Polymer Network Liquid Crystal Research Articles

Liquid Crystal Polymer‐Based Soft Robots

Soft robots outperform the conventional robots on enhanced safety for human–machine interaction, environmental adaptability, and continuous deformation. In this blooming area of fundamental and technological importance, liquid crystal polymer networks and liquid crystal elastomers (referred to as LCNs) have emerged as one of the most valuable candidates for soft robots due to their complex, large, and reversible shape change capabilities. To date, much research effort, mainly regarding chemical synthesis, fabrication technologies and soft robot design, has been dedicated to LCN robotic systems to endow them with versatile and complex actions controlled by various stimuli. Herein, starting with the principle that governs the stimuli‐responsiveness of LCNs, recent progress made in LCN soft robots is summarized while focusing on different robotic motions, such as grapping, walking, swimming, and oscillation. Especially, novel LCNs with intelligent functions such as reprocessability, reconfigurability, self‐regulating behavior and associative learning capability, are highlighted. This article aims to provide significant insights into the design and development of LCN‐based soft robots.

Tunable Photomechanics in Diarylethene-Driven Liquid Crystal Network Actuators.

The response of soft actuators made of stimuli-responsive materials can be phenomenologically described by a stimulus-deformation curve, depicting the controllability and sensitivity of the actuator system. Manipulating such stimulus-deformation curve allows fabricating soft microrobots with reconfigurable actuation behavior, which is not easily achievable using conventional materials. Here, we report a light-driven actuator based on a liquid crystal polymer network containing diarylethene (DAE) photoswitches as cross-links, in which the stimulus-deformation curve under visible-light illumination is tuned with UV light. The tuning is brought about by the reversible electrocyclization of the DAE units. Because of the excellent thermal stability of the visible-absorbing closed-form DAEs, the absorbance of the actuator can be optically fixed to a desired value, which in turn dictates the efficiency of photothermally induced deformation. We employ the controllability in devising a logical AND gate with macroscopic output, i.e., an actuator that bends negligibly under UV or visible light irradiation, but with profound shape change when addressed to both simultaneously. The results provide design tools for reconfigurable microrobotics and polymer-based logic gating.

Localized Liquid Secretion from a Photopatterned Liquid-Crystal Polymer Skin

Liquid-releasing artificial skins are made from films made of a smectic liquid-crystal polymer network (LCN) photopolymerized in the presence of a photoactive azobenzene chromophore and a liquid-crystal porogen. The nonreactive porogen phase separates during the polymerization process, and the polymer forms a spongy polymer network filled with liquid. The liquid is excreted from the film when exposed to UV light upon conversion of trans-azobenzene to its cis isomer. Here, localized liquid secretion at preset positions at the polymer film is described. The design principle is based on creating a hybrid molecular architecture with both smectic and nonordered isotropic alignments in a continuous LCN coating. This coating is fabricated by a maskwise photopolymerization of the monomer mixture in the smectic phase, followed by a flood exposure at an elevated temperature above the isotropic state of the unpolymerized region. The smectic regions that polymerized during the maskwise exposure are not affected by the heating needed for the second polymerization step of the isotropic area. Upon activation under light illumination, the embedded liquid is exclusively released from the area with the smectic alignment. This approach reveals films of which the excretion process is reversible. The secreted liquid is reabsorbed spontaneously when azobenzene takes its initial trans-form. This process occurs thermally in time or can be accelerated by light irradiation with visible light.

Controlled Dynamics of Neural Tumor Cells by Templated Liquid Crystalline Polymer Networks.

