Rotational multimaterial printing of filaments with subvoxel control.

Helical structures are ubiquitous in nature and impart unique mechanical properties and multifunctionality1. So far, synthetic architectures that mimic these natural systems have been fabricated by winding, twisting and braiding of individual filaments1-7, microfluidics8,9, self-shaping1,10-13 and printing methods14-17. However, those fabrication methods are unable to simultaneously create and pattern multimaterial, helically architected filaments with subvoxel control in arbitrary two-dimensional (2D) and three-dimensional (3D) motifs from a broad range of materials. Towards this goal, both multimaterial18-23 and rotational24 3D printing of architected filaments have recently been reported; however, the integration of these two capabilities has yet to be realized. Here we report a rotational multimaterial 3D printing (RM-3DP) platform that enables subvoxel control over the local orientation of azimuthally heterogeneous architected filaments. By continuously rotating a multimaterial nozzle with a controlled ratio of angular-to-translational velocity, we have created helical filaments with programmable helix angle, layer thickness and interfacial area between several materials within a given cylindrical voxel. Using this integrated method, we have fabricated functional artificial muscles composed of helical dielectric elastomer actuators with high fidelity and individually addressable conductive helical channels embedded within a dielectric elastomer matrix. We have also fabricated hierarchical lattices comprising architected helical struts containing stiff springs within a compliant matrix. Our additive-manufacturing platform opens new avenues to generating multifunctional architected matter in bioinspired motifs.

Statistical reprogramming of macroscopic self-assembly with dynamic boundaries.

Self-assembly is a ubiquitous process that can generate complex and functional structures via local interactions among a large set of simpler components. The ability to program the self-assembly pathway of component sets elucidates fundamental physics and enables alternative competitive fabrication technologies. Reprogrammability offers further opportunities for tuning structural and material properties but requires reversible selection from multistable self-assembling patterns, which remains a challenge. Here, we show statistical reprogramming of two-dimensional (2D), noncompact self-assembled structures by the dynamic confinement of orbitally shaken and magnetically repulsive millimeter-scale particles. Under a constant shaking regime, we control the rate of radius change of an assembly arena via moving hard boundaries and select among a finite set of self-assembled patterns repeatably and reversibly. By temporarily trapping particles in topologically identified stable states, we also demonstrate 2D reprogrammable stiffness and three-dimensional (3D) magnetic clutching of the self-assembled structures. Our reprogrammable system has prospective implications for the design of granular materials in a multitude of physical scales where out-of-equilibrium self-assembly can be realized with different numbers or types of particles. Our dynamic boundary regulation may also enable robust bottom-up control strategies for novel robotic assembly applications by designing more complex spatiotemporal interactions using mobile robots.

Bioinspired underwater locomotion of light-driven liquid crystal gels.

Soft-bodied aquatic invertebrates, such as sea slugs and snails, are capable of diverse locomotion modes under water. Recapitulation of such multimodal aquatic locomotion in small-scale soft robots is challenging, due to difficulties in precise spatiotemporal control of deformations and inefficient underwater actuation of existing stimuli-responsive materials. Solving this challenge and devising efficient untethered manipulation of soft stimuli-responsive materials in the aquatic environment would significantly broaden their application potential in biomedical devices. We mimic locomotion modes common to sea invertebrates using monolithic liquid crystal gels (LCGs) with inherent light responsiveness and molecular anisotropy. We elicit diverse underwater locomotion modes, such as crawling, walking, jumping, and swimming, by local deformations induced by selective spatiotemporal light illumination. Our results underpin the pivotal role of the physicomechanical properties of LCGs in the realization of diverse modes of light-driven robotic underwater locomotion. We envisage that our results will introduce a toolbox for designing efficient untethered soft robots for fluidic environments.

Heterogeneous Activation, Local Structure, and Softness in Supercooled Colloidal Liquids.

