-speed recording, and non-destructive readout capability based on the cooperative out-of-plane orientation of a fluorescent dye doped into azobenzene liquid crystalline polymer film. By employing the out-of-plane orientation switching upon irradiation with UV light and thermal heating, high-contrast turn-on fluorescence switching was successfully achieved and the optical recording was demonstrated with non-destructive fluorescence readout capability. Furthermore, the recording speed and the fluorescence on/off contrast in the present system were dramatically improved compared to the previous in-plane orientation mode.

Perspiring Soft Robotics Skin Constituted by Dynamic Polarity-Switching Porous Liquid Crystal Membrane.

Secretion of functional fluids is essential for affecting surface properties in ecosystems. The existing polymer membranes that mimic human skin functions are limited to secreting, either apolar or polar, liquid. However, the development of membranes that grant exchange liquid with different polarities remains a grand challenge. This process is prohibited by the mismatch of the polarity between the carrier polymer and the loaded liquid. To conquer this limitation, an innovative strategy is reported to dynamically switch the polarity of the porous membrane, thereby empowering the exchange of apolar liquid with polar liquid and vice versa. This approach incorporates a benzoic acid derivative into the original apolar polymer network. The benzoic acid dimerizes and forms hydrogen bonds, which supports the molecular alignment, but can be broken into the ionic state when subjected to alkaline treatment, changing the polarity of themembrane. Consequently, the apolar liquid can be replaced with a more polar one. This polar liquid is ejected upon safe-dose UV illumination from the membrane. Reabsorption occurs on demand by illumination of visible light or when left in contact with the membrane, spontaneously in the dark. Based on this, the consumed membrane is replenished with the same or different exchanging liquid.