Monodomain Liquid Crystal Elastomers Research Articles

Higher-Order Structural Analysis of a Transparent and Flexible High Thermal Conductive Liquid Crystalline Elastomer Sheet and Its Composite.

Transparency, flexibility, and high thermal conductivity are trade-offs. Specifically, we have investigated a cross-linked acrylic liquid crystal elastomer (LCE) that exhibits both transparency and flexibility while maintaining a high level of thermal conductivity. The transparent monodomain LCE sheet was achieved through a process of stretching an initially opaque polydomain sheet to 80% elongation and subsequently subjecting it to photocuring. The thermal conductivity in the stretching direction (x) of the monodomain LCE sheet was found to be 1.8 times higher than that of the prestretched polydomain sheet, consistent with findings from previous studies. However, in the orthogonal direction (y) to the stretching (x) direction, the thermal conductivity exhibited an even higher value, being 1.7 times greater than in the x-direction, with a value of 3.0 W/(m·K). This unique observation prompted us to conduct further investigation through higher-order structural analysis of these LCE sheets using 2D wide-angle X-ray scattering (WAXS) analysis. In the transparent sheet, the LCE molecules were aligned in the sheet in the stretching x-direction (monodomain structure) for the out-of-plane direction. However, in the in-plane x-direction, the molecular plane spacing exhibited random orientation at a period of 0.45 nm. In contrast, within the y-direction of the inner layer, the molecular plane spacing exhibited a uniaxial horizontal orientation at the same period length as in the x-direction. The heat energy entering into the y-direction once spreads to the x-direction, but it was considered that the reason for the higher thermal conductivity to the y-direction would be forming covalent bonds that function as new heat transmission paths, in the direction intersecting to the x-direction during photocuring. Therefore, we concluded that the synergistic effect of the high level of the ordered inner structure and covalent bonding structure due to cross-linking in the y-direction contributes to its higher thermal conductivity compared to that in the x-direction, which exhibits a random in-plane structure. Additionally, we have fabricated an LCE composite sheet filled with 75 vol % of alumina particles using a polydomain-type LCE as the base material. The composite sheet exhibits remarkable thermal conductivity in the thickness direction, measuring at 9.8 W/(m·K), while maintaining a flexibility characterized by an elastic modulus of 70 MPa. This thermal conductivity surpasses that of a nonmesogenic acrylic composite sheet with identical alumina particle filling, which measured at 3.9 W/(m·K), more than twice as much. The presence of the mesogen skeleton has been demonstrated to enhance heat transfer, even within soft composites, by facilitating the formation of an ordered structure.

Photothermal porous monodomain liquid crystal elastomer actuator based on confined expansion method

Light-driven monodomain liquid crystal elastomers (mLCEs) have the advantages of remote operation and local control, but the response time will increase rapidly with the increase of thickness due to the limitation of the incident light depth. In order to achieve fast response, porous AuNPs-mLCEs actuators are proposed and fabricated by a confined expansion method. The average pore size of the prepared rod-shaped porous mLCEs is 200 μm, the porosity is 46.5%, and the order parameter of mesogens is 0.41. When the diameter is 3 mm, the response time is 1.2 s at a wavelength of 532 nm and a light intensity of 2.6 W•cm−2. When the diameter increases to 10 mm, the response time only increases to 2.2 s. The contraction of porous mLCEs actuator caused by the photothermal effect enables it can not only to lift an object 321.5 times heavier than itself by contraction, but also raise-up an object 5.2 times heavier than itself by bending. This method can be used to design and manufacture various 3D porous photothermal actuators with fast response.

Light-Responsive Actuator of Azobenzene-Containing Main-Chain Liquid Crystal Elastomers with Allyl Sulfide Dynamic Exchangeable Linkages.

