Separating Charge Centers of Chain Segments in Dielectric Elastomer through Steric Hindrance Engineering.

Theoretically, separating the positive and negative charge centers of the chain segments of dielectric elastomers (DEs) is a viable alternative to the conventional decoration of chain backbone with polar handles, since it can dramatically increase the dipole vector and hence the dielectric constant (ε') of the DEs while circumvent the undesired impact of the decorated polar handles on the dielectric loss (tan δ). Herein, a novel and universal method is demonstrated to achieve effective separation of the charge centers of chain segments in homogeneous DEs by steric hindrance engineering, i.e., by incorporating a series of different included angle-containing building blocks into the networks. Both experimental and simulation results have shown that the introduction of these building blocks can create a spatially fixed included angle between two adjacent chain segments, thus separating the charge center of the associated region. Accordingly, incorporating a minimal amount of these building blocks (≈5 mol%) can lead to a considerably sharp increase (≈50%) in the ε' of the DEs while maintaining an extremely low tan δ (≈0.006@1 kHz), indicating that this methodology can substantially optimize the dielectric performance of DEs based on a completely different mechanism from the established methods.

Reprogramming Photoresponsive Liquid Crystalline Elastomer via Force-Directed Evaporation.

Incorporating photothermal agents into thermoresponsive liquid crystalline elastomers (LCEs) offers remote and spatio-temporal control in actuation. Typically, both the light responsiveness and actuation behaviors are fixed since the agent doping and mesogen alignment are conducted before network formation. Here, we report an approach that enables programming photoresponsive LCEs after synthesis via force-directed evaporation. Different photothermal agents can be doped or removed by swelling the fully cross-linked LCEs in a specific solution, achieving the introduction and erasing of the photoresponsiveness. Moreover, the network swelling deletes the registered alignment, which allows for redefining the molecular order via re-evaporating the solvent with force imposed. This "one stone, two birds" strategy paves the way to simultaneously program/reprogram the actuation mode and responsiveness of LCEs, even in a spatio-selective manner to achieve complex actuations. Our approach is expandable to three-dimensional (3D) printed LCEs to access geometrically sophisticated shape-changing.

Multimodal Autonomous Locomotion of Liquid Crystal Elastomer Soft Robot.

Self-oscillation phenomena observed in nature serve as extraordinary inspiration for designing synthetic autonomous moving systems. Converting self-oscillation into designable self-sustained locomotion can lead to a new generation of soft robots that require minimal/no external control. However, such locomotion is typically constrained to a single mode dictated by the constant surrounding environment. In this study, a liquid crystal elastomer (LCE) robot capable of achieving self-sustained multimodal locomotion, with the specific motion mode being controlled via substrate adhesion or remote light stimulation is presented. Specifically, the LCE is mechanically trained to undergo repeated snapping actions to ensure its self-sustained rolling motion in a constant gradient thermal field atop a hotplate. By further fine-tuning the substrate adhesion, the LCE robot exhibits reversible transitions between rolling and jumping modes. In addition, the rolling motion can be manipulated in real time through light stimulation to perform other diverse motions including turning, decelerating, stopping, backing up, and steering around complex obstacles. The principle of introducing an on-demand gate control offers a new venue for designing future autonomous soft robots.

Repeatedly Programmable Liquid Crystal Dielectric Elastomer with Multimodal Actuation.

Dielectric elastomers (DEs) are actuatable under an electric field, whose large strain and fast response speed compare favorably with natural muscles. However, the actuation of DE-based devices is generally limited to a single mode and cannot be reconfigured after fabrication, which pales in comparison to biological counterparts given the ability to alter actuation modes according to external conditions. To address this, liquid crystal dielectric elastomers (LC-DEs) that can alter the dielectric actuation modes based on the thermally triggered shape-changing are prepared. Specifically, the two shapes through the LC phase transition possess different bending stiffness, which leads to distinct actuation modes after an electric field is applied. Moreover, the two shapes can be individually programmed/reprogrammed, that is, the one before the transition is regulated through force-directed solvent evaporation and the one after the transition is via bond exchange-enabled stress relaxation. As such, the multimodal dielectric actuation behaviors upon temperature change can be readily diversified. Meanwhile, the space charge mechanism endows LC-DEs with the significantly reduced driving e-field (8 V µm-1) and bidirectional actuation manners. It is believed this unique adaptivity in the actuation modes under a low electric field shall offer versatile designs for practical soft robots.

Rotini-like MXene@LCE Actuator with Diverse and Programmable Actuation Based on Dual-mode Synergy.