We experimentally characterize heterogeneous nonexponential relaxation in bidisperse supercooled colloidal liquids utilizing a recent concept called "softness" [Phys. Rev. Lett. 114, 108001 (2015)PRLTAO0031-900710.1103/PhysRevLett.114.108001]. Particle trajectory and structure data enable classification of particles into subgroups with different local environments and propensities to hop. We determine residence times t_{R} between particle hops and show that t_{R} derived from particles in the same softness subgroup are exponentially distributed. Using the mean residence time t[over ¯]_{R} for each softness subgroup, and a Kramers' reaction rate model, we estimate the activation energy barriers E_{b} for particle hops, and show that both t[over ¯]_{R} and E_{b} are monotonic functions of softness. Finally, we derive information about the combinations of large and small particle neighbors that determine particle softness, and we explicitly show that multiple exponential relaxation channels in the supercooled liquid give rise to its nonexponential behavior.

Chiral structures from achiral liquid crystals in cylindrical capillaries.

We study chiral symmetry-broken configurations of nematic liquid crystals (LCs) confined to cylindrical capillaries with homeotropic anchoring on the cylinder walls (i.e., perpendicular surface alignment). Interestingly, achiral nematic LCs with comparatively small twist elastic moduli relieve bend and splay deformations by introducing twist deformations. In the resulting twisted and escaped radial (TER) configuration, LC directors are parallel to the cylindrical axis near the center, but to attain radial orientation near the capillary wall, they escape along the radius through bend and twist distortions. Chiral symmetry-breaking experiments in polymer-coated capillaries are carried out using Sunset Yellow FCF, a lyotropic chromonic LC with a small twist elastic constant. Its director configurations are investigated by polarized optical microscopy and explained theoretically with numerical calculations. A rich phenomenology of defects also arises from the degenerate bend/twist deformations of the TER configuration, including a nonsingular domain wall separating domains of opposite twist handedness but the same escape direction and singular point defects (hedgehogs) separating domains of opposite escape direction. We show the energetic preference for singular defects separating domains of opposite twist handedness compared with those of the same handedness, and we report remarkable chiral configurations with a double helix of disclination lines along the cylindrical axis. These findings show archetypally how simple boundary conditions and elastic anisotropy of confined materials lead to multiple symmetry breaking and how these broken symmetries combine to create a variety of defects.

Chiral symmetry breaking and surface faceting in chromonic liquid crystal droplets with giant elastic anisotropy.

Confined liquid crystals (LC) provide a unique platform for technological applications and for the study of LC properties, such as bulk elasticity, surface anchoring, and topological defects. In this work, lyotropic chromonic liquid crystals (LCLCs) are confined in spherical droplets, and their director configurations are investigated as a function of mesogen concentration using bright-field and polarized optical microscopy. Because of the unusually small twist elastic modulus of the nematic phase of LCLCs, droplets of this phase exhibit a twisted bipolar configuration with remarkably large chiral symmetry breaking. Further, the hexagonal ordering of columns and the resultant strong suppression of twist and splay but not bend deformation in the columnar phase, cause droplets of this phase to adopt a concentric director configuration around a central bend disclination line and, at sufficiently high mesogen concentration, to exhibit surface faceting. Observations of director configurations are consistent with Jones matrix calculations and are understood theoretically to be a result of the giant elastic anisotropy of LCLCs.

Liquid Crystal Elastomer Lattices with Thermally Programmable Deformation via Multi-Material 3D Printing.

An integrated design, modeling, and multi-material 3D printing platform for fabricating liquid crystal elastomer (LCE) lattices in both homogeneous and heterogeneous layouts with spatially programmable nematic director order and local composition is reported. Depending on their compositional topology, these lattices exhibit different reversible shape-morphing transformations upon cycling above and below their respective nematic-to-isotropic transition temperatures. Further, it is shown that there is good agreement between their experimentally observed deformation response and model predictions for all LCE lattice designs evaluated. Lastly, an inverse design model is established and the ability to print LCE lattices with the predicted deformation behavior is demonstrated. This work opens new avenues for creating architected LCE lattices that may find potential application in energy-dissipating structures, microfluidic pumping, mechanical logic, and soft robotics.

Liquid Crystal Elastomer-Based Magnetic Composite Films for Reconfigurable Shape-Morphing Soft Miniature Machines.

