Interface of gallium-based liquid metals: oxide skin, wetting, and applications.

Gallium-based liquid metals (GaLMs) are promising for a variety of applications-especially as a component material for soft devices-due to their fluidic nature, low toxicity and reactivity, and high electrical and thermal conductivity comparable to solid counterparts. Understanding the interfacial properties and behaviors of GaLMs in different environments is crucial for most applications. When exposed to air or water, GaLMs form a gallium oxide layer with nanoscale thickness. This "oxide nano-skin" passivates the metal surface and allows for the formation of stable microstructures and films despite the high-surface tension of liquid metal. The oxide skin easily adheres to most smooth surfaces. While it enables effective printing and patterning of the GaLMs, it can also make the metals challenging to handle because it adheres to most surfaces. The oxide also affects the interfacial electrical resistance of the metals. Its formation, thickness, and composition can be chemically or electrochemically controlled, altering the physical, chemical, and electrical properties of the metal interface. Without the oxide, GaLMs wet metallic surfaces but do not wet non-metallic substrates such as polymers. The topography of the underlying surface further influences the wetting characteristics of the metals. This review outlines the interfacial attributes of GaLMs in air, water, and other environments and discusses relevant applications based on interfacial engineering. The effect of surface topography on the wetting behaviors of the GaLMs is also discussed. Finally, we suggest important research topics for a better understanding of the GaLMs interface.

3D-Printing of Hierarchical Porous Copper-Based Metal-Organic-Framework Structures for Efficient Fixed-Bed Catalysts.

Metallic structures with hierarchical open pores that span several orders of magnitude are ideal candidates for various catalyst applications. However, porous metal materials prepared using alloy/dealloy methods still struggle to achieve continuous pore distribution across a broad size range. Herein, we report a printable copper (Cu)/iron (Fe) composite ink that produces a hierarchical porous Cu material with pores spanning over 4 orders of magnitude. The manufacturing process involves four steps: 3D-printing, annealing, dealloying, and reannealing. Because of the unique annealing process, the resulting hierarchical pore surface becomes coated with a layer of Cu-Fe alloy. This feature imparts remarkable catalytic ability and versatile functionality within fixed bed reactors for 4-nitrophenol (4-NP) reduction and Friedländer cyclization. Specifically, for 4-NP reduction, the porous Cu catalyst demonstrates an excellent reaction rate constant (kapp = 86.5 × 10-3 s-1) and a wide adaptability of the substrate (up to 1.26 mM), whilst for Friedländer cyclization, a conversion over 95% within a retention time of only 20 min can be achieved by metal-organic-framework-decorated porous Cu catalyst. The utilization of dual metallic particles as printable inks offers valuable insights for fabricating hierarchical porous metallic structures for applications, such as advanced fixed-bed catalysts.

Liquid Metal Nanoparticles Physically Hybridized with Cellulose Nanocrystals Initiate and Toughen Hydrogels with Piezoionic Properties.

Liquid metal (LM) particles can serve as initiators, functional fillers, and cross-linkers for hydrogels. Herein, we show that cellulose nanocrystals (CNCs) stabilize LM particles in aqueous solutions, such as those used to produce hydrogels. The CNC-coated LM particles initiate free-radical polymerization to form poly(acrylic acid) (PAA) hydrogel with exceptional properties─stretchability ∼2000%, excellent toughness ∼1.8 MJ/m3, mechanical resilience, and efficient self-healing─relative to cross-linked PAA networks polymerized using conventional molecular initiators. FTIR spectroscopy, rheology, and mechanical measurements suggest that physical bonds between PAA and both Ga3+ and LM-CNC particles contribute to the excellent mechanical properties. The gels are used to sense a wide range of strains, such as those associated with human motion, via changes in resistance through the gel. The sensitivity at low strains enables monitoring subtle physiological signals, such as pulse. Without significantly compromising the toughness, soaking the gels in salt solution brings about high ionic conductivity (3.8 S/m), enabling them to detect touch via piezoionic principles; the anions in the gel have higher mobility than cations, resulting in significant charge separation (current ∼30 µA, ∼10 µA/cm2) through the gel in response to touch. These attractive properties are promising for wearable sensors, energy harvesters, and self-powered ionic touch panels.

Surface Embedded Metal Nanowire-Liquid Metal-Elastomer Hybrid Composites for Stretchable Electronics.

Both liquid metal (LM) and metallic filler-based conductive composites are promising stretchable conductors. LM alloys exhibit intrinsically high deformability but present challenges for patterning on polymeric substrates due to high surface tension. On the other hand, conductive composites comprising metallic fillers undergo considerable decrease in electrical conductivity under mechanical deformation. To address the challenges, we present silver nanowire (AgNW)-LM-elastomer hybrid composite films, where AgNWs and LM are embedded below the surface of an elastomeric matrix, using two fabrication approaches, sequential and mixed. We investigate and understand the process-structure-property relationship of the AgNW-LM-elastomer hybrid composites fabricated using two approaches. Different weight ratios of AgNWs and LM particles provide tunable electrical conductivity. The hybrid composites show more stable electromechanical performance than the composites with AgNWs alone. In particular, 1:2.4 (AgNW:LMP w/w) sequential hybrid composite shows electromechanical stability similar to that of the LM-elastomer composite, with a resistance increase of 2.04% at 90% strain. The sequential approach is found to form AgIn2 intermetallic compounds which along with Ga-In bonds, imparts large deformability to the sequential hybrid composite as well as mechanical robustness against scratching, cutting, peeling, and wiping. To demonstrate the application of the hybrid composite for stretchable electronics, a laser patterned stretchable heater on textile and a stretchable circuit including a light-emitting diode are fabricated.