Liquid crystalline elastomer (LCE) exhibits muscle-like actuation upon order-disturbed stimulus, offering ample room for designing soft robotic systems. Multimodal LCE is demonstrated to unleash the potential to perform multitasks. However, each actuation mode is typically isolated. In contrast, coordination between different actuation modes based on an MXene-doped LCE is realized, whose actuation can be triggered either by directly heating/cooling or using near-infrared light due to the photo-thermal effect of MXene. As such, the two activation modes (heat and light) not only can work individually to offer stable actuation under different conditions but also can collaborate synergistically to generate more intelligent motions, such as achieving the brake and turn of an autonomous rolling. The principle therefore can diversify the design principles for multifunctional soft actuators and robotics.

High speed underwater hydrogel robots with programmable motions powered by light.

Stimuli-responsive shape-changing hydrogels are attractive candidates for use as underwater soft robots. The bottleneck lies in the low actuation speed inherently limited by the water diffusion between hydrogels and their surrounding environment. In addition, accessing complex motions is restricted by the material fabrication methods. Here we report a hitherto unknown mechanism to achieve high-speed and programmable actuations for a disulfide crosslinked thermally responsive hydrogel. The dynamic photo-activated disulfide bond exchange allows photo-mechanical programming to introduce spatio-selective network anisotropy. This gives rise to an actuation behavior dominated by thermally driven conformation change of the locally oriented polymer chains instead of the common mass-diffusion-based mechanism. With the incorporation of photothermal fillers, light-powered oscillation at frequencies as high as 1.7 Hz is realized. This, coupled with the versatility of the programming, allows access to robots with diverse high-speed motions including continuous swimming, step-wise walking, and rotating.

Network Topology Optimization for Alignment Programming of a Dynamic Liquid Crystalline Organo-Gel.

Liquid crystalline elastomers (LCEs) exhibit muscle-like actuation upon an external stimulus. To control this, various alignment programming strategies have been developed over the past decades. Among them, force-directed solvent evaporation, namely, that the alignment depends on the applied external force during solvent evaporation, is appreciated for its universality in material design and versatility in attainable actuations. Here, we investigate the influence of network topology on the alignment programming of a liquid crystalline (LC) organo-gel via varying feeding ratios of the monomers. As a result, distinct self-supporting actuations can be repeatedly introduced into a topology-optimized LC organo-gel. Beyond this, the bond exchange reaction of the embedded ester groups can be activated upon heating, which enables alignment manipulation based on dynamic network reconfiguration after drying. The availability of inviting two distinct programming strategies into one LCE network allows us to regulate the LCE alignment at both the gel and dried states, offering ample room to diversify actuation manners. Our design principle shall be adopted by other dynamic LCE systems owing to its maneuverability.

Programming actuation onset of a liquid crystalline elastomer via isomerization of network topology.

Tuning actuation temperatures of liquid crystalline elastomers (LCEs) achieves control of their actuation onsets, which is generally accomplished in the synthesis step and cannot be altered afterward. Multiple actuation onsets in one LCE can be encoded if the post-synthesis regulation of actuation temperature can be spatiotemporally achieved. This would allow realizing a logical time-evolution of actuation, desired for future soft robots. Nevertheless, this task is challenging given the additional need to ensure mesogen alignment required for actuation. We achieved this goal with a topology isomerizable network (TIN) of LCE containing aromatic and aliphatic esters in the mesogenic and amorphous phases, respectively. These two ester bonds can be distinctly activated for transesterification. The homolytic bond exchange between aliphatic esters allows mechanically induced mesogen alignment without affecting the mesogenic phase. Most importantly, the heterolytic exchange between aromatic and aliphatic esters changes the actuation temperature under different conditions. Spatial control of the two mechanisms via a photo-latent catalyst unleashes the freedom in regulating actuation temperature distribution, yielding unusual controllability in actuation geometries and logical sequence. Our principle is generally applicable to common LCEs containing both aromatic and aliphatic esters.

Soft Mechanical Metamaterials with Transformable Topology Protected by Stress Caching.

Maxwell lattices possess distinct topological states that feature mechanically polarized edge behaviors and asymmetric dynamic responses protected by the topology of their phonon bands. Until now, demonstrations of non-trivial topological behaviors from Maxwell lattices have been limited to fixed configurations or have achieved reconfigurability using mechanical linkages. Here, a monolithic transformable topological mechanical metamaterial is introduced in the form of a generalized kagome lattice made from a shape memory polymer (SMP). It is capable of reversibly exploring topologically distinct phases of the non-trivial phase space via a kinematic strategy that converts sparse mechanical inputs at free edge pairs into a biaxial, global transformation that switches its topological state. All configurations are stable in the absence of confinement or a continuous mechanical input. Its topologically-protected, polarized mechanical edge stiffness is robust against broken hinges or conformational defects. More importantly, it shows that the phase transition of SMPs that modulate chain mobility, can effectively shield a dynamic metamaterial's topological response from its own kinematic stress history, referred to as "stress caching". This work provides a blueprint for monolithic transformable mechanical metamaterials with topological mechanical behavior that is robust against defects and disorder while circumventing their vulnerability to stored elastic energy, which will find applications in switchable acoustic diodes and tunable vibration dampers or isolators.