The ability to control the alignment and organization of cell populations has great potential for tissue engineering and regenerative medicine. A variety of approaches such as nano/microtopographical patterning, mechanical loading, and nanocomposite synthesis have been developed to engineer scaffolds able to control cellular properties and behaviors. In this work, a patterned liquid crystal polymer network (LCN) film is synthesized by using a nematic liquid crystal template in which the molecular orientations are predesigned by photopatterning technique. Various configurations of polymer networks such as linear and circular patterns are created. When neural tumor cells are plated onto the templated LCN films, the cell alignment, migration, and proliferation are directed in both linear and curvilinear fashions following the pattern of the aligned polymer chains. A complex LCN pattern with zigzag geometry is also fabricated and found to be capable of controlling cell alignment and collective cellular organization. The demonstrated control of cell dynamics and organization by LCN films with various molecular alignments opens new opportunities to design scaffolds to control cultured cell organization in a manner resembling that found in tissues and to develop novel advanced materials for nerve repair, tissue engineering, and regenerative medicine applications.

Reactive mesogens for ultraviolet-transparent liquid crystal polymer networks

ABSTRACT Transparency and stability to UV light are important and desirable properties for modern tunable optical elements and active soft robots. A library of novel reactive mesogens for liquid crystal polymer networks resilient and transparent to UV light has been synthetised and characterised. Phase behaviours of the reactive mesogens have been determined by polarised optical microscopy and differential scanning calorimetry. Liquid crystal polymer networks based on the combination of these novel reactive mesogens have been evaluated and compared to those based on common commercially available compounds. The results showed a twofold increase in transparency in a broad UV spectral region (200–400 nm) and importantly showed no degradation upon prolonged UV exposure contrary to the networks composed from commercial counterparts.

Electroplasticization of Liquid Crystal Polymer Networks.

Shape-shifting liquid crystal networks (LCNs) can transform their morphology and properties in response to external stimuli. These active and adaptive polymer materials can have impact in a diversity of fields, including haptic displays, energy harvesting, biomedicine, and soft robotics. Electrically driven transformations in LCN coatings are particularly promising for application in electronic devices, in which electrodes are easily integrated and allow for patterning of the functional response. The morphing of these coatings, which are glassy in the absence of an electric field, relies on a complex interplay between polymer viscoelasticity, liquid crystal order, and electric field properties. Morphological transformations require the material to undergo a glass transition that plasticizes the polymer sufficiently to enable volumetric and shape changes. Understanding how an alternating current can plasticize very stiff, densely cross-linked networks remains an unresolved challenge. Here, we use a nanoscale strain detection method to elucidate this electric-field-induced devitrification of LCNs. We find how a high-frequency alternating field gives rise to pronounced nanomechanical changes at a critical frequency, which signals the electrical glass transition. Across this transition, collective motion of the liquid crystal molecules causes the network to yield from within, leading to network weakening and subsequent nonlinear expansion. These results unambiguously prove the existence of electroplasticization. Fine-tuning the induced emergence of plasticity will not only enhance the surface functionality but also enable more efficient conversion of electrical energy into mechanical work.

High-Contrast and Scattering-Type Transflective Liquid Crystal Displays Based on Polymer-Network Liquid Crystals.

The methods to enhance contrast ratios (CRs) in scattering-type transflective liquid crystal displays (ST-TRLCDs) based on polymer-network liquid crystal (PNLC) cells are investigated. Two configurations of ST-TRLCDs are studied and are compared with the common ST-TRLCDs. According to the comparisons, CRs are effectively enhanced by assembling a linear polarizer at the suitable position to achieve better dark states in the transmissive and reflective modes of the reported ST-TRLCDs with the optimized configuration, and its main trade-off is the loss of brightness in the reflective modes. The PNLC cell, which works as an electrically switchable polarizer herein, can be a PN-90° twisted nematic LC (PN-90° TNLC) cell or a homogeneous PNLC (H-PNLC) cell. The optoelectric properties of PN-90° TNLC and those of H-PNLC cells are compared in detail, and the results determine that the ST-TRLCD with the optimized configuration using an H-PNLC cell can achieve the highest CR. Moreover, no quarter-wave plate is used in the ST-TRLCD with the optimized configuration, so a parallax problem caused by QWPs can be solved. Other methods for enhancing the CRs of the ST-TRLCDs are also discussed.