Herein, a light-responsive and light-induced bond-exchange-reaction (BER)-capable actuator of the monodomain liquid crystal elastomer (xMLCEazo), developed using main-chain mesogenic oligomers containing azobenzene and allyl sulfide linkages, is investigated. Large quantities of the azobenzene and allyl dithiol linkages are incorporated into the main-chain mesogenic oligomer prepared via thiol-acrylate Michael addition polymerization (TAMAP). The xMLCEazo film is generated via visible-light-induced BER of the drawn polydomain xLCEazo (xPLCEazo) film prepared via TAMAP of tetrathiol cross-linkers and diacrylate-terminated mesogenic oligomers. The xMLCEazo film exhibits large length actuation (38%) through the photothermal effect, along with excellent self-healing and reprogramming properties, under ultraviolet (UV) light irradiation. UV light induced BER of the xMLCEazo film is used to develop complex-shaped actuators with a bilayer film, containing the xMLCEazo and xPLCEazo films, which are bonded by the UV light induced BER without glue. The individual arm of the complex eight-arm flower is remotely actuated under UV light irradiation, and a circular band is rolled under blue laser light irradiation, demonstrating the local remote-controlled actuation and fuel-free motion of the motile soft robot using light irradiation, respectively. Thus, the xMLCEazo film can be expanded to other interesting applications requiring reprogrammable, self-healing, reprocessable, patternable, and remote-controlled light-triggered elastic, rubber-like actuators.

Exceptional stress-director coupling at the crack tip of a liquid crystal elastomer

A liquid crystal elastomer (LCE) is a special elastomer containing rod-like liquid crystals, which align in a certain direction, called the director. The director of a LCE can rotate under stress, resulting in large spontaneous strain and soft elastic behavior. This study unravels how the strong stress-director coupling in a monodomain LCE induces unique crack-tip fields and fracture behavior. Through stretching edge-cracked LCEs with various initial directors, we characterize the displacement and director fields theoretically and experimentally. The results reveal that the directors undergo significant and inhomogeneous rotation at the crack tips, leading to very different stress/strain distributions from traditional elastomers. Particularly, when the initial director is tilted to the loading direction, the stress/strain distributions are asymmetrical about the crack plane. Notably, we discover a domain wall forms along a certain polar angle at the crack tip, with opposite director rotation, and thereby shear strain, on the two sides of the domain wall. Moreover, LCEs with a tilted initial director to the loading exhibit much smaller crack openings and energy release rates than those of neo-Hookean materials, while LCEs with a parallel director exhibit higher values. We attribute these findings to a combined effect of bulk softening at the remote region and the formation of domains of opposite director rotation near the crack tip. This study provides an understanding of how the stress-director coupling of LCEs triggers their unique crack-tip fields, and insights into strategies to enhance the fracture properties of LCEs for future applications.

Ionic Conductivity Switchable and Shape Changeable Smart Skins with Azobenzene‐Based Ionic Reactive Mesogens

AbstractTo develop smart ionic skins capable of multi‐responsiveness and switchable ionic conductivity, a stimuli‐responsive and ionic conductive azobenzene‐based monomer is newly synthesized, uniaxially oriented, and polymerized for anisotropic liquid crystal elastomers (LCEs). Since the uniaxially oriented monodomain LCE with ionic asymmetric azobenzene monomers (i‐AAM) is prepared by thermal oligomerization, uniaxial stretching, and subsequent photopolymerization, the stimuli‐responsive i‐AAM LCE is thermally contracted by increasing the temperature above TNI as well as is bent along the aligned direction by irradiating it with UV light. In addition to the change of shape, the ionic conductivity of the LCE is reversible in response to heat and light stimuli. Polydomain i‐AAM LCE polymerized without the stretching process exhibits higher ionic conductivity than stretched monodomain LCE due to the initially formed stable ionic pathways. Ionic conductivity can also be switched simultaneously by polarity changes in response to the photoisomerization of i‐AAM, increased mobility from heat, and an elastic mechanoresponse from external stresses. These i‐AAM LCE‐based soft grippers exhibit stimuli‐responsive grasping and releasing actuation and detect ionic conductivity switches finely, suggesting potential as smart skins for advanced soft robots.

Modeling the thermo-responsive behaviors of polydomain and monodomain nematic liquid crystal elastomers

Liquid crystal elastomers (LCEs) are polymeric materials that combine liquid crystal orientation and rubber elasticity. The mechanical responses of LCEs strongly depend on the nematic order and temperature. Developing a thermo-order-mechanical coupling model is important for the engineering applications of LCEs. In this work, we first synthesize both polydomain and monodomain LCEs. The shape change with temperature under a certain stress level is further characterized. In the theoretical part, the Landau–de Gennes model and neo-classical model are combined to construct the free energy density of LCEs. A linear term accounting for the effect of interior stress on nematic–isotropic transition is incorporated into the Landau–de Gennes free energy density, while a macro-order parameter is defined to describe the polydomain–monodomain transition for polydomain LCEs induced by the external force. Comparison between the model predictions and experimental results shows acceptably consistency for both polydomain and monodomain LCEs. Therefore, this work provides an efficient approach to predict the shape change of LCEs in various scenarios.