Regenerative Living 4D Printing via Reversible Growth of Polymer Networks.

Living creatures possess complex geometries, exceptional adaptability, and continuous growing and regenerating characteristics, which are difficult for synthetic materials to imitate simultaneously. A living polymer network with these features is reported. The polymer can be digitally printed into arbitrary 3D shapes and subsequently undergoes growth via living polymerization of a monomer as the nutrient. This leads to macroscopic dimensional growth and transforms the printed amorphous network into a crystallizable network, resulting in geometric adaptability via a shape-memory mechanism. By controlling the localized growth, an initial homogeneous structure can be converted into a geometrically different heterogeneous structure composed of materials with different properties (crystallization and mechanical properties). After growth, the original network can be chemically regenerated for regrowth. With this regenerative living 4D printing, one 3D-printed seed template can be turned into different derivatives with distinct geometries and mechanical properties when repeated regeneration is conducted in different localized regions and the degree of regrowth is varied.

Dielectric Polymer with Designable Large Motion under Low Electric Field.

Dielectric elastomers (DEs) can demonstrate fast and large in-plane expansion/contraction due to electric field (e-field)-induced Maxwell stress. For robotic applications, it is often necessary that the in-plane actuation is converted into out-of-plane motions with mechanical frames. Despite their performance appeal, their high driving e-field (20-100 V µm-1 ) demands bulky power accessories and severely compromises their durability. Here, a dielectric polymer that can be programmed into diverse motions actuated under a low e-field (2-10 V µm-1 ) is reported. The material is a crystalline dynamic covalent network that can be reconfigured into arbitrary 3D geometries. This gives rise to a geometric effect that markedly amplifies the actuation, leading to designable large motions when the dielectric polymer is heated above its melting temperature to become a DE. Additionally, the crystallization transition enables dynamic multimodal motions and active deployability. These attributes result in unique design versatility for soft robots.

Rapidly and Repeatedly Reprogrammable Liquid Crystalline Elastomer via a Shape Memory Mechanism.

Realization of muscle-like actuation for a liquid crystal elastomer (LCE) requires mesogen alignment, which is typically achieved/fixed chemically during the synthesis. Post-synthesis regulation of the alignment in a convenient and repeatable manner is highly desirable yet challenging. Here, a dual-phase LCE network is designed and synthesized with a crystalline melting transition above a liquid crystalline transition. The crystalline phase can serve as an "alignment frame" to fix any mechanical deformation via a shape memory mechanism, leading to corresponding mesogen alignment in the liquid crystalline phase. The alignment can be erased by melting, which can be the starting point for reprogramming. This strategy that relies on a physical shape memory transition for mesogen alignment permits repeated reprogramming in a timescale of seconds, in stark contrast to typical methods. It further leads to unusual versatility in designing 3D printed LCE with unlimited programmable actuation modes.

An Orthogonal Dynamic Covalent Polymer Network with Distinctive Topology Transformations for Shape- and Molecular Architecture Reconfiguration.

Bond exchange in a typical dynamic covalent polymer network allows access to macroscopic shape reconfigurability, but the network architecture is not altered. An alternative possibility is that the network architecture can be designed to switch to various topological states corresponding to different material properties. Achieving both in one network can expand the material scope, but their intrinsically conflicting mechanisms make it challenging. We design a dynamic covalent network that can undergo two orthogonal topological transformations, namely transesterification on the branched chains and olefin metathesis on the mainframe. This allows independent control of the macroscopic shape and molecular architecture. With this design, we illustrate a bottlebrush network with programmable shape and spatially definable mechanical properties. Our strategy paves a way to on-demand regulation of network polymers.

Solvent-Assisted 4D Programming and Reprogramming of Liquid Crystalline Organogels.

Encoding molecular ordering during liquid crystalline network (LCN) formation endows preprogrammed but fixed shape morphing in response to external stimuli. The incorporation of dynamic covalent bonds enables shape reprogramming but also permanently alters the network structures. Here, an entropic approach that can program complex shapes via directed solvent evaporation from an isotropic LCN organogel is discoursed. Different shapes can be erased and reprogrammed from the same LCN on demand depending on the modes of deformation of the organogel during solvent evaporation. The ability to decouple network synthesis and molecular alignment relaxes the requirements to LCN chemistry and alignment methods, allowing for the realization of a variety of origami/kirigami structures and 4D shape morphing of LCNs printed from the digital light processing technique with unattainable spatial and temporal controls.