Self-Assembly of Aqueous Soft Matter Patterned by Liquid-Crystal Polymer Networks for Controlling the Dynamics of Bacteria.

The study of controlling the molecular self-assembly of aqueous soft matter is a fundamental scheme across multiple disciplines such as physics, chemistry, biology, and materials science. In this work, we use liquid-crystal polymer networks (LCNs) to control the superstructures of one aqueous soft material called lyotropic chromonic liquid crystals (LCLCs), which shows spontaneous orientational order by stacking the plank-like molecules into elongated aggregates. We synthesize a layer of patterned LCN films by a nematic liquid-crystal host in which the spatially varying molecular orientations are predesigned by plasmonic photopatterning. We demonstrate that the LCLC aggregates are oriented parallel to the polymer filaments of the LCN film. This patterned aqueous soft material shows immediate application for controlling the dynamics of swimming bacteria. The demonstrated control of the supramolecular assembly of aqueous soft matter by using a stimuli-responsive LCN film will find applications in designing dynamic advanced materials for bioengineering applications.

Normally Transparent Tribo-Induced Smart Window.

Self-powered smart windows are desirable with the expectations of their energy-saving, weather-independent, user-controllable, and miniature performance. Recently developed solar- or thermal-powered smart windows largely depend on the weather conditions and have an extremely slow response, and only a certain portion of thesaved energy can be utilized by the external circuit for mode conversion. In this work, a self-powered normally transparent smart window was developed by the conjunction of a rotary freestanding sliding triboelectric nanogenerator (RFS-TENG) and a polymer network liquid crystal (PNLC) cell. To fabricate the PNLC cell, the alignment layer with randomly distributed microdomains was constructed to encapsulate a mixture of LC polymers and nematic LCs. The opacity of the smart window exposed to an alternating electric field was considerably improved owing to the embedded microdomains and a dense web of LC polymers. The ultrahigh haziness greatly alleviates the charge density required for the LC actuation and thus enables the driving by the TENG where the charge amount is usually limited. The RFS-TENG was elaborately designed with six periodic bent triboelectric films and Ag electrodes, which presented an ultralow friction wear and met the frequency requirement to achieve the steady opacity. By harvesting the mechanical energies from ambient environments, the tribo-induced smart window can benefit a wide variety of fields, such as self-powered sunroofs, wind-driven smart farming systems etc.

The relationship between hole size and the voltage-driven formation of surface structures in an ITO/liquid crystal polymer/perforated metal electrode system

A device consisting of a multidomain liquid crystal polymer network sandwiched between a continuous electrode and a perforated silver electrode shows strong surface deformations upon application of an electric field between the electrodes. Here, a new method is presented for the preparation of such a device, in which a silver film with circular holes of a well-controlled diameter was made by evaporating silver onto a monolayer of polystyrene spheres. Due to multilayer defects of the polystyrene microparticle lithography template, larger combined holes were present, which provided interesting information about the effect of pore size on the deformation behavior. The results were compared to an electrostatic field distribution, from which the conclusion could be drawn that there is a minimum hole size that allows deformation. This knowledge is important for the development of applications for this kind of device, as the aspect ratio of the deformations is of crucial importance for effects such as switchable wetting and self-cleaning.

Traveling Wave Rotary Micromotor Based on a Photomechanical Response in Liquid Crystal Polymer Networks.

The photomechanical response of liquid crystal polymer networks (LCNs) can be used to directly convert light energy into different forms of mechanical energy. In this study, we demonstrate how a traveling deformation, induced in a liquid crystal polymer ring by a spatially modulated laser beam, can be used to drive the ring (the rotor) to rotate around a stationary element (the stator), thus forming a light-powered micromotor. The photomechanical response of the polymer film is modeled numerically, different LCN molecular configurations are studied, and the performance of a 5.5 mm diameter motor is characterized.

