Liquid Crystal Elastomers Research Articles

Programmable and Self‐Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding

AbstractShape‐changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape‐morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self‐healing ability. Here, we report halogen‐bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape‐programmed and that self‐heal under mild thermal or photothermal stimulation. We incorporate halogen‐bond‐donating diiodotetrafluorobenzene molecules as dynamic supramolecular crosslinks into the LCEs and show that these relatively weak crosslinks are pertinent for their mechanical programming and self‐healing. Utilizing the halogen‐bonded LCEs, we demonstrate proof‐of‐concept soft robotic motions such as crawling and rolling with programmed velocities. Our results showcase halogen bonding as a promising, yet unexplored tool for the preparation of smart supramolecular constructs for the development of advanced soft actuators.

Programmable and Self-Healable Liquid Crystal Elastomer Actuators Based on Halogen Bonding.

Shape-changing polymeric materials have gained significant attention in the field of bioinspired soft robotics. However, challenges remain in versatilizing the shape-morphing process to suit different tasks and environments, and in designing systems that combine reversible actuation and self-healing ability. Here, we report halogen-bonded liquid crystal elastomers (LCEs) that can be arbitrarily shape-programmed and that self-heal under mild thermal or photothermal stimulation. We incorporate halogen-bond-donating diiodotetrafluorobenzene molecules as dynamic supramolecular crosslinks into the LCEs and show that these relatively weak crosslinks are pertinent for their mechanical programming and self-healing. Utilizing the halogen-bonded LCEs, we demonstrate proof-of-concept soft robotic motions such as crawling and rolling with programmed velocities. Our results showcase halogen bonding as a promising, yet unexplored tool for the preparation of smart supramolecular constructs for the development of advanced soft actuators.

Matrix‐Driving Stretchable Structural Colors in Multi‐Pixels Operation Using Chiral Liquid Crystal Elastomers

AbstractStretchable structural color technologies are garnering significant attention in photonics for various applications owing to its stretchable flexibility and ability to control the photonic wavelength of light. However, stretchable photonic media, such as chiral liquid crystal elastomers (CLCEs), are subjected to uncontrollable nonuniform strain distribution and position‐dependent color change during the stretching‐assisted color tuning process. Therefore, controlling the colors of the mechanochromic structures is limited to just single‐unit operation level and practically desirable matrix driving mechanochromic devices for multi‐pixel applications have not been realized yet. The study reports position‐independent and multi‐pixel‐driven uniform stretchable structural color switching realized through row and column matrix switching operations by electrically stretchable CLCEs. The uniform strain‐induced color control mechanism and operations of a multi‐arrayed matrix‐driven stretchable color structure are theoretically and experimentally investigated. This breakthrough of a uniform and multi‐pixel color switching of a seven‐segment matrix driving stretchable CLCEs will be a technological leap into full‐scale use of mechanochromic structural colors in practical applications.

Ultra Rate‐Dependent Pressure Sensitive Adhesives Enabled by Soft Elasticity of Liquid Crystal Elastomers

AbstractThe fabrication of pressure sensitive adhesives (PSAs) using liquid crystal elastomers (LCEs), which are known for their excellent dissipation properties, is explored in this work. The adhesive properties of the PSAs are evaluated using the 180° peeling test at various conditions. The performance of the LCE adhesives is found to show significant rate and temperature dependence. When the adhesion energy is plotted against the rate, LCE shows an anomalously large power law exponent (n ≈ 1.17) compared to existing PSAs (n ≈ 0.1–0.6). The unusual rate sensitivity is hypothesized to originate from the synergy of soft elasticity and non‐linear viscoelasticity. The adhesive properties at various rates and temperatures are correlated to the results from dynamic mechanical analysis. Moreover, the large strain stiffening behavior of LCE under uniaxial tension reveals the distinctive advantages offered by LCE as adhesives. Time‐temperature superposition is used to obtain a master curve of adhesion energy that spans rates beyond typical experimental limits. The extreme rate dependence and the large strain stiffening of LCE yield a new category of adhesives that possess special properties, such as reversible adhesion and impact resistance, unlike traditional adhesives.

4D Printing of Reprogrammable Liquid Crystal Elastomers with Synergistic Photochromism and Photoactuation.

