Architected Poly(ionic liquid) Composites with Spatially Programmable Mechanical Properties and Mixed Conductivity.

Structural electrolytes present advantages over liquid varieties, which are critical to myriad applications. In particular, structural electrolytes based on polymerized ionic liquids or poly(ionic liquids) (pILs) provide wide electrochemical windows, high thermal stability, nonvolatility, and modular chemistry. However, current methods of fabricating structural electrolytes from pILs and their composites present limitations. Recent advances have been made in 3D printing pIL electrolytes, but current printing techniques limit the complexity of forms that can be achieved, as well as the ability to control mechanical properties or conductivity. We introduce a method for fabricating architected pIL composites as structural electrolytes via embedded 3D (EMB3D) printing. We present a modular design for formulating ionic liquid (IL) monomer composite inks that can be printed into sparse, lightweight, free-standing lattices with different functionalities. In addition to characterizing the rheological and mechanical behaviors of IL monomer inks and pIL lattices, we demonstrate the self-sensing capabilities of our printed structural electrolytes during cyclic compression. Finally, we use our inks and printing method to spatially program self-sensing capabilities in pIL lattices through heterogeneous architectures as well as ink compositions that provide mixed ionic-electronic conductivity. Our free-form approach to fabricating structural electrolytes in complex, 3D forms with programmable, anisotropic properties has broad potential use in next-generation sensors, soft robotics, bioelectronics, energy storage devices, and more.

Chemically fueling new microrobot abilities.

A combustion-powered soft actuator takes microrobots to new heights and speeds.

Embedded 3D Printing of Architected Ceramics via Microwave-Activated Polymerization.

Light- and ink-based 3D printing methods have vastly expanded the design space and geometric complexity of architected ceramics. However, light-based methods are typically confined to a relatively narrow range of preceramic and particle-laden resins, while ink-based methods are limited in geometric complexity due to layerwise assembly. Here, embedded 3D printing is combined with microwave-activated curing to generate architected ceramics with spatially controlled composition in freeform shapes. Aqueous colloidal inks are printed within a support matrix, rapidly cured via microwave-activated polymerization, and subsequently dried and sintered into dense architectures composed of one or more oxide materials. This integrated manufacturing method opens new avenues for the design and fabrication of complex ceramic architectures with programmed composition, density, and form for myriad applications.

Embedded 3D Printing of Multimaterial Polymer Lattices via Graph-Based Print Path Planning.

Recent advances in computational design and 3D printing enable the fabrication of polymer lattices with high strength-to-weight ratio and tailored mechanics. To date, 3D lattices composed of monolithic materials have primarily been constructed due to limitations associated with most commercial 3D printing platforms. Here, freeform fabrication of multi-material polymer lattices via embedded three-dimensional (EMB3D) printing is demonstrated. An algorithm is developed first that generates print paths for each target lattice based on graph theory. The effects of ink rheology on filamentary printing and the effects of the print path on resultant mechanical properties are then investigated. By co-printing multiple materials with different mechanical properties, a broad range of periodic and stochastic lattices with tailored mechanical responses can be realized opening new avenues for constructing architected matter.

Motorized, untethered soft robots via 3D printed auxetics.

Untethered operation remains a fundamental challenge in soft robotics. Soft robotic actuators are generally unable to produce the forces required for carrying essential power and control hardware on-board. Moreover, current untethered soft robots often have low operating times given soft actuators' limited efficiency and lifetime. Here, we 3D print cylindrical handed shearing auxetics (HSAs) from single-cure polyurethane resins for use as scalable, motorized soft robotic actuators for untethered machines. Mechanical characterization of individual HSAs confirms their auxetic behaviors and suitability as actuators. HSA pairs of opposite handedness are assembled to form multi-degree-of-freedom legs for untethered quadrupeds. We explore several leg designs to understand the role of length and auxetic pattern density on overall motion and blocked force generated. Finally, we demonstrate untethered locomotion with two soft robotic quadrupeds. We find that our taller soft robot is capable of walking at 2 body lengths per min (BL min-1) for 65 min, all while carrying a payload of at least 1.5 kg. We compare our soft robots' capabilities to those of previously reported untethered, terrestrial systems and find that our motorized HSAs lead to the second highest operating time with an above average velocity. We anticipate that these methods will open new avenues for designing untethered soft robots with the robustness, operating times, and payload capacities required for future fundamental investigations in embodied intelligence and adaptive, physical learning.

Fluidic innervation sensorizes structures from a single build material.

Multifunctional materials with distributed sensing and programmed mechanical properties are required for myriad emerging technologies. However, current fabrication techniques constrain these materials' design and sensing capabilities. We address these needs with a method for sensorizing architected materials through fluidic innervation, where distributed networks of empty, air-filled channels are directly embedded within an architected material's sparse geometry. By measuring pressure changes within these channels, we receive feedback regarding material deformation. Thus, this technique allows for three-dimensional printing of sensorized structures from a single material. With this strategy, we fabricate sensorized soft robotic actuators on the basis of handed shearing auxetics and accurately predict their kinematics from the sensors' proprioceptive feedback using supervised learning. Our strategy for facilitating structural, sensing, and actuation capabilities through control of form alone simplifies sensorized material design for applications spanning wearables, smart structures, and robotics.