Stimuli-responsive and active materials promise radical advances for many applications. In particular, soft magnetic materials offer precise, fast, and wireless actuation together with versatile functionality, while liquid crystal elastomers (LCEs) are capable of large reversible and programmable shape-morphing with high work densities in response to various environmental stimuli, e.g., temperature, light, and chemical solutions. Integrating the orthogonal stimuli-responsiveness of these two kinds of active materials could potentially enable new functionalities and future applications. Here, magnetic microparticles (MMPs) are embedded into an LCE film to take the respective advantages of both materials without compromising their independent stimuli-responsiveness. This composite material enables reconfigurable magnetic soft miniature machines that can self-adapt to a changing environment. In particular, a miniature soft robot that can autonomously alter its locomotion mode when it moves from air to hot liquid, a vine-like filament that can sense and twine around a support, and a light-switchable magnetic spring are demonstrated. The integration of LCEs and MMPs into monolithic structures introduces a new dimension in the design of soft machines and thus greatly enhances their use in applications in complex environments, especially for miniature soft robots, which are self-adaptable to environmental changes while being remotely controllable.

Innervated, Self-Sensing Liquid Crystal Elastomer Actuators with Closed Loop Control.

The programmable assembly of innervated LCE actuators (iLCEs) with prescribed contractile actuation, self-sensing, and closed loop control via core-shell 3D printing is reported. This extrusion-based direct ink writing method enables coaxial filamentary features composed of pure LM core surrounded by an LCE shell, whose director is aligned along the print path. Specifically, the thermal response of the iLCE fiber-type actuators is programmed, measured, and modeled during Joule heating, including quantifying the concomitant changes in fiber length and resistance that arise during simultaneous heating and self-sensing. Due to their reversible, high-energy actuation and their resistive feedback, it is also demonstrated that iLCEs can be regulated with closed loop control even when perturbed with large bias loads. Finally, iLCE architectures capable of programmed, self-sensing 3D shape change with closed loop control are fabricated.

Precise Control of Lyotropic Chromonic Liquid Crystal Alignment through Surface Topography.

Many emerging applications, such as water-based electronic devices and biological sensors, require local control of anisotropic properties. Lyotropic chromonic liquid crystals (LCLCs) are an exciting class of materials, which are usually biocompatible and provide uniaxial anisotropy through a director field but, to date, remain difficult to control. In this work, we introduce a simple strategy to realize an arbitrary orientation of LCLCs director field in two dimensions (2D). Our alignment strategy relies on surface topographical micro/nanostructures fabricated by two-photon laser writing. We show that the alignment of LCLCs can be: (a) precisely controlled with a remarkable pixel resolution of 2.5 µm and (b) patterned into an arbitrary 2D alignment (e.g., +2 topological defect) by a pixelated design and arrangement of micro/nanostructures. Using a similar strategy, we achieve a patternable homeotropic alignment of LCLCs with nanopillars. Finally, we demonstrate that a self-assembled three-dimensional alignment of LCLCs can be obtained due to the versatility of our alignment strategy. Our demonstration of LCLC director field control, which is not only straightforward to achieve but also compatible with other conventional micro/nanofabrication techniques, will provide new opportunities for the manufacturing of LC-based electronic and biological devices.

Monolithic shape-programmable dielectric liquid crystal elastomer actuators.

Soft robotics may enable many new technologies in which humans and robots physically interact, yet the necessary high-performance soft actuators still do not exist. The optimal soft actuators need to be fast and forceful and have programmable shape changes. Furthermore, they should be energy efficient for untethered applications and easy to fabricate. Here, we combine desirable characteristics from two distinct active material systems: fast and highly efficient actuation from dielectric elastomers and directed shape programmability from liquid crystal elastomers. Via a top-down photoalignment method, we program molecular alignment and localized giant elastic anisotropy into the liquid crystal elastomers. The linearly actuated liquid crystal elastomer monoliths achieve strain rates over 120% per second with an energy conversion efficiency of 20% while moving loads over 700 times the elastomer weight. The electric actuation mechanism offers unprecedented opportunities toward miniaturization with shape programmability, efficiency, and more degrees of freedom for applications in soft robotics and beyond.