4D printing of liquid crystal elastomers (LCEs) via direct ink writing has opened up great opportunities to create stimuli-responsive actuations for applications such as soft robotics. However, most 4D-printed LCEs are limited to thermal actuation and fixed shape morphing, posing a challenge for achieving multiple programmable functionalities and reprogrammability. Here, a 4D-printable photochromic titanium-based nanocrystal (TiNC)/LCE composite ink is developed, which enables the reprogrammable photochromism and photoactuation of a single 4D-printed architecture. The printed TiNC/LCE composite exhibits reversible color-switching between white and black in response to ultraviolet (UV) irradiation and oxygen exposure. Upon near-infrared (NIR) irradiation, the UV-irradiated region can undergo photothermal actuation, allowing for robust grasping and weightlifting. By precisely controlling the structural design and the light irradiation, the single 4D-printed TiNC/LCE object can be globally or locally programmed, erased, and reprogrammed to achieve desirable photocontrollable color patterns and 3D structure constructions, such as barcode patterns and origami- and kirigami-inspired structures. This work provides a novel concept for designing and engineering adaptive structures with unique and tunable multifunctionalities, which have potential applications in biomimetic soft robotics, smart construction engineering, camouflage, multilevel information storage, etc.

Tunable circular polarization room temperature phosphorescence with ultrahigh dissymmetric factor by cholesteric liquid crystal elastomers

Tunable circular polarization room temperature phosphorescence with ultrahigh dissymmetric factor by cholesteric liquid crystal elastomers

Tough and Photo-Plastic Liquid Crystal Elastomer with a 2-Fold Dynamic Linker for Artificial Muscles.

Liquid crystal elastomers (LCEs) have been optimized by combining cross-linkers and dynamic bonds to achieve a reversible actuation behavior comparable to living skeletal muscles. In this study, one unique type of segment with 2-fold dynamic properties was introduced into LCEs, which offered not only dynamic diselenide covalent bonds for thermo-/photoplasticity but also H-bond arrays for dynamic cross-linking and mechanical robustness. Besides self-healing, self-welding, and recyclability, the LCEs were reprogrammable with elevated temperature or intensive visible light irradiation. The resultant LCEs gave an actuation blocking stress of 1.96 MPa and an elastic modulus of 14.4 MPa at 80 °C. The actuation work capacity reached 135.2 kJ m-3. When incorporating the Joule electrode or photothermal materials, the LCEs could be programmed as the electricity-driven and photothermal artificial muscles and thereby promised the application both as a biomimetic artificial hand and as an energy collector from sunlight. Thus, the 2-fold dynamic LCEs offered the pathway of enabling the reversible actuation behavior comparable to living skeletal muscles and promising applications in sustainable actuators, artificial muscles, and soft robots.

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A generalised WI1,I2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$W\\left({I}_{1},{I}_{2}\\right)$$\\end{document} strain energy function, a generalisation of previously devised response functions W1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${W}_{1}$$\\end{document} and W2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${W}_{2}$$\\end{document}, of binomial form is presented in this work for application to the finite deformation of isotropic incompressible soft solids. It is shown that the proposed model is the parent to many of the well-known existing invariants-based models in the literature. The first-order expansion of the model, with six model parameters, is then applied to extant multiaxial deformation of a wide range of materials, from filled and unfilled rubbers to hydrogels, liquid crystal elastomers and biomaterials. The model captures the experimental data accurately, with typical relative errors below 4%, while favourably modelling various challenging mechanical behaviours such as the asymmetry of compression—tension, high nonlinearity of the simple shear response, deformation softening effects, pronounced Payne effect, the soft elasticity phenomenon, and the reverse Poynting effect. The predictive capabilities of the model are also demonstrated and verified against experimental data. Given the analyses and results presented here, the devised model is proposed to serve as a standard choice for a priori selection for application to the finite deformation of isotropic incompressible soft materials.

Shape-Programmable Liquid-Crystalline Polyurethane-Based Multimode Actuators Triggered by Light-Driven Molecular Motors.

In recent years, light-driven soft actuators have been rapidly developed as enablers in the fabrication of artificial robots and biomimetic devices. However, it remains challenging to amplify molecular isomerization to multiple modes of macroscopic actuation with large amplitude and complex motions. Here, a strategy is reported to build a light-responsive liquid-crystalline polyurethane elastomer by phototriggered overcrowded alkene-based molecular motors. A trifunctional molecular motor modified with an ethylene glycol spacer on the rotor and stator functions as a crosslinker and unidirectional stirrer that amplifies molecular motion into macroscopic movement. The shape-programmable polymeric film presents superior mechanical properties and characteristic shape-memory effect. Furthermore, diverse modes of motions including bending, unwinding, and contracting with tunable actuation speed over a wide range are achieved. Such research is hoped to pave a new way for the design of advanced light-responsive soft actuators and robots.

