Silky Liquid Metal Electrodes for On-Skin Health Monitoring.

Next generation on-skin electrodes will require soft, flexible, and gentle materials to provide both high-fidelity sensing and wearer comfort. However, many commercially available on-skin electrodes lack these key properties due to their use of rigid hardware, harsh adhesives, uncomfortable support structures, and poor breathability. To address these challenges, this work presents a new device paradigm by joining biocompatible electrospun spider silk with printable liquid metal to yield an incredibly soft and scalable on-skin electrode that is strain-tolerant, conformable, and gentle on-skin. These electrodes, termed silky liquid metal (SLiM) electrodes, are found to be over five times more breathable than commercial wet electrodes, while the silk's intrinsic adhesion mechanism allows SLiM electrodes to avoid the use of harsh artificial adhesives, potentially decreasing skin irritation and inflammation over long-term use. Finally, the SLiM electrodes provide comparable impedances to traditional wet and other liquid metal electrodes, offering a high-fidelity sensing alternative with increased wearer comfort. Human subject testing confirmed the SLiM electrodes ability to sense electrophysiological signals with high fidelity and minimal irritation to the skin. The unique properties of the reported SLiM electrodes offer a comfortable electrophysiological sensing solution especially for patients with pre-existing skin conditions or surface wounds.

Mechanical integrated circuit materials.

Recent developments in autonomous engineered matter have introduced the ability for intelligent materials to process environmental stimuli and functionally adapt1-4. To formulate a foundation for such an engineered living material paradigm, researchers have introduced sensing5-11 and actuating12-16 functionalities in soft matter. Yet, information processing is the key functional element of autonomous engineered matter that has been recently explored through unconventional techniques with limited computing scalability17-20. Here we uncover a relation between Boolean mathematics and kinematically reconfigurable electrical circuits to realize all combinational logic operations in soft, conductive mechanical materials. We establish an analytical framework that minimizes the canonical functions of combinational logic by the Quine-McCluskey method, and governs the mechanical design of reconfigurable integrated circuit switching networks in soft matter. The resulting mechanical integrated circuit materials perform higher-level arithmetic, number comparison, and decode binary data to visual representations. We exemplify two methods to automate the design on the basis of canonical Boolean functions and individual gate-switching assemblies. We also increase the computational density of the materials by a monolithic layer-by-layer design approach. As the framework established here leverages mathematics and kinematics for system design, the proposed approach of mechanical integrated circuit materials can be realized on any length scale and in a wide variety of physics.

Textile-Integrated Liquid Metal Electrodes for Electrophysiological Monitoring.

Next generation textile-based wearable sensing systems will require flexibility and strength to maintain capabilities over a wide range of deformations. However, current material sets used for textile-based skin contacting electrodes lack these key properties, which hinder applications such as electrophysiological sensing. In this work, a facile spray coating approach to integrate liquid metal nanoparticle systems into textile form factors for conformal, flexible, and robust electrodes is presented. The liquid metal system employs functionalized liquid metal nanoparticles that provide a simple "peel-off to activate" means of imparting conductivity. The spray coating approach combined with the functionalized liquid metal system enables the creation of long-term reusable textile-integrated liquid metal electrodes (TILEs). Although the TILEs are dry electrodes by nature, they show equal skin-electrode impedances and sensing capabilities with improved wearability compared to commercial wet electrodes. Biocompatibility of TILEs in an in vivo skin environment is demonstrated, while providing improved sensing performance compared to previously reported textile-based dry electrodes. The "spray on dry-behave like wet" characteristics of TILEs opens opportunities for textile-based wearable health monitoring, haptics, and augmented/virtual reality applications that require the use of flexible and conformable dry electrodes.

3D-Printed Self-Healing Elastomers for Modular Soft Robotics.