Liquid crystal elastomer film actuators with anti-strain robustness

Thermotropic monodomain liquid crystal elastomers (mLCEs) exhibit reversible contractile actuation properties along the collimated direction of mesogens when stimulated by external temperature, similar to those of biological skeletal muscle, and have great potential applications in flexible actuators and artificial muscles. However, the existence of flexible chain segments causes mLCEs to elongate under a small load, making calibration under different loads necessary when they are used as an actuator. In this study, a physical crosslinking point between flexible segments is provided through the introduction of designed long-chain molecules (LHS) containing amide bonds on the main chain of LCEs. The 5% LHS-mLCEs with enhanced anti-strain robustness achieved essentially constant original length over a range of loads (0–0.25 MPa) and maintained a reversible contraction ratio of 39.4%, comparable to biological skeletal muscle. Furthermore, a nonreconfigurable topological structure of a metal electrothermal layer with lossless compression properties was designed and prepared on the surface of mLCEs. The film actuators exhibit higher frequency oscillatory actuation (0.1 Hz 9.2%; 0.2 Hz 6.3%; 0.5 Hz 2%) relative to previously reported actuators, benefitting from the optimized heat dissipation structure of LCEs/Ag/air. This study provides valuable references and ideas for applying thermotropic mLCEs in practice.

Wireless Power Transfer to Electrothermal Liquid Crystal Elastomer Actuators.

Wireless actuation of electrically driven soft actuators is of paramount importance for the development of bioinspired soft robotics without physical connection or on-board batteries. Here, we demonstrate untethered electrothermal liquid crystal elastomer (LCE) actuators based on emerging wireless power transfer (WPT) technology. We first design and fabricate electrothermal LCE-based soft actuators that consist of an active LCE layer, a conductive liquid metal-filled polyacrylic acid (LM-PA) layer, and a passive polyimide layer. LM can function not only as an electrothermal transducer to endow resulting soft actuators with electrothermal responsiveness but also as an embedded sensor to track the resistance changes. Various shape-morphing and locomotive modes such as directional bending, chiral helical deformation, and inchworm-inspired crawling can be facilely obtained through appropriately controlling the molecular alignment direction of monodomain LCEs, and the reversible shape-deformation behaviors of resulting soft actuators can be monitored in real-time through resistance changes. Interestingly, untethered electrothermal LCE-based soft actuators have been achieved by designing a closed conductive LM circuit within the actuators and combining it with inductive-coupling WPT technology. When the resulting soft actuator approaches a commercially available wireless power supply system, an induced electromotive force can be generated within the closed LM circuit, which results in Joule heating and wireless actuation. As proof-of-concept illustrations, wirelessly driven soft actuators that can exhibit programmable shape-morphing behaviors are demonstrated. The research disclosed herein can provide insights into the development of bioinspired somatosensory soft actuators, battery-free wireless soft robots, and beyond.

Low-temperature reprogrammable dual light-responsive liquid crystalline elastomer films

The liquid crystal elastomers (LCEs) possessing azobenzene moieties and boron ester bonds were prepared using Michael addition reaction and photopolymerisation. The azobenzene moieties imparted the LCEs with photoresponsiveness, whereas the boron ester bonds enabled the LCEs to undergo director alignment, reprogramming, and self-healing through a dynamic bond exchange reaction (DBER). This combined strategy overcame the competition between actuation and a DBER at high temperatures, which has been a drawback in the previously developed LCE vitrimers. Interestingly, the developed monodomain LCEs (MLCEs) showed the bending actuation in responsive to both UV and blue lights and unbending motion in responsive to green light, which paves the way for the design of new actuators for biomedical applications. Furthermore, taking advantage of the dynamic nature of boron ester chemistry, bilayer-structured actuators capable of thermo- or photo-controllable bending/unbending motions were fabricated by welding the MLCE film with a poly(ethylene terephthalate) substrate or itself below their nematic-to-isotropic transition temperatures via a ‘glue-free’ method. The MLCEs developed in this study can undergo multidirectional movements in response to different stimuli and can be used in applications such as microrobots, untethered biomimetic grippers, and surgical instruments.

