Robust and Multi-Functional Electrically Responsive Gold/Polydopamine-Coated Liquid Crystalline Elastomer Artificial Muscles

The development of smart actuators that integrate robust mechanical properties with rapid responsiveness remains a critical challenge for advancing artificial muscles. To address this, this study incorporates lignin—a renewable resource—into liquid crystalline elastomer (LCE) to fabricate a high‐performance photothermal‐responsive artificial muscle material. By leveraging the inherent aromatic conjugated structure of lignin as an efficient photothermal unit, we successfully integrated it with mesogens to construct a liquid crystalline network featuring a nanoscale microphase‐separated architecture. This network incorporates lignin‐based phenolic carbamate bonds and disulfide bonds concurrently, forming a dual dynamic crosslinking architecture that significantly enhances the mechanical properties of LCE, achieving a tensile strength of 21.5 MPa and an elongation at break exceeding 754%, thereby substantially surpassing conventional single‐network LCEs. It also confers outstanding photothermal response, enabling rapid, self‐actuated reversible deformation (33% strain). As a light‐driven artificial muscle, it achieves 40% reversible strain and 30.0 kJ/m 3 output power density. This work presents a novel strategy for developing high‐performance light‐driven LCEs through the integration of biomass lignin as both a reinforcing phase and an intrinsic photothermal converter. This approach not only enhances the material's performance but also offers promising pathways for the design and fabrication of next‐generation soft robots and artificial muscles.

Synthesis-Processing-Property Relationships in Thermomechanics of Liquid Crystal Elastomers

Human muscles, including skeletal, smooth, and cardiac muscles, are able to perform diverse deformations and execute complex biofunctions stimulated by nerve signals. Similarly, liquid crystal elastomer (LCE), which can respond to external stimuli with large and reversible deformations, demonstrates superior advantages to mimic nature muscles to fabricate artificial muscles. Till now, LCE has been utilized to simulate deformations and related functions of skeletal and smooth muscles. However, limited by the existing fabrication strategy, employing LCE to mimic the motion of cardiac muscles and further realizing the structure‐determined pumping functions, is still an open challenge. Learning from the specific spatial arrangements and synergistic actuation of cardiac muscle fibers within human heart, a simple and general strategy to construct artificial cardiac muscles with LCE fibers is proposed. In this work, LCE fibers with similar modulus and actuation behavior to muscle fibers are fabricated and spatially arranged in biological architectures as cardiac muscle fibers. As a result, artificial cardiac muscles are constructed and are able to perform simultaneous contraction and torsion motions, realizing heart‐pumping functions. This general strategy should be also applicable for other smart materials to conduct challenging tasks.

This dissertation demonstrates the design of reversibly self-morphing novel liquid crystalline elastomer (LCE) antennas that can dynamically change electromagnetic performance in response to temperature. This change in performance can be achieved by programming the shape change of stimuli-responsive (i.e., temperature-responsive) LCEs, and using these materials as substrates for reconfigurable antennas. Existing reconfigurable antennas rely on external circuitry such as Micro-Electro-Mechanical-Systems (MEMS) switches, pin diodes, and shape memory alloys (SMAs) to reconfigure their performance. Antennas using MEMS or diodes exhibit low efficiency due to the losses from these components. Also, antennas based on SMAs can change their performance only once as SMAs response to the stimuli and is not reversible. Flexible electronics are capable of morphing from one shape to another using various techniques, such as liquid metals, hydrogels, and shape memory polymers. LCE antennas can reconfigure their electromagnetic performance, (e.g., frequency of operation, polarization, and radiation pattern) and enable passive (i.e., battery-less) temperature sensing and monitoring applications, such as passive radio frequency identification device (RFID) sensing tags. Limited previous work has been performed on shape-changing antenna structures based on LCEs. To date, self-morphing flexible electronics, including antennas, which rely on stimuli-responsive LCEs that reversibly change shape in response to temperature changes, have not been previously explored. Here, LCE antennas will be studied and developed. Also, the metallization of LCEs with different metal conductors and their fabrication process, by either electron beam (E-Beam) evaporation or optical gluing of the metal film will be observed. The LCE material can have a significant impact on sensing applications due to its reversible actuation that can enable a sensor to work repeatedly. This interdisciplinary research (material polymer science and electrical engineering) is expected to contribute to the development of morphing electronics, including sensors, passive antennas, arrays, and frequency selective surfaces (FSS).

