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.

Three-dimensional structures that undergo reversible shape changes in response to mild stimuli enable a wide range of smart devices, such as soft robots or implantable medical devices. Herein, a dual thiol-ene reaction scheme is used to synthesize a class of liquid crystal (LC) elastomers that can be 3D printed into complex shapes and subsequently undergo controlled shape change. Through controlling the phase transition temperature of polymerizable LC inks, morphing 3D structures with tunable actuation temperature (28 ± 2 to 105 ± 1 °C) are fabricated. Finally, multiple LC inks are 3D printed into single structures to allow for the production of untethered, thermo-responsive structures that sequentially and reversibly undergo multiple shape changes.

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.

Strategies for obtaining materials that respond to external stimuli by changing shape are of intense interest for the replacement of traditional actuators. We here present a strategy that enables programmable, multi-responsive actuators that use either visible light or electric current to drive shape change in composites comprising carbon nanotubes (CNTs) in liquid crystal elastomers (LCEs). In our nanocomposites, the CNTs function not only in the traditional roles of mechanical reinforcement and enhancers of thermal and electrical conductivity but also serve as an alignment layer for the LCEs. By controlling the orientation, location, and quantity of layers of CNTs in LCE/CNT composites, we build programmed, patterned actuators that respond to visible light or electrical current. Photothermal LCE/CNT film actuators undergo fast shape change, within 1.2 s using 280 mW/cm 2 light input, and complex, programmed localized deformations. Furthermore, twisting LCE/CNT composite films into a fiber increases uniaxial muscle stroke and work capacity for electrothermal actuation, thereby enabling about 12% actuation strain and 100 kJ/m 3 of work capacity in response to an applied DC voltage of 15.1 V/cm.Received: ((will be filled in by the editorial staff))Revised: ((will be filled in by the editorial staff))

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.

Shape-switching behavior,w here at ransient stimulus induces an indefinitely stable deformation that can be recovered on exposure to another transient stimulus,iscritical 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) functionalizedw ith supramolecular crosslinks, dynamic covalent crosslinks,a nd azobenzene.T he salient property of shape-switching LCEs is that light induces longlived, deformation that can be recovered on-demand by heating.U V-light isomerizes azobenzene from trans to cis, and temporarily breaks the supramolecular crosslinks,r esulting in ap rogrammed deformation. After UV,t he shapeswitching LCEs fix more than 90 %o ft he deformation over 3daysb yt he reformed supramolecular crosslinks.U sing the shape-switching properties,weprint Braille-like actuators that can be photoswitched to displaydifferent letters.This new class of photoswitchable actuators may impact applications such as deployable devices where continuous application of power is impractical.

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.

A shape-morphing composite exhibits tunable actuation properties (stroke and force output) that are influenced by liquid metal particle size.