Liquid-phase drawing of LCE/CNT composites for electrothermal actuators

Monodomain liquid crystal elastomers with excellent reversible contraction deformation under a heat stimulus have broad application prospects in artificial muscles, soft robots, and micromechanical systems. Greater control can be achieved in a flexible actuation process through the generation of Joule heat by electricity. Herein, a highly conductive liquid crystal elastomer fibre actuator (c-LCF) was continuously prepared via liquid-phase drawing, with a conductivity of up to 12.5 S/m at 30 ℃. High conductivity is realised by the semi-wrapping combination of the main-chain liquid crystal prepolymer and carbon nanotube/carbon black to achieve a high-concentration dispersion of multi-dimensional conductive carbon nanomaterials. The fabricated c-LCF had a negative temperature coefficient, which is favourable for controllability and fast electrothermal actuation. The c-LCF contracted by approximately 30 % under a load of 1 MPa with a current of 9 mA (28 V/cm, 252 mW/cm). Its output power density reached 0.94 kJ/kg, indicating a better performance than biological muscle fibres; thus, it can be used to construct high-load bio-muscles. The different structures constructed by the c-LCF and fibre bundles can realise different electric actuation modes. In addition, fast driving can be realised using an elastic instability structure. The applications of liquid-crystal elastomers will be significantly broadened by this research.

Monodomain liquid crystal elastomer bionic muscle fibers with excellent mechanical and actuation properties.

Monodomain liquid crystal elastomers (m-LCEs) exhibit large reversible deformations when subjected to light and heat stimuli. Herein, we developed a new method for the large-scale continuous preparation of m-LCE fibers. These m-LCE fibers exhibit a reversible contraction ratio of 55.6%, breaking strength of 162MPa (withstanding a load of 1 million times its weight), and maximum output power density of 1250J/kg, surpassing those of previously reported m-LCEs. These excellent mechanical properties are mainly attributed to the formation of a homogeneous molecular network. Furthermore, the fabrication of m-LCEs with permanent plasticity using m-LCEs with impermanent instability without external intervention was realized by the synergistic effects of the self-restraint of mesogens and the prolonged relaxation process of LCEs. The designed LCE fibers, which are similar to biological muscle fibers and can be easily integrated, exhibit broad application prospects in artificial muscles, soft robots, and micromechanical systems.

Attenuating liquid crystal elastomers’ stress concentration by programming initial orientation

Liquid crystal elastomers (LCEs) are a kind of soft smart materials with fascinating programmability and have a broad application prospect. The monodomain LCEs under loading exhibit the semi-soft elasticity due to the stress-induced director rotation and the resulting spontaneous strain. In this article, we aim to reduce the severe stress concentration of LCEs by programming the initial director orientations. We numerically studied the stress concentration behaviors of a LCE sheet containing a small circular hole with different distribution of initial director under uniaxial loading. For monodomain LCE sheets, the stress concentration factor monotonically decreases as the initial director orientation deviates from the loading direction, and achieves its minimum when the deviation angle reaches 45°. This reduction of stress concentration is attributed to the smaller relative net director rotation and the lower resulting spontaneous strain near the hole edge as the deviation angle increases. Since the director rotation near the hole edge is critical for the attenuation of stress concentration, we only program the initial director orientation near the hole edge, and achieve up to 50% reduction in stress concentration factor. Increasing the size of programming area also enhances the attenuation of stress concentration. This work provides a new strategy to reduce the stress concentration in LCEs with geometric defects.