A method for fabricating long, soft, and reversibly actuatable liquid crystal elastomer (LCE) fibers by using direct ink write (DIW) printing was developed. Here, the LCE was produced based on a two-stage thermal-photo curingreaction between a difunctional acrylate monomer and thiol. The LCE ink, mixed with nanoclay to increase the viscosity, was extruded through a nozzle onto a rotating mandrel to obtain a long fiber. After printing, the fiber was first thermally cured on the mandrel, then mechanically stretched, and photocured to achieve liquid crystal chain alignment for stress-free reversible activation. Upon optimizing the ink viscosity and DIW printing parameters, long fibers (up to 1.5 m long from the laboratory) were obtained. The resulting fiber had a modulus of 2 MPa, 51% actuation strain, and a failure strain of well over 100%. The potential of these fibers for applications was demonstrated. The LCE fibers were knit, sewn, and woven to form a variety of smart textiles. The fiber was also used to mimic bicep muscles with both large activation force and activation strain. By incorporating further intelligent characteristics, such as conductivity and biosensing into a single fiber, the LCE fibers could be potentially used for smart clothing, soft robotics, and biomedical devices.

ABSTRACTA novel liquid crystal elastomer (LCE) synthesized by melt polymerization, which exhibits the capacity of shape memory, is reported here for the first time. The method of synthesize the shape memory LCE has been explored. A facile two‐step method to synthesize these anisotropic materials to realize reversible shape change behavior is reported. The first reaction is the addition of nematic liquid crystal molecules to form a kind of liquid crystal polymer. Subsequently, the polymer is crosslinked to trap the order of the liquid crystal into a crosslinked LCE. The LCE exhibits liquid crystalline behavior which has shape memory with excellent fixity and recovery. Its shape memory and actuating properties also have been studied. When reheating the LCE to 165 °C, the shape will recover. The main chains and crosslinked bonds of the LCE contain ester groups, which are sensitive to alkaline and acidic condition. It turns out that the LCE is intact under acidic condition, but it can be degraded under alkaline condition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 389–394

Liquid crystal elastomers (LCEs) are shape-morphing materials whose large and reversible shape transformations are caused by the coupling between the mobile anisotropic properties of liquid crystal (LC) units and the rubber elastic of polymer networks. Their shape-changing behaviors under certain stimuli are largely directed by the LC orientation; therefore, various strategies have been developed to spatially modulate the LC alignments. However, most of these methods are limited as they require complex fabrication technologies or have intrinsic limitations in applicability. To address this issue, programmable complex shape changes in some LCE types, such as polysiloxane side-chain LCEs, thiol-acrylate main-chain LCEs, etc., were achieved by using a mechanical alignment programming process coupled with two-step crosslinking. Here, we report a polysiloxane main-chain LCE with programmable 2- and 3D shape-changing abilities that were created by mechanically programming the polydomain LCE with two crosslinking steps. The resulting LCEs exhibited a reversible thermal-induced shape transformation between the initial and programmed shapes due to the two-way memory between the first and second network structures. Our findings expand on the applications of LCE materials in actuators, soft robotics, and smart structures where arbitrary and easily programmed shape morphing is needed.

The monodomain nematic liquid crystal elastomer (LCE) is a nonporous material with one-dimension (1D) negative thermal expansion (NTE) along the direction of orientation. This stimuli-responsive size change is comparable with the contractile response of a muscle fibre. Recently, LCEs have become more and more popular and increasingly investigated as a full-fledged class of stimuli-responsive materials. However, the nematic LCE is limited to a single, unidirectional deformation unless complex hybrid architectures are made. We develop here a special LCE based on a liquid crystal polymer with an extraordinary phase transition sequence, “re-entrant nematic (NRe) – smectic A (SmA) – nematic (N) – isotropic (I) phase”, along with “prolate – oblate – weakly oblate – spherical” chain conformation evolution. In the aligned LCE film, these conformational changes of polymer chain are observed with the naked eye through their macroscopic translations into a unique sequence of “contraction – expansion – second expansion” deformations. Notably, a switch from NTE to positive thermal expansion (PTE) occurs upon heating. Moreover, a bilayer actuator composed of aligned and non-aligned LCE layers can perform 2D to 3D shape transformation with “curling – uncurling – second uncurling” actuation sequence. This LCE capable of multiple deformations in response to a single stimulus paves the way to multimodal single-material actuators. It provides a new strategy for the development of advanced materials with adjustable and multidirectional deformations.

Morphing of stiffness-heterogeneous liquid crystal elastomers via mechanical training and locally controlled photopolymerization

This paper summarises the properties of archiral and chiral liquid crystalline (LC) elastomers, the latter of which have found interest due to their piezoelectric properties. In addition the formation of new LC elastomers by a radical polymerization of acrylate groups covalently linked to LC polymers was investigated. This was done concerning the progress of the crosslinking reaction, concerning the influence of the crosslinking on the LC phases and concerning the network properties (swelling ratio and elastic modulus) of the resulting elastomers. It turns out that the networks prepared in this way are very soft and their crosslinking density is low. This can be explained assuming that the radical polymerization of the acrylates leads only to short oligomers, due to steric restrictions. Photo crosslinking initiated by a photoinitiator in the LC phase creates a memory of the orientation before crosslinking.