Deposition and drying dynamics of liquid crystal droplets.

Drop drying and deposition phenomena reveal a rich interplay of fundamental science and engineering, give rise to fascinating everyday effects (coffee rings), and influence technologies ranging from printing to genotyping. Here we investigate evaporation dynamics, morphology, and deposition patterns of drying lyotropic chromonic liquid crystal droplets. These drops differ from typical evaporating colloidal drops primarily due to their concentration-dependent isotropic, nematic, and columnar phases. Phase separation occurs during evaporation, and in the process creates surface tension gradients and significant density and viscosity variation within the droplet. As a result, the drying multiphase drops exhibit different convective currents, drop morphologies, and deposition patterns (coffee-rings).

Vibrational properties of quasi-two-dimensional colloidal glasses with varying interparticle attraction.

We measure the vibrational modes and particle dynamics of quasi-two-dimensional colloidal glasses as a function of interparticle interaction strength. The interparticle attractions are controlled via a temperature-tunable depletion interaction. Specifically, the interparticle attraction energy is increased gradually from a very small value (nearly hard-sphere) to moderate strength (∼4k_{B}T), and the variation of colloidal particle dynamics and vibrations are concurrently probed. The particle dynamics slow monotonically with increasing attraction strength, and the particle motions saturate for strengths greater than ∼2k_{B}T, i.e., as the system evolves from a nearly repulsive glass to an attractive glass. The shape of the phonon density of states is revealed to change with increasing attraction strength, and the number of low-frequency modes exhibits a crossover for glasses with weak compared to strong interparticle attraction at a threshold of ∼2k_{B}T. This variation in the properties of the low-frequency vibrational modes suggests a new means for distinguishing between repulsive and attractive glass states.

Tunable depletion potentials driven by shape variation of surfactant micelles.

Depletion interaction potentials between micron-sized colloidal particles are induced by nanometer-scale surfactant micelles composed of hexaethylene glycol monododecyl ether (C_{12}E_{6}), and they are measured by video microscopy. The strength and range of the depletion interaction is revealed to arise from variations in shape anisotropy of the surfactant micelles. This shape anisotropy increases with increasing sample temperature. By fitting the colloidal interaction potentials to theoretical models, we extract micelle length and shape anisotropy as a function of temperature. This work introduces shape anisotropy tuning as a means to control interparticle interactions in colloidal suspensions, and it shows how the interparticle depletion potentials of micron-scale objects can be employed to probe the shape and size of surrounding macromolecules at the nanoscale.

Chiral structures and defects of lyotropic chromonic liquid crystals induced by saddle-splay elasticity.

An experimental and theoretical study of lyotropic chromonic liquid crystals (LCLCs) confined in cylinders with degenerate planar boundary conditions elucidates LCLC director configurations. When the Frank saddle-splay modulus is more than twice the twist modulus, the ground state adopts an inhomogeneous escaped-twisted configuration. Analysis of the configuration yields a large saddle-splay modulus, which violates Ericksen inequalities but not thermodynamic stability. Lastly, we observe point defects between opposite-handed domains, and we explain a preference for point defects over domain walls.

Vibrational and structural signatures of the crossover between dense glassy and sparse gel-like attractive colloidal packings.

We investigate the vibrational modes of quasi-two-dimensional disordered colloidal packings of hard colloidal spheres with short-range attractions as a function of packing fraction. Certain properties of the vibrational density of states (vDOS) are shown to correlate with the density and structure of the samples (i.e., in sparsely versus densely packed samples). Specifically, a crossover from dense glassy to sparse gel-like states is suggested by an excess of phonon modes at low frequency and by a variation in the slope of the vDOS with frequency at low frequency. This change in phonon mode distribution is demonstrated to arise largely from localized vibrations that involve individual and/or small clusters of particles with few local bonds. Conventional order parameters and void statistics did not exhibit obvious gel-glass signatures as a function of volume fraction. These mode behaviors and accompanying structural insights offer a potentially new set of indicators for identification of glass-gel transitions and for assignment of gel-like versus glass-like character to a disordered solid material.