Advances in materials, designs, and controls are propelling the field of soft robotics at an incredible rate; however, current methods for prototyping soft robots remain cumbersome and struggle to incorporate desirable geometric complexity. Herein, a vat photopolymerizable self-healing elastomer system capable of extreme elongations up to 1000% is presented. The material is formed from a combination of thiol/acrylate mixed chain/step-growth polymerizations and uses a combination of physical processes and dynamic-bond exchange via thioethers to achieve full self-healing capacity over multiple damage/healing cycles. These elastomers can be three dimensional (3D) printed with modular designs capable of healing together to form highly complex and large functional soft robots. Additionally, these materials show reprogrammable resting shapes and compatibility with self-healing liquid metal electronics. Using these capabilities, subcomponents with multiple internal channel systems were printed, healed together, and combined with functional liquid metals to form a high-wattage pneumatic switch and a humanoid-scale soft robotic gripper. The combination of 3D printing and self-healing elastomeric materials allows for facile production of support-free parts with extreme complexity, resulting in a paradigm shift for the construction of modular soft robotics.

Digital logic gates in soft, conductive mechanical metamaterials.

Integrated circuits utilize networked logic gates to compute Boolean logic operations that are the foundation of modern computation and electronics. With the emergence of flexible electronic materials and devices, an opportunity exists to formulate digital logic from compliant, conductive materials. Here, we introduce a general method of leveraging cellular, mechanical metamaterials composed of conductive polymers to realize all digital logic gates and gate assemblies. We establish a method for applying conductive polymer networks to metamaterial constituents and correlate mechanical buckling modes with network connectivity. With this foundation, each of the conventional logic gates is realized in an equivalent mechanical metamaterial, leading to soft, conductive matter that thinks about applied mechanical stress. These findings may advance the growing fields of soft robotics and smart mechanical matter, and may be leveraged across length scales and physics.

Oxidation of Gallium-based Liquid Metal Alloys by Water.

Gallium alloys with other low melting point metals, such as indium or tin, to form room-temperature liquid eutectic systems. The gallium in the alloys rapidly forms a thin surface oxide when exposed to ambient oxygen. This surface oxide has been previously exploited for self-stabilization of liquid metal nanoparticles, retention of metastable shapes, and imparting stimuli-responsive behavior to the alloy surface. In this work, we study the effect of water as an oxidant and its role in defining the alloy surface chemistry. We identify several pathways that can lead to the formation of gallium oxide hydroxide (GaOOH) crystallites, which may be undesirable in many applications. Furthermore, we find that some crystallite formation pathways can be reinforced by typical top-down particle synthesis techniques like sonication. This improved understanding of interfacial interactions provides critical insight for process design and implementation of advanced devices that utilize the unique coupling of flexibility and conductivity offered by these gallium-based liquid metal alloys.

Graphene-based encapsulation of liquid metal particles.

Liquid metals are a promising functional material due to their unique combination of metallic properties and fluidity at room temperature. They are of interest in wide-ranging fields including stretchable and flexible electronics, reconfigurable devices, microfluidics, biomedicine, material synthesis, and catalysis. Transformation of bulk liquid metal into particles has enabled further advances by allowing access to a broader palette of fabrication techniques for device manufacture or by increasing area available for surface-based applications. For gallium-based liquid metal alloys, particle stabilization is typically achieved by the oxide that forms spontaneously on the surface, even when only trace amounts of oxygen are present. The utility of the particles formed is governed by the chemical, electrical, and mechanical properties of this oxide. To overcome some of the intrinsic limitations of the native oxide, it is demonstrated here for the first time that 2D graphene-based materials can encapsulate liquid metal particles during fabrication and imbue them with previously unattainable properties. This outer encapsulation layer is used to physically stabilize particles in a broad range of pH environments, modify the particles' mechanical behavior, and control the electrical behavior of resulting films. This demonstration of graphene-based encapsulation of liquid metal particles represents a first foray into the creation of a suite of hybridized 2D material coated liquid metal particles.

Chemically modifying the mechanical properties of core-shell liquid metal nanoparticles.