Patterns perceived as regular by humans are ubiquitous and can be classified into non-biological patterns like cloud formations and sand dune stripes, biological patterns like zebra stripes, and artificial patterns like tiles. This paper focuses on three examples of non-biological self-organized patterns: wrinkles on material surfaces, alignment defect structures in liquid crystals, and a layered structure in liquid crystal elastomers. These non-biological patterns exhibiting useful functions are advantageous due to their low fabrication costs compared to biological and artificial patterns.

Liquid crystal elastomers (LCEs) are promising building blocks for soft robots, given their large, programmable, reversible, and stimuli‐responsive shape change. Enhancing LCEs’ stiffness and toughness has been a longstanding desire previously explored by reinforcing them with fillers, crystalline microdomains, and interpenetrating polymer networks. While promising, these methods adversely affect molecular order and thermal strain. Here, a significant enhancement of the stiffness of LCEs is reported by loading them with low molecular weight liquid crystals (LMWLCs) without sacrificing thermal strain and molecular order. While pristine LCEs rapidly transition to a soft elastic plateau when strained from poly‐ to monodomain, LC‐loaded samples (LC‐LCEs) first experience a pronounced linear elasticity, followed by a soft elastic plateau at higher stresses. Further thermomechanical and X‐ray analysis confirm the emergence of an additional mesophase in polydomain LC‐LCEs, which evolves to short‐range smectic (cybotactic) during the poly‐ to monodomain transition. Monodomain LC‐LCEs show between 6.5‐ and 9.0‐fold stiffness enhancement with improved molecular order and thermal strain. Their work densities are more than double that of pristine LCEs, with active thermal stroke of up to 25% under loads of over 2000 times their weight. Such remarkable behaviors are attributed to the interplay between post‐polymerization phase separation of LCs and their strain‐enhanced smectic ordering. The results suggest that LMWLC inclusion can be a simple yet robust method to significantly improve the mechanical properties of LCEs.

Fiber actuators underpin soft robots, artificial muscles, and smart textiles. A persistent bottleneck is the fabrication of monodomain liquid crystal elastomer (LCE) microfibers with narrow size distributions while preserving axial alignment. This work establishes a melt-centrifugal spinning (MCS) route with two-step UV fixation that separates flow-induced alignment from network crosslinking. High-speed rotation creates a long extensional jet; an obliquely incident, on-the-fly UV dose at touchdown locks the director, and a post-cure consolidates the network. The obtained LCE microfiber can achieve large reversible contraction (L/L0 = 0.56), lift a weight, and trigger the tweezers. The method produces a new approach for the fabrication of device-ready LCE actuators, establishes a general design principle for diameter control via curing sequence, and opens a practical path toward artificial muscles and flexible micro robotics.

To study the effect of the content of the nematic cross-linking units on the mesophase behaviors, the optical and mesomorphic properties of liquid crystalline elastomers (LCEs), aseries of LCEs have been synthesized by hydrosilylation reaction with poly(methylhydrogeno)siloxane, a cholesteric liquid crystalline monomer, and a nematic cross-linking agent. The chemical structures and properties of the synthesized LCEs have been investigated by use of various techniques. Homopolymer P0 bearing only cholesteric component displays a smectic A phase, but elastomers P1-P5 containing different content of nematic cross-linking units show a cholesteric mesophase. The reflection wavelengths of theLCEs show a weak temperature dependence at lower temperatures but a strong temperature dependence at higher temperatures. Furthermore, the maximum reflection wavelengths of the LCEs can be stabilized over a wide temperature range when the LCEs are heated, suggesting that the helical structure and pitch of the cholesteric phase can be stabilized with a polymer network.

Liquid crystal elastomers (LCEs), a class of elastomers combining liquid crystals with a polymer network, have garnered significant interest for applications in the field of soft robotics. However, the fracture and fatigue characteristics of LCEs remain poorly understood. This study presents a comprehensive investigation into the fracture and fatigue characteristics of LCEs, focusing on polydomain and monodomain variants subjected to different loading directions. The fracture energy (also called toughness) and fatigue threshold of polydomain and monodomain LCEs were quantitatively measured and compared with selected elastomers. Our experimental results demonstrate that polydomain LCEs exhibit superior fracture energy and fatigue threshold compared to monodomain LCEs. Within the monodomain category, LCEs subjected to parallel loading exhibit larger fracture energy than those under vertical loading, while their fatigue thresholds remain comparable. These findings enhance our understanding of the deformation and failure characteristics of LCEs, which are crucial for their applications in various fields.