Integrating chemical fuels and artificial muscles for untethered microrobots.

Continued development of untethered insect-scale robots will require codesigned power and actuation strategies.

Shape-shifting structured lattices via multimaterial 4D printing.

Shape-morphing structured materials have the ability to transform a range of applications. However, their design and fabrication remain challenging due to the difficulty of controlling the underlying metric tensor in space and time. Here, we exploit a combination of multiple materials, geometry, and 4-dimensional (4D) printing to create structured heterogeneous lattices that overcome this problem. Our printable inks are composed of elastomeric matrices with tunable cross-link density and anisotropic filler that enable precise control of their elastic modulus (E) and coefficient of thermal expansion [Formula: see text] The inks are printed in the form of lattices with curved bilayer ribs whose geometry is individually programmed to achieve local control over the metric tensor. For independent control of extrinsic curvature, we created multiplexed bilayer ribs composed of 4 materials, which enables us to encode a wide range of 3-dimensional (3D) shape changes in response to temperature. As exemplars, we designed and printed planar lattices that morph into frequency-shifting antennae and a human face, demonstrating functionality and geometric complexity, respectively. Our inverse geometric design and multimaterial 4D printing method can be readily extended to other stimuli-responsive materials and different 2-dimensional (2D) and 3D cell designs to create scalable, reversible, shape-shifting structures with unprecedented complexity.

Biomanufacturing of organ-specific tissues with high cellular density and embedded vascular channels.

Engineering organ-specific tissues for therapeutic applications is a grand challenge, requiring the fabrication and maintenance of densely cellular constructs composed of ~108 cells/ml. Organ building blocks (OBBs) composed of patient-specific-induced pluripotent stem cell-derived organoids offer a pathway to achieving tissues with the requisite cellular density, microarchitecture, and function. However, to date, scant attention has been devoted to their assembly into 3D tissue constructs. Here, we report a biomanufacturing method for assembling hundreds of thousands of these OBBs into living matrices with high cellular density into which perfusable vascular channels are introduced via embedded three-dimensional bioprinting. The OBB matrices exhibit the desired self-healing, viscoplastic behavior required for sacrificial writing into functional tissue (SWIFT). As an exemplar, we created a perfusable cardiac tissue that fuses and beats synchronously over a 7-day period. Our SWIFT biomanufacturing method enables the rapid assembly of perfusable patient- and organ-specific tissues at therapeutic scales.

Viscoplastic Matrix Materials for Embedded 3D Printing.

Embedded three-dimensional (EMB3D) printing is an emerging technique that enables free-form fabrication of complex architectures. In this approach, a nozzle is translated omnidirectionally within a soft matrix that surrounds and supports the patterned material. To optimize print fidelity, we have investigated the effects of matrix viscoplasticity on the EMB3D printing process. Specifically, we determine how matrix composition, print path and speed, and nozzle diameter affect the yielded region within the matrix. By characterizing the velocity and strain fields and analyzing the dimensions of the yielded regions, we determine that scaling relationships based on the Oldroyd number, Od, exist between these dimensions and the rheological properties of the matrix materials and printing parameters. Finally, we use EMB3D printing to create complex architectures within an elastomeric silicone matrix. Our methods and findings will both facilitate future characterization of viscoplastic matrices and motivate the development of new materials for EMB3D printing.

Soft Somatosensitive Actuators via Embedded 3D Printing.

Humans possess manual dexterity, motor skills, and other physical abilities that rely on feedback provided by the somatosensory system. Herein, a method is reported for creating soft somatosensitive actuators (SSAs) via embedded 3D printing, which are innervated with multiple conductive features that simultaneously enable haptic, proprioceptive, and thermoceptive sensing. This novel manufacturing approach enables the seamless integration of multiple ionically conductive and fluidic features within elastomeric matrices to produce SSAs with the desired bioinspired sensing and actuation capabilities. Each printed sensor is composed of an ionically conductive gel that exhibits both long-term stability and hysteresis-free performance. As an exemplar, multiple SSAs are combined into a soft robotic gripper that provides proprioceptive and haptic feedback via embedded curvature, inflation, and contact sensors, including deep and fine touch contact sensors. The multimaterial manufacturing platform enables complex sensing motifs to be easily integrated into soft actuating systems, which is a necessary step toward closed-loop feedback control of soft robots, machines, and haptic devices.

3D Printing of Liquid Crystal Elastomeric Actuators with Spatially Programed Nematic Order.

Liquid crystal elastomers (LCEs) are soft materials capable of large, reversible shape changes, which may find potential application as artificial muscles, soft robots, and dynamic functional architectures. Here, the design and additive manufacturing of LCE actuators (LCEAs) with spatially programed nematic order that exhibit large, reversible, and repeatable contraction with high specific work capacity are reported. First, a photopolymerizable, solvent-free, main-chain LCE ink is created via aza-Michael addition with the appropriate viscoelastic properties for 3D printing. Next, high operating temperature direct ink writing of LCE inks is used to align their mesogen domains along the direction of the print path. To demonstrate the power of this additive manufacturing approach, shape-morphing LCEA architectures are fabricated, which undergo reversible planar-to-3D and 3D-to-3D' transformations on demand, that can lift significantly more weight than other LCEAs reported to date.