Formation of lamellar domains in liquid crystal elastomers under compression

Liquid crystal elastomers (LCEs) are lightly cross-linked polymer materials containing liquid crystal (LC) molecules with unique strain-induced director reorientation properties. Compressive studies on LCEs have been very little given the difficulty synthesizing sufficiently large monodomain block samples. Based on the continuum mechanics model of LCEs, the compressive behaviors of monodomain LCE blocks in plane stain with different initial directors between two rigid plates are systematically studied in this paper. The rotation of the director, especially the formation of lamellar domains, significantly changes the characteristics of the compressive stress-strain curves. Compression along the initial director will induce the formation of lamellar domains orthogonal to the loading axis due to the alternating rotation of the director after loading to a critical strain. The rotation of the director also leads to the stress plateau on the stress-strain curves. When the initial director is nearly parallel to the compression axis, the lamellar domains can still be observed in the central region of the sample bonded to the rigid plates, which is also related to the deformed morphology of the stress-free boundaries. If the initial director is slightly deviated from the loading axis, almost uniform rotation occurs in the central region of the sample, while the stress increases monotonically with strain hardening. The formation of lamellar domains is not only related to the angles between the initial director and the compressive loading axis, but also strongly depends on the geometrical and material parameters of the samples. For large aspect ratios or small anisotropy constants, the formation of lamellar domains may require compression sufficiently parallel to the initial director. Our work provides a deeper understanding of the behavior of LCEs under compression.

Analysis of stress and strain concentration around a centralized elliptical hole in a monodomain liquid crystal elastomer sheet

Liquid crystal elastomers (LCEs) are a kind of soft materials which couple the high elastic deformability with the unique properties of liquid crystals. Such combination endows notched LCEs unusual stress and strain concentration behaviors, which is preliminary discussed by us in the case of a large sheet with a centralized circular hole. Here we extend our study from circular holes to more generalized, elliptical holes. We investigate the stress and strain fields around a centralized elliptical hole in a LCE sheet subjected to uniaxial stretches by finite element methods. The effects of the shape factor, defined as the ratio of the minor-to-major axis of the ellipse, are mainly concerned. Compared with common elastomers like neoHookean, LCEs get higher stress and strain concentration factors (SCFs), and the location of maximal strain deviates slightly from that of maximal stress. With the decrease of the shape factor (a sharper ellipse) the SCFs of LCEs rise much severer than those of neoHookean, and the deviation is diminishing. In addition, as the stretch increases, the region near the root is getting close to an approximately uniaxial stress state, and the high strain region will extend non-monotonously along the hole edge, which differs from a monotonous extension of the high stress region. All the unusual behaviors of LCEs above are attributed to the spontaneous strain induced by director rotation. Attempts to correlate stress and strain concentration behaviors to the spontaneous strain are made in this article.

Skin-friendly and antibacterial monodomain liquid crystal elastomer actuator

Monodomain liquid crystal elastomers (mLCEs) are flexible and biocompatible smart materials that show unique behaviors of soft elasticity, anisotropy, and reversible shape changes above the nematic-isotropic transition temperature. Therefore, it has great potential for application in wearable devices and biologically. However, most of the reported mLCEs have nematic-isotropic transition temperature (TNI) higher than 60 °C; and above this TNI, the tensile strength of the mLCEs decreases by orders of magnitude. These issues have received little attention, limiting their application in humans. Herein, the TNI of mLCEs was reduced from 78.4 °C to 23.5 °C by substituting part of the rigid LC mesogens with a flexible backbone. The physical entanglement of hydrogen bonds between molecular chains alleviated the molecular chain slip caused by the long flexible backbone. The tensile strength remained constant during the phase transformation. Furthermore, dynamic disulfide bonds were used to modify the LC polymer network, imparting it with excellent antimicrobial, programmable, and self-healing properties. To realize its application in the closure of skin wounds, a porous PHG–mLCE/hydrogel patch that was breathable and waterproof was designed to increase skin adhesion (262 N/m).

Multiple shapes from a single nematic elastomer sheet activated via patterned illumination

Liquid crystal elastomers (LCEs) undergo a large uniaxial contraction upon thermal or optical stimulation. LCE sheets are often fabricated with a spatially patterned direction of contraction, which can sculpt the sheet into a Gauss-curved surface. Here, we instead consider LCE sheets subject to patterned stimulation intensity, leading to a control of contraction strength. We show such patterns may also sculpt a complex surface, but with the advantage that arbitrarily many surfaces may be achieved sequentially in the same sample, thus breaking the link between microstructure and shape. We first consider a monodomain LCE in which some regions are actuated and others are not. We discuss how to join actuated and unactuated regions compatibly, and use this design rule to generate patterns for cones, anti-cones, arrays of cones and a rolling bi-strip. We validate the patterns numerically via elastic shell simulations and demonstrate them experimentally via patterned photo-chemical actuation. Secondly, we consider an LCE disk with an azimuthal director profile actuated by a radially varying stimulus. We show, theoretically and numerically, how to design a stimulation profile to sculpt any surface of revolution. Such re-configurable actuation offers enticing possibilities for haptics, robotics and locomotion.

