Optomechanical computing in liquid crystal elastomers.

Embodied decision-making in soft, engineered matter has sparked recent interest towards the development of intelligent materials. Such decision-making capabilities can be realized in soft materials via digital information processing with combinational logic operations. Although previous research has explored soft material actuators and embedded logic in soft materials, achieving a high degree of autonomy in these material systems remains a challenge. Light is an ideal stimulus to trigger information processing in soft materials due to its low thermal effect and remote use. Thus, one approach for developing soft, autonomous materials is to integrate optomechanical computing capabilities in photoresponsive materials. Here, we establish a methodology to embed combinational logic circuitry in a photoresponsive liquid crystal elastomer (LCE) film. These LCEs are designed with embedded switches and integrated circuitry using liquid metal-based conductive traces. The resulting optomechanical computing LCEs can effectively process optical information via light, thermal, and mechanical energy conversion. The methods introduced in this work to fabricate a material capable of optical information processing can facilitate the implementation of a sense of sight in soft robotic systems and other compliant devices.

Recent Advances in Electro-Optic Response of Polymer-Stabilized Cholesteric Liquid Crystals.

Cholesteric liquid crystals (CLC) are molecules that can self-assemble into helicoidal superstructures exhibiting circularly polarized reflection. The facile self-assembly and resulting optical properties makes CLCs a promising technology for an array of industrial applications, including reflective displays, tunable mirror-less lasers, optical storage, tunable color filters, and smart windows. The helicoidal structure of CLC can be stabilized via in situ photopolymerization of liquid crystal monomers in a CLC mixture, resulting in polymer-stabilized CLCs (PSCLCs). PSCLCs exhibit a dynamic optical response that can be induced by external stimuli, including electric fields, heat, and light. In this review, we discuss the electro-optic response and potential mechanism of PSCLCs reported over the past decade. Multiple electro-optic responses in PSCLCs with negative or positive dielectric anisotropy have been identified, including bandwidth broadening, red and blue tuning, and switching the reflection notch when an electric field is applied. The reconfigurable optical response of PSCLCs with positive dielectric anisotropy is also discussed. That is, red tuning (or broadening) by applying a DC field and switching by applying an AC field were both observed for the first time in a PSCLC sample. Finally, we discuss the potential mechanism for the dynamic response in PSCLCs.

Photo-Crosslinkable Inorganic/Organic Sulfur Polymers.

Inverse vulcanization techniques are used to fabricate thermodynamically stable, sulfur polymers. Sulfur-based polymers exhibit higher refractive indices and improved transparency in the mid-wave infrared region compared with most organic polymers. Herein, the postsynthetic modification of sulfur polymers created via inverse vulcanization to generate novel, inorganic/organic photoresists is discussed. Amine-containing sulfur resins are postfunctionalized with cross-linkable alkynes. The sulfur-based materials undergo rapid photo-crosslinking to generate patternable films within 10 min under UV irradiation (365 nm). The development of these resins enables sulfur polymers to be utilized in processes where spatial and hierarchical control is necessary. The generation of this class of materials also expands on sulfur-based organic polymer systems with optical applications.

Liquid crystal elastomer based dynamic device for urethral support: Potential treatment for stress urinary incontinence.

Stress urinary incontinence (SUI) is characterized by the involuntary loss of urine due to increased intra-abdominal pressure during coughing, sneezing, or exercising. SUI affects 20-40% of the female population and is exacerbated by aging. Severe SUI is commonly treated with surgical implantation of an autologous or a synthetic sling underneath the urethra for support. These slings, however, are static, and their tension cannot be non-invasively adjusted, if needed, after implantation. This study reports the fabrication of a novel device based on liquid crystal elastomers (LCEs) capable of changing shape in response to temperature increase induced by transcutaneous IR light. The shape change of the LCE-based device was characterized in a scar tissue phantom model. An in vitro urinary tract model was designed to study the efficacy of the LCE-based device to support continence and adjust sling tension with IR illumination. Finally, the device was acutely implanted and tested for induced tension changes in female multiparous New Zealand white rabbits. The LCE device achieved 5.6% ± 1.1% actuation when embedded in an agar gel with an elastic modulus of 100 kPa. The corresponding device temperature was 44.9 °C ± 0.4 °C, and the surrounding agar temperature stayed at 42.1 °C ± 0.4 °C. Leaking time in the in vitro urinary tract model significantly decreased (p < 0.0001) when an LCE-based cuff was sutured around the model urethra from 5.2min ± 1min to 2min ±0.5min when the cuff was illuminated with IR light. Normalized leak point force (LPF) increased significantly (p = 0.01) with the implantation of an LCE-CB cuff around the bladder neck of multiparous rabbits. It decreased significantly (p = 0.023) when the device was actuated via IR light illumination. These results demonstrate that LCE material could be used to fabricate a dynamic device for treating SUI in women.