Surfactants Synergistically Contributes to Reduction of Driving Voltage of Reverse-Mode Polymer Network Liquid Crystals with UV-Curable Nanoparticles

Proceedings of the International Display Workshops Volume 26 (IDW '19),Surfactants Synergistically Contributes to Reduction of Driving Voltage of Reverse-Mode Polymer Network Liquid Crystals with UV-Curable Nanoparticles

Surfactants Synergistically Contributes to Reduction of Driving Voltage of Reverse-Mode Polymer Network Liquid Crystals with UV-Curable Nanoparticles

Surfactants Synergistically Contributes to Reduction of Driving Voltage of Reverse-Mode Polymer Network Liquid Crystals with UV-Curable Nanoparticles

Tunable Diffraction Gratings in Copolymer Network Liquid Crystals Driven with Interdigitated Electrodes

The diffraction behavior of a polymer network liquid crystal (PNLC) was studied in in-plane switching (IPS) test cells and compared to the behavior seen in a neat liquid crystal. Due to the presence of polymer, the diffraction behavior was varied drastically: PNLCs are composites, which possess a specific domain size. The size of such polymer-induced domains was investigated with polarized optical microscopy and scanning electron microscopy. PNLCs are capable of continuous optical-phase modulation. It was found that electrical addressing with nonhomogenous electric fields can be useful to vary the phase modulation profile as compared to a neat LC. The diffraction patterns seen in a nematic LC were influenced by the applied addressing voltage and showed some limited tunability already. However, in the PNLC, the diffraction patterns were drastically varied as compared to a neat nematic LC. These gratings showed responses localized to the electrodes, had higher tuneability, and could also be useful to partially suppress the zeroth-diffraction order. Depending on the applied voltage, the diffraction efficiency could be tuned, efficiently. The presented results are instructive to understand the impact of a polymer network on the field-dependent reorientation of the liquid crystal director: if addressed with the same electric field profile, the responses were much more localized than in a neat nematic LC. In a straightforward numerical approach, domains in the PNLC samples were described by using cuboids. Diffraction patterns were then calculated based on the director reorientations seen and compared to the experimental data.

Mechanical adaptability of artificial muscles from nanoscale molecular action

The motion of artificial molecular machines has been amplified into the shape transformation of polymer materials that have been compared to muscles, where mechanically active molecules work together to produce a contraction. In spite of this progress, harnessing cooperative molecular motion remains a challenge in this field. Here, we show how the light-induced action of artificial molecular switches modifies not only the shape but also, simultaneously, the stiffness of soft materials. The heterogeneous design of these materials features inclusions of free liquid crystal in a liquid crystal polymer network. When the magnitude of the intrinsic interfacial tension is modified by the action of the switches, photo-stiffening is observed, in analogy with the mechanical response of activated muscle fibers, and in contrast to melting mechanisms reported so far. Mechanoadaptive materials that are capable of active tuning of rigidity will likely contribute to a bottom-up approach towards human-friendly and soft robotics.

26.6: Spectroscopic Response of Polymer Network Liquid Crystal Cell

The Polymer Network Liquid Crystal (PNLC) cell we fabricated is operating in a reverse mode of voltage‐off transparent state. It is found that when we apply voltage to the PNLC cells, the transmitted light color changed gradually and finally became a bit blue. This effect is not found in Polymer Dispersed LC (PDLC) window. The wavelength dependent transmittance voltage curves are reported and we will try to explain this effect by applying the anomalous diffraction theory.

Liquid Crystal Beam Steering Devices: Principles, Recent Advances, and Future Developments

Continuous, wide field-of-view, high-efficiency, and fast-response beam steering devices are desirable in a plethora of applications. Liquid crystals (LCs)—soft, bi-refringent, and self-assembled materials which respond to various external stimuli—are especially promising for fulfilling these demands. In this paper, we review recent advances in LC beam steering devices. We first describe the general operation principles of LC beam steering techniques. Next, we delve into different kinds of beam steering devices, compare their pros and cons, and propose a new LC-cladding waveguide beam steerer using resistive electrodes and present our simulation results. Finally, two future development challenges are addressed: Fast response time for mid-wave infrared (MWIR) beam steering, and device hybridization for large-angle, high-efficiency, and continuous beam steering. To achieve fast response times for MWIR beam steering using a transmission-type optical phased array, we develop a low-loss polymer-network liquid crystal and characterize its electro-optical properties.