Multisensory Flexible Braille Interactive Device Based on Liquid Crystal Elastomers

Traditional electronic braille devices’ rigid and complex structure limits their portability while satisfying braille output. Main-chain monodomain liquid crystal elastomers (m-LCEs) can achieve high contraction deformation under external stimulation conditions; it has broad application prospects in the human–machine interaction with the biological tissue safety and flexibility of LCEs. A multisensory flexible braille interactive device based on LCEs is proposed in this article. It utilizes the good reversible shape-memory performance of m-LCEs to solve the problems of complex structure design, poor portability, high cost, and low control stability in traditional rigid mechanical braille readers. The fixed-point stretchable convex lattice and the nonactuation performance-based film are accurately distinguished and fabricated by compression molding. Combined with the ultrathin flexible electric heating layer, the reversible contraction of the braille point is realized, and the braille point is given the dual perception of height difference and temperature difference. Moreover, matching circuit design can realize braille input by press and braille output by convex–concave conversion. Furthermore, we try to introduce thermochromic powders, referring to the principle of light-emitting diode (LED) imaging, to transform the pattern concept of visually impaired people in minds into color information that ordinary people can observe.

A High-Fidelity Preparation Method for Liquid Crystal Elastomer Actuators.

Three-dimensional (3D) structural actuators based on monodomain liquid crystal elastomers (mLCEs) show a wide range of potential applications. A direct ink writing technique has been developed to print LCE structures. It is still a challenge to print high-precision 3D-mLCE actuators. Here, a method of wet 3D printing combined with freeze-drying is proposed. The coagulation bath is designed to restrain the nascent fiber disturbance of the capillary wave and weight by adjusting the ink viscosity and printing speed to control the LC molecular order, enabling uniform (B = 1.02) fibers with a high degree of orientational alignment (S = 0.45) of the mesogens. Furthermore, dynamic disulfide bond formation was used as the cross-linking point, which can allow the LCE network structure to be continuously cured to ensure adjacent layers are effectively bonded and, in combination with freeze-drying, produce the 3D-mLCE actuators of fidelity architecture (98.37 vol %) by printing. The actuators have excellent actuating strain (45.12%), and the dynamic disulfide bond makes them programmable. Finally, a printed bionic starfish and a printed bionic hand can easily grab regular and irregular objects. This work provides a feasible scheme for fabricating complex 3D-mLCEs with reversible changes in shape.

Effects of network structure of main-chain liquid crystal elastomer on its thermal actuation performance

The effect of the network structure on the thermal actuation of the main-chain liquid crystal elastomers (LCEs) was studied by controlling the strand length and crosslinking density of the network. The LCEs were prepared with the thiol-terminated oligomers synthesized via a thiol-acrylate Michael addition reaction between dithiol and diacrylate monomers. The LCE network structure was formed by crosslinking the oligomers using the pentaerythritol tetraacylate crosslinkers and coupling between the thiol end groups in the oligomer to form disulfide linkages. The monodomain LCE (MLCE) films were fixed by the dynamic exchange reaction between disulfide linkages through ultraviolet irradiation after drawing the polydomain LCE films. The maximum degree of actuation was obtained when 50% of the available thiol groups were crosslinked with the acrylate groups of the crosslinkers. The degree of actuation increased with the oligomer length for sufficiently high crosslinking density. However, the degree of actuation decreased with the oligomer length after reaching the maximum especially for low crosslinker density because crosslinking with long oligomers did not provide enough crosslinking sites and disulfide linkages. Thus, the oligomer length and crosslinking density of the MLCE are important control factors during LCE preparation to obtain the best actuation performance of the MLCE film.

Stress-Induced Self-Alignment Monodomain Liquid Crystal Elastomer Fiber

Stress-Induced Self-Alignment Monodomain Liquid Crystal Elastomer Fiber