Anti-Hertz bulging of actuated liquid crystal elastomers

We consider the ‘anti-Hertz’ elastic problem of inverse indentation, which happens when the surface of an elastic material is pressed down with a plate with a round hole to form a bulge. This classical problem takes on a new life when a polydomain nematic liquid crystal elastomer is used. In this case, the nematic director aligns with the leading principal direction of local stress distribution created by bulging. When the deformed material is crosslinked a second time, this alignment pattern and the resulting permanent protrusion are preserved as pressure is removed, creating a bulge that can be reversibly actuated from a flat surface upon cooling. Experimentally, we also observe a dimple ring around the bulge and a punt (indentation) underneath it at the bottom. Theoretically, we model the deformation by coupling linear elastic and anelastic deformations using non-monotonic nematic elasticity and the singular stress-order relation of the polydomain-monodomain transition. The theory is in excellent agreement with the experiments, and predicts the emergence of all observed features.

Caloric effects in liquid crystal-based soft materials

With the increased environmental awareness, the search for environmentally friendlier heat-management techniques has been the topic of many scientific studies. The caloric materials with large caloric effects, such as the electrocaloric (EC) and elastocaloric (eC) effects, have increased interest due to their potential to realize new solid-state refrigeration devices. Recently, caloric properties of soft materials, such as liquid crystals (LCs) and LC elastomers (LCEs), are getting more in the focus of caloric materials investigations, stimulated by large caloric effects observed in these materials. Here, an overview of recent direct measurements of large caloric effects in smectic LC 14CB and main-chain LCEs is given. Specifically, high-resolution thermometric measurements revealed a large EC response in 14CB LC exceeding 8 K. Such a large effect was obtained at a relatively moderate electric field of 30 kV cm−1 compared to solid EC materials. We demonstrate that such a small field can induce the isotropic to smectic A phase transition in 14CB, releasing or absorbing relatively large latent heat that enhances the EC response. Furthermore, it is demonstrated that in main-chain LCEs, the character of the nematic to isotropic transition can be tuned from the supercritical towards the first-order regime by decreasing the crosslinkers’ density. Such tuning results in a sharper phase transition and latent heat that enhance the eC response, exceeding 2 K and with the eC responsivity of 24 K MPa−1, about three orders of magnitude larger than the average eC responsivity found in the best shape memory alloys. Significant caloric effects in soft LC-based materials, observed at much smaller fields than in solid caloric materials, demonstrate their ability to play an important role as new cooling elements, thermal diodes, and caloric-active regeneration material in new heat-management devices.

Flexible Capacitive Sensors Based on Liquid Crystal Elastomer.

The disordered transformation of the ordered aligned polar liquid crystal molecules in liquid crystal elastomers (LCEs) under the influence of an external field imbues them with the unique property of thermally reversible shape memory, making them highly valuable for various applications, particularly in actuators. In this study, we examined the high dielectric constant exhibited by the orientation polarization of polar liquid crystal molecules in RM257-LCE films, which holds significant potential for developing flexible capacitive sensors. By manipulating the flexibility of the molecular chain network and introducing hydrogen bonds and metal ions into the main chain, we were able to enhance the relative dielectric constant of LCEs to an impressive value of 62 (at 100 Hz), which is approximately 23 times higher than for polydimethylsiloxane (PDMS). This elevated dielectric constant displays a noteworthy positive temperature coefficient within a specific temperature range, starting from room temperature and extending to the clearing point. Using this property, we fabricated highly sensitive capacitive, flexible temperature sensors. Moreover, we successfully engineered a flexible pressure sensor with an excellent pressure-sensing range of 0-2 MPa by combining the porous structure of the prepared LCEs with mushroom electrodes. Additionally, the sensor showcases a remarkable capacitance recovery time of 0.8 s at 90 °C. These outstanding features collectively contribute to the excellent pressure-sensing characteristics of our sensor. The findings of this study offer valuable insights and serve as a reference for the design of innovative flexible sensors, enabling advancements in sensor technology.