Printing soft matter in three dimensions.

Light- and ink-based three-dimensional (3D) printing methods allow the rapid design and fabrication of materials without the need for expensive tooling, dies or lithographic masks. They have led to an era of manufacturing in which computers can control the fabrication of soft matter that has tunable mechanical, electrical and other functional properties. The expanding range of printable materials, coupled with the ability to programmably control their composition and architecture across various length scales, is driving innovation in myriad applications. This is illustrated by examples of biologically inspired composites, shape-morphing systems, soft sensors and robotics that only additive manufacturing can produce.

An integrated design and fabrication strategy for entirely soft, autonomous robots.

Soft robots possess many attributes that are difficult, if not impossible, to achieve with conventional robots composed of rigid materials. Yet, despite recent advances, soft robots must still be tethered to hard robotic control systems and power sources. New strategies for creating completely soft robots, including soft analogues of these crucial components, are needed to realize their full potential. Here we report the untethered operation of a robot composed solely of soft materials. The robot is controlled with microfluidic logic that autonomously regulates fluid flow and, hence, catalytic decomposition of an on-board monopropellant fuel supply. Gas generated from the fuel decomposition inflates fluidic networks downstream of the reaction sites, resulting in actuation. The body and microfluidic logic of the robot are fabricated using moulding and soft lithography, respectively, and the pneumatic actuator networks, on-board fuel reservoirs and catalytic reaction chambers needed for movement are patterned within the body via a multi-material, embedded 3D printing technique. The fluidic and elastomeric architectures required for function span several orders of magnitude from the microscale to the macroscale. Our integrated design and rapid fabrication approach enables the programmable assembly of multiple materials within this architecture, laying the foundation for completely soft, autonomous robots.

Embedded 3D printing of strain sensors within highly stretchable elastomers.

A new method, embedded-3D printing (e-3DP), is reported for fabricating strain sensors within highly conformal and extensible elastomeric matrices. e-3DP allows soft sensors to be created in nearly arbitrary planar and 3D motifs in a highly programmable and seamless manner. Several embodiments are demonstrated and sensor performance is characterized.

3D bioprinting of vascularized, heterogeneous cell-laden tissue constructs.

A new bioprinting method is reported for fabricating 3D tissue constructs replete with vasculature, multiple types of cells, and extracellular matrix. These intricate, heterogeneous structures are created by precisely co-printing multiple materials, known as bioinks, in three dimensions. These 3D micro-engineered environments open new -avenues for drug screening and fundamental studies of wound healing, angiogenesis, and stem-cell niches.

In vivo pulsed magneto-motive ultrasound imaging using high-performance magnetoactive contrast nanoagents.

Previously, pulsed magneto-motive ultrasound (pMMUS) imaging has been introduced as a contrast-agent-assisted ultrasound-based imaging modality capable of visualizing biological events at the cellular and molecular level. In pMMUS imaging, a high intensity pulsed magnetic field is used to excite cells or tissue labeled with magnetic nanoparticles. Then, ultrasound (US) imaging is used to monitor the mechanical response of the tissue to an externally applied magnetic field (i.e., tissue displacement). Signal to noise ratio (SNR) in pMMUS imaging can be improved by using superparamagnetic nanoparticles with larger saturation magnetization. Metal-doped magnetic nanoparticles with enhanced tunable nanomagnetism are suitable candidates to improve the SNR and, therefore, sensitivity of pMMUS imaging, which is essential for in vivo pMMUS imaging. In this study, we demonstrate the capability of pMMUS imaging to identify the presence and distribution of zinc-doped iron oxide nanoparticles in live nude mice bearing A431 (human epithelial carcinoma) xenograft tumors.

Ligand-mediated self-assembly of hybrid plasmonic and superparamagnetic nanostructures.

Hybrid nanostructures with unique optical and magnetic properties have attracted considerable interest as effective mediators for medical imaging and therapy. An aqueous-based, self-assembly approach to synthesizing hybrid plasmonic-superparamagnetic nanostructures is presented. The building blocks of the hybrid nanostructure include plasmonic gold nanorods (AuNRs) and superparamagnetic iron oxide nanoparticles (SPIONs). The AuNRs were functionalized via carboxyl-bearing surface ligands, and the SPIONs were kept "bare" after synthesis via a surfactant-free thermal decomposition reaction in triethylene glycol. Hybrid SPION-studded AuNR nanostructures were produced upon simple mixing of the components because of the chemisorption of the AuNRs' free carboxyl groups to the SPIONs' surfaces. The reported synthesis strategy is modular in nature and can be expanded to build hybrid nanostructures with a multitude of other plasmonic nanoparticles. With tunable near-infrared absorption peaks and a sufficient number of bound SPIONs, the self-assembled hybrid nanostructures are suitable for biomedical imaging and therapy applications.