Ultrafast Digital Fabrication of Designable Architectured Liquid Crystalline Elastomer.

The muscle-like activities of liquid crystalline elastomers (LCEs) offer great potential for designing future soft machines. Their motion complexity, however, relies on inflexible and cumbersome mesogen alignment techniques. Here, a digital photocuring method for ultrafast template-free fabrication of LCE artificial muscles capable of designable complex motions is reported. This method utilizes the intrinsic light attenuation in the through-plane direction to create mesogen alignment for reversible bending action. To turn this simple actuation into complex motions, the principles of muscles are borrowed which realize diverse motions through the cooperative actions of otherwise simple contraction/expansion of individual muscle bundles. Specifically, the spatiotemporal digital light is utilized to design LCE architectures composed of strategically arranged bending modules. As such, LCE capable of highly designable motions can be fabricated within 25 s light curing without employing any physical alignment templates, which offers an attractive option toward designing functionally diverse soft machines.

On demand shape memory polymer via light regulated topological defects in a dynamic covalent network.

The ability to undergo bond exchange in a dynamic covalent polymer network has brought many benefits not offered by classical thermoplastic and thermoset polymers. Despite the bond exchangeability, the overall network topologies for existing dynamic networks typically cannot be altered, limiting their potential expansion into unexplored territories. By harnessing topological defects inherent in any real polymer network, we show herein a general design that allows a dynamic network to undergo rearrangement to distinctive topologies. The use of a light triggered catalyst further allows spatio-temporal regulation of the network topology, leading to an unusual opportunity to program polymer properties. Applying this strategy to functional shape memory networks yields custom designable multi-shape and reversible shape memory characteristics. This molecular principle expands the design versatility for network polymers, with broad implications in many other areas including soft robotics, flexible electronics, and medical devices.

Light-triggered topological programmability in a dynamic covalent polymer network.

Dynamic covalent polymer networks exhibit unusual adaptability while maintaining the robustness of conventional covalent networks. Typically, their network topology is statistically nonchangeable, and their material properties are therefore nonprogrammable. By introducing topological heterogeneity, we demonstrate a concept of topology isomerizable network (TIN) that can be programmed into many topological states. Using a photo-latent catalyst that controls the isomerization reaction, spatiotemporal manipulation of the topology is realized. The overall result is that the network polymer can be programmed into numerous polymers with distinctive and spatially definable (thermo-) mechanical properties. Among many opportunities for practical applications, the unique attributes of TIN can be explored for use as shape-shifting structures, adaptive robotic arms, and fracture-resistant stretchable devices, showing a high degree of design versatility. The TIN concept enriches the design of polymers, with potential expansion into other materials with variations in dynamic covalent chemistries, isomerizable topologies, and programmable macroscopic properties.

Synergetic Chemical and Physical Programming for Reversible Shape Memory Effect in a Dynamic Covalent Network with Two Crystalline Phases.

A recently emerged reversible shape memory effect greatly extends the capability of shape memory polymers and their practical potential. Physical confinement and chemical fixation are individually known to be effective in introducing network anisotropy essential for reversible shape memory. Herein, we demonstrate that synergetic combination of these two mechanisms effectively diversifies the shape-shifting behavior. Specifically, we introduce a transesterification catalyst into a network containing two crystalline phases: poly(ε-caprolactone) (PCL) and poly(ω-pentadecalactone) (PPDL). The reversible shape memory behavior of the resulting system can be programmed via the physical confinement by the PPDL phase and the chemical plasticity by the dynamic ester exchange. We illustrate that the two programming mechanisms can operate in a noninterfering way that allows achieving a synergetic benefit, notably realizing a zero-set reversible shape memory behavior. Our study points to a direction in diversifying the behaviors of reversible shape memory polymers and expands the scope for potential engineering devices.

Programming a crystalline shape memory polymer network with thermo- and photo-reversible bonds toward a single-component soft robot.

The need to support the two most basic functions [three-dimensional (3D)-shaped support and actuation] independently for a typical robot demands that at least two components should be used in its construction. Therefore, component assembly is unavoidable despite the ultimate dream of creating assembly-free robots. We devise a strategy that uses a programmable crystalline shape memory polymer with thermo- and photo-reversible bonds to create a single-component robot. The global 3D-shaped structural support is fabricated via a plasticity-based origami technique enabled by the thermo-reversible bonds. More critically, precisely controlled localized actuation can be programmed into the 3D origami via spatially defined reversible shape memory using the photo-reversible bonds. The overall result is that a polymer thin film can be programmed into various soft robots including a 3D crane and an elephant. Besides reversible shape memory, other types of actuation mechanisms can be potentially introduced via a similar principle. Thus, our strategy represents a general method to create single-component soft robots.