Temperature‐ and Light‐Regulated Gas Transport in a Liquid Crystal Polymer Network

AbstractAzobenzene‐containing liquid crystal polymer networks (LCNs) are developed for temperature‐ and light‐regulated gas permeation. The order in a chiral‐nematic LCN (LCN*) is found to be essential to couple the unique structure of the membrane and its gas permeation responses to external stimuli such as temperature and varying irradiation conditions. An LCN membrane polymerized in the isotropic phase exhibits enhanced N2 permeation with increasing temperature, like most traditional polymers, but barely responds to exposure with 455 and 365 nm light. In sharp contrast, a reversible decrease of N2 transport is observed for the LCN* membrane of exactly the same chemical composition, but molecularly ordered, when submitted to an elevated temperature. More importantly, alternating in situ illumination with 455 and 365 nm light modulates reversibly N2 permeation performance of the LCN* membrane, through the trans–cis isomerization of azo moieties. The authors postulate that, besides the anisotropic deformation of LCN*, the decreased order in LCN* membrane caused by external stimuli (i.e., increasing temperature or UV light illumination) is responsible for an inhibition of gas permeation. These results show potential applications of liquid crystal polymers in the gas transport and separation, and also contribute to the development of “smart” membranes.

Normal- and Reverse-Mode Thermoresponsive Controllability in Optical Attenuation of Polymer Network Liquid Crystals.

A simple nonuniform irradiation method for photopolymerization-induced phase separation (PPIPS) was developed to produce unconventional mesoscale domain structures composed of liquid crystal (LC) and reactive mesogen (RM) phases. The LC/RM phase formations and their molecular orientation ordering through PPIPS were comprehensively investigated as a function of LC/RM molar ratio, curing temperature, and the use of uniform or nonuniform irradiation. Then, two different optical-anisotropic structures that can cause normal- or reverse-mode thermoresponsive light attenuation were formed by nonuniform irradiation at different curing temperatures at the same molar ratios. These two structures consist of mesoscale domains organized with multiaxially orientation-ordered LCs and orientation-disordered RMs for normal-mode thermoresponse and uniaxially orientation-ordered LCs and RMs for reverse-mode thermoresponse. Phase-separation nuclei were generated by nonuniform irradiation at the incipient stage during the PPIPS process under nonuniform irradiation and subsequently coalesced to form mesoscale polymer networks while maintaining their molecular orientation order. This is a promising method to overcome the restraint of structural controllability due to intrinsic material properties and thus to provide unconventional optical and photonic devices, such as thermoresponsive smart windows and thermometric sheets.

Shining Light on Liquid Crystal Polymer Networks: Preparing, Reconfiguring, and Driving Soft Actuators

AbstractSoft actuators based on liquid crystal polymer networks (LCNs) have emerged as an exciting research topic due to many envisioned applications in areas such as soft robotics and self‐regulating devices. The infatuation stems from the amazing ability of LCNs to display reversible, large amplitude, and complex shape change as well as locomotion upon a stimuli‐triggered phase transition of mesogens between ordered liquid crystal and disordered isotropic state. Among the various stimuli, light arguably is the most attractive choice. Light can easily be adjusted for its wavelength, intensity, or polarization, structured by means of photomasks or interference patterns, and applied to a target remotely and with high spatiotemporal resolution. Indeed, much research effort is dedicated to LCN actuators that are designed to respond to light in many ways, with light being used not only as an external energy source to drive the shape changes or motion of LCN actuators, but also as a versatile tool in their fabrication and reconfiguration. In this Review, recent achievements are highlighted, a number of important issues are discussed, and critical analysis on the use of light in making, reconfiguring, and driving LCN actuators is provided.