Programmable Shape Change in Semicrystalline Liquid Crystal Elastomers.

Liquid crystal elastomers (LCEs) are stimuli-responsive materials capable of reversible and programmable shape change in response to an environmental stimulus. Despite the highly responsive nature of these materials, the modest elastic modulus and blocking stress exhibited by these actuating materials can be limiting in some engineering applications. Here, we engineer a semicrystalline LCE, where the incorporation of semicrystallinity in a lightly cross-linked liquid crystalline network yields tough and highly responsive materials. Directed self-assembly can be employed to program director profiles through the thickness of the semicrystalline LCE. In short, we use the alignment of a liquid crystal monomer phase to pattern the anisotropy of a semicrystalline polymer network. Both the semicrystalline-liquid crystalline and liquid crystalline-isotropic phase transition temperatures provide controllable shape transformations. A planarly aligned sample's normalized dimension parallel to the nematic director decreases from 1 at room temperature to 0.42 at 250 °C. The introduction of the semicrystalline nature also enhances the mechanical properties exhibited by the semicrystalline LCE. Semicrystalline LCEs have a storage modulus of 390 MPa at room temperature, and monodomain samples are capable of generating a contractile stress of 2.7 MPa on heating from 25 to 50 °C, far below the nematic to isotropic transition temperature. The robust mechanical properties of this material combined with the high actuation strain can be leveraged for applications such as soft robotics and actuators capable of doing significant work.

4D-Printing of Photoswitchable Actuators.

Shape-switching behavior, where a transient stimulus induces an indefinitely stable deformation that can be recovered on exposure to another transient stimulus, is critical to building smart structures from responsive polymers as continue power is not needed to maintain deformations. Herein, we 4D-print shape-switching liquid crystalline elastomers (LCEs) functionalized with supramolecular crosslinks, dynamic covalent crosslinks, and azobenzene. The salient property of shape-switching LCEs is that light induces long-lived, deformation that can be recovered on-demand by heating. UV-light isomerizes azobenzene from trans to cis, and temporarily breaks the supramolecular crosslinks, resulting in a programmed deformation. After UV, the shape-switching LCEs fix more than 90 % of the deformation over 3 days by the reformed supramolecular crosslinks. Using the shape-switching properties, we print Braille-like actuators that can be photoswitched to display different letters. This new class of photoswitchable actuators may impact applications such as deployable devices where continuous application of power is impractical.

4D-Printable Liquid Metal-Liquid Crystal Elastomer Composites.

Soft actuators that undergo programmable shape change in response to a stimulus are enabling components of future soft robots and other soft machines. Strategies to power these actuators often require the incorporation of rigid, electrically conductive materials into the soft actuator, thus limiting the compliance and shape change of the material. In this study, we develop a 4D-printable composite composed of liquid crystal elastomer (LCE) matrix with dispersed droplets of eutectic gallium indium alloy (EGaIn). Using deformable EGaIn droplets in place of rigid conductive fillers preserves the compliance and shape-morphing properties of the LCE. The process enables 4D-printed LCE actuators capable of photothermal and electrothermal actuation. At low liquid metal (LM) concentrations (71 wt %), the composite actuator exhibits a photothermal response upon irradiation of near-IR light. Printed actuators with a twisted nematic configuration are capable of bending angles of 150° at 800 mW cm-2. At higher LM concentrations (88 wt %), the embedded LM droplets can form percolating networks that conduct electricity and enable electrical Joule heating of the LCE. Actuation strain ranging from 5 to 12% is controlled by the amount of electrical power that is delivered to the composite. We also introduce a method for multimaterial printing of monolithic structures where the LM filler loading is spatially varied. These multifunctional materials exhibit innate responsivity where the actuator behaves as an electrical switch and can report one of two states (on/off). These multiresponsive, 4D-printable composites enable multifunctional, mechanically active structures that can be powered with IR light or low DC voltages.

Processing advances in liquid crystal elastomers provide a path to biomedical applications.