Reversible Information Storage Based on Rhodamine Derivative in Mechanochromic Cholesteric Liquid Crystalline Elastomer

AbstractWith the demand for the diversity and security of information deliveries increasing, advanced security tag for data encryption has attracted great interest from the scientific community. It is promising to achieve composite dynamic information storage by the combination of multisource stimuli‐responsive mechanism. Here, mechano‐ and chemochromism cholesteric liquid crystal elastomers (CLCEs) are prepared by introducing a rhodamine lactam‐based functional trigger by two different strategies, one of which is one‐pot method and another is postfunctionalization method. The performances of the CLCEs from two strategies are investigated, which are demonstrated to be effective methods in endowing material with new function, and suitable for different application scenarios. The composite material combines the force‐induced structural periodicity variation of CLCE and the pigmentary and fluorescent properties changes of the functional trigger caused by the chemical environment. The orthogonal construction of dynamic structural color pattern and reversible pigmentary and fluorescent colors pattern enable the information in the CLCE to display double encryption mode, which exhibits great potential in the information storage and anti‐counterfeiting.

Fully (Re)configurable Interactive Material through a Switchable Photothermal Charge Transfer Complex Gated by a Supramolecular Liquid Crystal Elastomer Actuator.

Charge transfer complexes (CTCs) based on self-assembled donor and acceptor molecules allow light absorption of significantly redshifted wavelengths to either the donor or acceptor. In this work, we demonstrate a CTC embedded in a hydrogen-bonded liquid crystal elastomer (LCE), which in itself is fully reformable and reprocessable. The LCE host acts as a gate, directing the self-assembly of the CTC. When hydrogen bonding is present, the CTC behaves as a near-infrared (NIR) dye allowing photothermal actuation of the LCE. The CTC can be disassembled in specific regions of the LCE film by disrupting the hydrogen bond interactions, allowing selective NIR heating and localized actuation of the films. The metastable non-CTC state may persist for weeks or can be recovered on demand by heat treatment. Besides the CTC variability, the capability of completely reforming the shape, color, and actuation mode of the LCE provides an interactive material with unprecedented application versatility.

Second-Generation Soft Actuators Driven by NIR Light Based on Croconaine Dye-Doped Vitrimers.

Soft actuators with photo-response can be selectively driven by the light source, but it is challenging to achieve a selective response of multiple components under a uniform light field, which is actually of great importance for the development of soft robots. In this work, a series of near-infrared light (NIR)-responsive vitrimers (CR-vitrimers) are synthesized by carboxylate transesterification using carboxyl-bearing croconaine dye (CR-800) as a photothermal agent (PTA). NIR-responsive liquid crystalline elastomers (CR-vitrimer-LCEs) under NIR laser (λmax = 808 nm) without the template can be further prepared. More importantly, the dynamic covalent bonding properties of vitrimer allow for the fabrication of a hand-shaped actuator by hot pressing, consisting of "fingers" with different NIR-response threshold values. After programming as needed, the hand-shaped actuator successfully achieves local and sequential control under a uniform NIR light field.

The Synergistic Effects Between Liquid Crystal and Crystalline Phase on Photo-Responsive Elastomers Toward Quick Photo-Responsive Performance.

Adopting only a small amount of azobenzene molecular to design liquid crystal photo-responsive materials capable of quick response and flexible adjustability is in high demand but is challenging. Herein, we introduced azobenzene molecules into polyurethane elastomer containing crystalline structure for preparing azobenzene liquid-crystal elastomers (ALCEs) and discovered this phenomenon of the synergistic effects between liquid crystal and crystalline phase. The key point of the work is that the synthetic ALCEs can utilize the reversible isomerism capability of azobenzene molecules under light irradiation, which can pry the motion of the macromolecular crystalline region in system to realize the large macroscopic deformation of the photo-responsive behavior. Obviously, the ALCEs sample containing azobenzene molecule and polyethylene glycol (PEG) crystallization can quickly bend illuminated by UV light and rapidly straighten under green light. Under the same UV irradiation, the bending speed, final bending angle, recovery rate and recovery ratio of ALCEs are larger than that of ALCEs without any crystalline structure. This devised ALCEs based on the synergistic effects between liquid crystal and crystalline phase can break through the current dilemma that the application of traditional azobenzene photo-responsive materials is limited by their concentration, greatly expanding the design thought and their scope of application. This article is protected by copyright. All rights reserved.

