Tunable Photocontrolled Motions Using Stored Strain Energy in Malleable Azobenzene Liquid Crystalline Polymer Actuators

A new strategy for enhancing the photoinduced mechanical force is demonstrated using a reprocessable azobenzene‐containing liquid crystalline network (LCN). The basic idea is to store mechanical strain energy in the polymer beforehand so that UV light can then be used to generate a mechanical force not only from the direct light to mechanical energy conversion upon the trans–cis photoisomerization of azobenzene mesogens but also from the light‐triggered release of the prestored strain energy. It is shown that the two mechanisms can add up to result in unprecedented photoindued mechanical force. Together with the malleability of the polymer stemming from the use of dynamic covalent bonds for chain crosslinking, large‐size polymer photoactuators in the form of wheels or spring‐like “motors” can be constructed, and, by adjusting the amount of prestored strain energy in the polymer, a variety of robust, light‐driven motions with tunable rolling or moving direction and speed can be achieved. The approach of prestoring a controllable amount of strain energy to obtain a strong and tunable photoinduced mechanical force in azobenzene LCN can be further explored for applications of light‐driven polymer actuators.     

Photoinduced Plasticity in Cross‐Linked Liquid Crystalline Networks

Photoactivated reversible addition fragmentation chain transfer (RAFT)‐based dynamic covalent chemistry is incorporated into liquid crystalline networks (LCNs) to facilitate spatiotemporal control of alignment, domain structure, and birefringence. The RAFT‐based bond exchange process, which leads to stress relaxation, is used in a variety of conditions, to enable the LCN to achieve a near‐equilibrium structure and orientation upon irradiation. Once formed, and in the absence of subsequent triggering of the RAFT process, the (dis)order in the LCN and its associated birefringence are evidenced at all temperatures. Using this approach, the birefringence, including the formation of spatially patterned birefringent elements and surface‐active topographical features, is selectively tuned by adjusting the light dose, temperature, and cross‐linking density.     

A Cut‐and‐Weld Process to 3D Architectures from Multiresponsive Crosslinked Liquid Crystalline Polymers

Crosslinked liquid crystalline polymers (CLCPs) have garnered extensive attention in recent years for their significant values in the design of light‐driven soft actuators. However, poor processabilities due to the insoluble and infusible crosslinked networks prevent their practical applications severely. In this study, a weldable azobenzene‐containing CLCP is designed with photo‐ and humidity‐responsive actuations, which enables a cut‐and‐weld process to 3D CLCP architectures. The tensile properties and stability are almost unchanged after welding, much better than those of the films pasted by common adhesive tapes. Meanwhile, the mechanisms of the welding process are clarified on the base of surface hydrogen bonding and further crosslinking. By taking advantage of the cut‐and‐weld process, a 3D “claw” integrated into a robotic arm is realized for grabbing millimeter‐scale objects by remote control. This work enhances significantly not only the processability of CLCP films but also the utilization of leftover pieces, which provides an efficient approach to create functional 3D structures from film precursors for the potential application in the smart materials.     

Gold Nanoparticles Thin Films with Thermo‐ and Photoresponsive Plasmonic Properties Realized with Liquid‐Crystalline Ligands

Robust synthesis of large‐scale self‐assembled nanostructures with long‐range organization and a prominent response to external stimuli is critical to their application in functional plasmonics. Here, the first example of a material made of liquid crystalline nanoparticles which exhibits UV‐light responsive surface plasmon resonance in a condensed state is presented. To obtain the material, metal cores are grafted with two types of organic ligands. A promesogenic derivative softens the system and induces rich liquid crystal phase polymorphism. Second, an azobenzene derivative endows nanoparticles with photoresponsive properties. It is shown that nanoparticles covered with a mixture of these ligands assemble into long‐range ordered structures which exhibit a novel dual‐responsivity. The structure and plasmonic properties of the assemblies can be controlled by a change in temperature as well as by UV‐light irradiation. These results present an efficient way to obtain bulk quantities of self‐assembled nanostructured materials with stability that is unattainable by alternative methods such as matrix‐assisted or DNA‐mediated organization.     

A Liquid‐Metal–Elastomer Nanocomposite for Stretchable Dielectric Materials

Stretchable high‐dielectric‐constant materials are crucial for electronic applications in emerging domains such as wearable computing and soft robotics. While previous efforts have shown promising materials architectures in the form of dielectric nano‐/microinclusions embedded in stretchable matrices, the limited mechanical compliance of these materials significantly limits their practical application as soft energy‐harvesting/storage transducers and actuators. Here, a class of liquid metal (LM)–elastomer nanocomposites is presented with elastic and dielectric properties that make them uniquely suited for applications in soft‐matter engineering. In particular, the role of droplet size is examined and it is found that embedding an elastomer with a polydisperse distribution of nanoscale LM inclusions can enhance its electrical permittivity without significantly degrading its elastic compliance, stretchability, or dielectric breakdown strength. In contrast, elastomers embedded with microscale droplets exhibit similar improvements in permittivity but a dramatic reduction in breakdown strength. The unique enabling properties and practicality of LM–elastomer nanocomposites for use in soft machines and electronics is demonstrated through enhancements in performance of a dielectric elastomer actuator and energy‐harvesting transducer.