Liquid crystal elastomers (LCEs) are a class of stimuli-responsive polymers that undergo reversible shape-change in response to environmental changes. The shape change of LCEs can be programmed during processing by orienting the liquid crystal phase prior to crosslinking. The suite of processing techniques that has been developed has resulted in a myriad of LCEs with different shape-changing behavior and mechanical properties. Aligning LCEs via mechanical straining yields large uniaxial actuators capable of a moderate force output. Magnetic fields are utilized to control the alignment within LCE microstructures. The generation of out-of-plane deformations such as bending, twisting, and coning is enabled by surface alignment techniques within thin films. 4D printing processes have emerged that enable the fabrication of centimeter-scale, 3D LCE structures with a complex alignment. The processing technique also determines, to a large extent, the potential applications of the LCE. For example, 4D printing enables the fabrication of LCE actuators capable of replicating the forces generated by human muscles. Employing surface alignment techniques, LCE films can be designed for use as coatings or as substrates for stretchable electronics. The growth of new processes and strategies opens and strengthens the path for LCEs to be applicable within biomedical device designs.

Size of liquid metal particles influences actuation properties of a liquid crystal elastomer composite.

Composites of liquid crystal elastomer (LCE) that are electrically conductive have the potential to function as soft "artificial muscle" actuators that can be reversibly stimulated with electrical Joule-heating. Conductivity can be achieved by embedding the LCE with droplets of an alloy of gallium and indium that is liquid at room temperature. These soft artificial muscles are capable of >50% reversible actuation with an applied load. The key to actuation at high loadings of liquid metal (LM) is that the droplets deform with the surrounding matrix. By controlling the size of LM droplets through simple processing techniques, we show that the actuator properties of the LM-LCE muscle can be tuned. For example, composites with smaller liquid metal particles (ca. 10 µm or less) are stiffer than those with larger liquid metal particles (ca. >100 µm) and are capable of greater force output. However, smaller particles reduce actuation strain and composites with large particles exhibit significantly greater stroke length. Such tunability in actuation properties permits the fabrication of specialized soft artificial muscles, where processing of the composite controls actuation strain and actuation force.

Degradation-Induced Actuation in Oxidation-Responsive Liquid Crystal Elastomers.

Stimuli-responsive materials that exhibit a mechanical response to specific biological conditions are of considerable interest for responsive, implantable medical devices. Herein, we report the synthesis, processing and characterization of oxidation-responsive liquid crystal elastomers that demonstrate programmable shape changes in response to reactive oxygen species. Direct ink writing (DIW) is used to fabricate Liquid Crystal Elastomers (LCEs) with programmed molecular orientation and anisotropic mechanical properties. LCE structures were immersed in different media (oxidative, basic and saline) at body temperature to measure in vitro degradation. Oxidation-sensitive hydrophobic thioether linkages transition to hydrophilic sulfoxide and sulfone groups. The introduction of these polar moieties brings about anisotropic swelling of the polymer network in an aqueous environment, inducing complex shape changes. 3D-printed uniaxial strips exhibit 8% contraction along the nematic director and 16% orthogonal expansion in oxidative media, while printed LCEs azimuthally deform into cones 19 times their original thickness. Ultimately, these LCEs degrade completely. In contrast, LCEs subjected to basic and saline solutions showed no apparent response. These oxidation-responsive LCEs with programmable shape changes may enable a wide range of applications in target specific drug delivery systems and other diagnostic and therapeutic tools.

A multifunctional shape-morphing elastomer with liquid metal inclusions.

Natural soft tissue achieves a rich variety of functionality through a hierarchy of molecular, microscale, and mesoscale structures and ordering. Inspired by such architectures, we introduce a soft, multifunctional composite capable of a unique combination of sensing, mechanically robust electronic connectivity, and active shape morphing. The material is composed of a compliant and deformable liquid crystal elastomer (LCE) matrix that can achieve macroscopic shape change through a liquid crystal phase transition. The matrix is dispersed with liquid metal (LM) microparticles that are used to tailor the thermal and electrical conductivity of the LCE without detrimentally altering its mechanical or shape-morphing properties. Demonstrations of this composite for sensing, actuation, circuitry, and soft robot locomotion suggest the potential for versatile, tissue-like multifunctionality.

Four-dimensional Printing of Liquid Crystal Elastomers.

Three-dimensional structures capable of reversible changes in shape, i.e., four-dimensional-printed structures, may enable new generations of soft robotics, implantable medical devices, and consumer products. Here, thermally responsive liquid crystal elastomers (LCEs) are direct-write printed into 3D structures with a controlled molecular order. Molecular order is locally programmed by controlling the print path used to build the 3D object, and this order controls the stimulus response. Each aligned LCE filament undergoes 40% reversible contraction along the print direction on heating. By printing objects with controlled geometry and stimulus response, magnified shape transformations, for example, volumetric contractions or rapid, repetitive snap-through transitions, are realized.