Self-Vibration of Liquid Crystal Elastomer Strings under Steady Illumination.

Self-vibrating systems based on active materials have been widely developed, but most of the existing self-oscillating systems are complex and difficult to control. To fulfill the requirements of different functions and applications, it is necessary to construct more self-vibrating systems that are easy to control, simple in material preparation and fast in response. This paper proposes a liquid crystal elastomer (LCE) string-mass structure capable of continuous vibration under steady illumination. Based on the linear elastic model and the dynamic LCE model, the dynamic governing equations of the LCE string-mass system are established. Through numerical calculation, two regimes of the LCE string-mass system, namely the static regime and the self-vibration regime, are obtained. In addition, the light intensity, contraction coefficient and elastic coefficient of the LCE can increase the amplitude and frequency of the self-vibration, while the damping coefficient suppresses the self-oscillation. The LCE string--mass system proposed in this paper has the advantages of simple structure, easy control and customizable size, which has a wide application prospect in the fields of energy harvesting, autonomous robots, bionic instruments and medical equipment.

Self-Vibration of a Liquid Crystal Elastomer Fiber-Cantilever System under Steady Illumination.

A new type of self-oscillating system has been developed with the potential to expand its applications in fields such as biomedical engineering, advanced robotics, rescue operations, and military industries. This system is capable of sustaining its own motion by absorbing energy from the stable external environment without the need for an additional controller. The existing self-sustained oscillatory systems are relatively complex in structure and difficult to fabricate and control, thus limited in their implementation in practical and complex scenarios. In this paper, we creatively propose a novel light-powered liquid crystal elastomer (LCE) fiber-cantilever system that can perform self-sustained oscillation under steady illumination. Considering the well-established LCE dynamic model, beam theory, and deflection formula, the control equations for the self-oscillating system are derived to theoretically study the dynamics of self-vibration. The LCE fiber-cantilever system under steady illumination is found to exhibit two motion regimes, namely, the static and self-vibration regimes. The positive work done by the tension of the light-powered LCE fiber provides some compensation against the structural resistance from cantilever and the air damping. In addition, the influences of system parameters on self-vibration amplitude and frequency are also studied. The newly constructed light-powered LCE fiber-cantilever system in this paper has a simple structure, easy assembly/disassembly, easy preparation, and strong expandability as a one-dimensional fiber-based system. It is expected to meet the application requirements of practical complex scenarios and has important application value in fields such as autonomous robots, energy harvesters, autonomous separators, sensors, mechanical logic devices, and biomimetic design.

Modeling Viscoelasticity and Dynamic Nematic Order of Exchangeable Liquid Crystal Elastomers.

Exchangeable liquid crystal elastomers (XLCEs), an emerging class of recyclable polymer materials, consist of liquid crystalline polymers which are dynamically crosslinked. We develop a macroscopic continuum model by incorporating the microscopic dynamic features of the cross-links, which can be utilized to understand the viscoelasticity of the materials together with the dynamic nematic order. As applications of the model, we study the rheological responses of XLCEs in three cases: stress relaxation, strain ramp, and creep compliance, where the materials show interesting rheology as an interplay between the dynamic nematic order of the mesogenic units, the elasticity from the network structure, and the dissipation due to chain exchange reactions. Not only being useful in understanding the physical mechanism underlying the fascinating characteristics of XLCEs, this work can also guide their future fabrications with desired rheological properties.

Mechanism of Pressure-Sensitive Adhesion in Nematic Elastomers.

Nematic liquid crystal elastomers (LCEs) have anomalously high vibration damping, and it has been assumed that this is the cause of their anomalously high-pressure-sensitive adhesion (PSA). Here, we investigate the mechanism behind this enhanced PSA by first preparing thin adhesive tapes with LCE of varying cross-linking densities, characterizing their material and surface properties, and then studying the adhesion characteristics with a standard set of 90° peel, lap shear, and probe tack tests. The study confirms that the enhanced PSA is only present in (and due to) the nematic phase of the elastomer, and the strength of bonding takes over 24 h to fully reach its maximum value. Such a long saturation time is caused by the slow relaxation of local stress and director orientation in the nematic domains after pressing against the surface. We confirm this mechanism by showing that freshly pressed and annealed tape reaches the same maximum bonding strength on cooling, when the returning nematic order is forming in its optimal configuration in the pressed film.