Eutectic gallium-indium (EGaIn) is a room temperature liquid metal that can be readily fabricated into nanoparticles which naturally form a thin, passivating gallium oxide shell. These core-shell nanoparticles are of interest for a variety of stimuli-responsive applications, which often utilize physical deformation of the particles to release the molten, conductive payload from within the gallium oxide shell. In the present work, we introduce a variety of chemical strategies to produce EGaIn nanoparticles which exhibit a wide range of gallium oxide shell thicknesses. These chemically modified oxide thicknesses are then correlated to the core-shell liquid nanoparticles' mechanical properties by subjecting the particles to orthogonal characterization techniques; XPS for measurement of the gallium oxide shell thickness and nanoindentation for measurement of particle stiffness and elastic modulus. Additionally, nanoindentation is used to determine the onset of particle rupture and resultant conductivity. Ultimately, quantification of the relationships between chemical treatment and derivative mechanical properties in liquid metal nanoparticles will enable advanced applications of these colloids, such as in tailored self-healing and responsive electronic devices.

Mechanoresponsive Polymerized Liquid Metal Networks.

Room-temperature liquid metals, such as nontoxic gallium alloys, show enormous promise to revolutionize stretchable electronics for next-generation soft robotic, e-skin, and wearable technologies. Core-shell particles of liquid metal with surface-bound acrylate ligands are synthesized and polymerized together to create cross-linked particle networks comprising >99.9% liquid metal by weight. When stretched, particles within these polymerized liquid metal networks (Poly-LMNs) rupture and release their liquid metal payload, resulting in a rapid 108 -fold increase in the network's conductivity. These networks autonomously form hierarchical structures that mitigate the deleterious effects of strain on electronic performance and give rise to emergent properties. Notable characteristics include nearly constant resistances over large strains, electronic strain memory, and increasing volumetric conductivity with strain to over 20 000 S cm-1 at >700% elongation. Furthermore, these Poly-LMNs exhibit exceptional performance as stretchable heaters, retaining 96% of their areal power across relevant physiological strains. Remarkable electromechanical properties, responsive behaviors, and facile processing make Poly-LMNs ideal for stretchable power delivery, sensing, and circuitry.

Patterning and Reversible Actuation of Liquid Gallium Alloys by Preventing Adhesion on Rough Surfaces.

This work reports a simple approach to form, study, and utilize rough coatings that prevent the adhesion of gallium-based liquid metal alloys. Typically, liquids with large interfacial tension do not wet nonreactive surfaces, regardless of surface topography. However, these alloys form a surface oxide "skin" that adheres to many substrates, even those with low surface energy. This work reports a simple approach to render closed channels and surfaces, including soft materials, to be "oxide-phobic" via spray-coating (NeverWet, which is commercially available and inexpensive). Surface spectroscopic techniques and metrology tools elucidate the coatings to comprise silica nanoparticles grafted with silicones that exhibit dual length scales of roughness. Although prior work shows the importance of surface roughness in preventing adhesion, the present work confirms that both hydrophobic and hydrophilic rough surfaces prevent oxide adhesion. Furthermore, the coating enables reversible actuation through submillimeter closed channels to form a reconfigurable antenna in the gigahertz range without the need for corrosive acids or bases that remove the oxide. In addition, the coating enables open surface patterning of conductive traces of liquid metal. This shows it is possible to actuate liquid metals in air without leaving neither metal nor oxide residue on surfaces to enable reconfigurable electronics, microfluidics, and soft electrodes.

A new catalytically active colloidal platinum nanocatalyst: the multiarmed nanostar single crystal.

Nanocatalysts that possess large amounts of atoms on sharp corners and edges and high indexed sites are known to be more catalytically active. We report here on a novel yet simple method to synthesize in large yields a very active platinum nanocatalyst; the multiarmed nanostar single crystal. We utilize a seed mediated method using tetrahedral nanoparticles that are also synthesized by a new and simple technique. High-resolution TEM shows that the nanostar has many arms, varying from a few to over 30, whereby even the largest ones are found to have single-crystal structures. This strongly suggests that they are formed by a growth mechanism of the seed crystals and not by the aggregation of seed crystals, which should produce twinning planes. Due to the reduction reaction of ferrricyanide by thiosulfate, the nanostars are found to have an activation energy, which is nearly 60% of that of the tetrahedral seeds themselves, both having the same PVP capping agent. This is undoubtedly due to the multiarms with edges, corners, and the presence of high indexed facets in the nanostar catalyst.