Injection Molding of Liquid Metal by Harnessing Nonstick Molds.

The fluid nature of liquid metals combined with their ability to form a solid native oxide skin enables them to be patterned in ways that would be challenging for solid metals. The present work shows a unique way of patterning liquid metals by injecting liquid metals into a mold. The mold contains a nonstick coating that enables the removal of the mold, thereby leaving just the liquid metal on the target substrate. This approach offers the simplicity and structural control of molding but without having the mold become part of the device. Thus, the metal can be encapsulated with very soft polymers that collapse if used as microchannels. The same mold can be used multiple times for high-volume patterning of liquid metal. The injection molding method is rapid and reliably produces structures with complex geometries on both flat and curved surfaces. We demonstrate the method by fabricating an elastomeric Joule heater and an electroadhesive soft gripper to show the potential of the method for soft and stretchable devices.

Protocol for 3D and 4D printing of highly conductive metallic composite using liquid metal gels.

3D or 4D printing of metal structures requires extreme conditions or a multistage process. Here, we present a protocol for the preparation of highly conductive metallic composites using liquid metal gels at ambient conditions. We describe the steps to prepare ternary gels composed of copper particles, liquid metal, and water. We then detail procedures for 3D or 4D printing gels into highly conductive structures after adding a small amount of rheological modifier (methyl cellulose) using direct ink writing techniques. For complete details on the use and execution of this protocol, please refer to Xing et al. (2023).1.

Harvesting and manipulating sweat and interstitial fluid in microfluidic devices.

Microfluidic devices began to be used to facilitate sweat and interstitial fluid (ISF) sensing in the mid-2010s. Since then, numerous prototypes involving microfluidics have been developed in different form factors for sensing biomarkers found in these fluids under in vitro, ex vivo, and in vivo (on-body) settings. These devices transport and manipulate biofluids using microfluidic channels composed of silicone, polymer, paper, or fiber. Fluid flow transport and sample management can be achieved by controlling the flow rate, surface morphology of the channel, and rate of fluid evaporation. Although many devices have been developed for estimating sweat rate, electrolyte, and metabolite levels, only a handful have been able to proceed beyond laboratory testing and reach the stage of clinical trials and commercialization. To further this technology, this review reports on the utilization of microfluidics towards sweat and ISF management and transport. The review is distinguished from other recent reviews by focusing on microfluidic principles of sweat and ISF generation, transport, extraction, and management. Challenges and prospects are highlighted, with a discussion on how to transition such prototypes towards personalized healthcare monitoring systems.

A Guide to Printed Stretchable Conductors.

Printing of stretchable conductors enables the fabrication and rapid prototyping of stretchable electronic devices. For such applications, there are often specific process and material requirements such as print resolution, maximum strain, and electrical/ionic conductivity. This review highlights common printing methods and compatible inks that produce stretchable conductors. The review compares the capabilities, benefits, and limitations of each approach to help guide the selection of a suitable process and ink for an intended application. We also discuss methods to design and fabricate ink composites with the desired material properties (e.g., electrical conductance, viscosity, printability). This guide should help inform ongoing and future efforts to create soft, stretchable electronic devices for wearables, soft robots, e-skins, and sensors.

Printable Liquid Metal Foams That Grow When Watered.

Pastes and "foams" containing liquid metal (LM) as the continuous phase (liquid metal foams, LMFs) exhibit metallic properties while displaying paste or putty-like rheological behavior. These properties enable LMFs to be patterned into soft and stretchable electrical and thermal conductors through processes conducted at room temperature, such as printing. The simplest LMFs, featured in this work, are made by stirring LM in air, thereby entraining oxide-lined air "pockets" into the LM. Here, it is reported that mixing small amounts of water (as low as 1 wt%) into such LMFs gives rise to significant foaming by harnessing known reactions that evolve hydrogen and produce oxides. The resulting structures can be ≈4-5× their original volume and possess a fascinating combination of attributes: porosity, electrical conductivity, and responsiveness to environmental conditions. This expansion can be utilized for a type of 4D printing in which patterned conductors "grow," fill cavities, and change shape and density with respect to time. Excessive exposure to water in the long term ultimately consumes the metal in the LMF. However, when exposure to water is controlled, the metallic properties of porous LMFs can be preserved.

Examining cortical tracking of the speech envelope in post-stroke aphasia.

Introduction: People with aphasia have been shown to benefit from rhythmic elements for language production during aphasia rehabilitation. However, it is unknown whether rhythmic processing is associated with such benefits. Cortical tracking of the speech envelope (CTenv) may provide a measure of encoding of speech rhythmic properties and serve as a predictor of candidacy for rhythm-based aphasia interventions. Methods: Electroencephalography was used to capture electrophysiological responses while Spanish speakers with aphasia (n = 9) listened to a continuous speech narrative (audiobook). The Temporal Response Function was used to estimate CTenv in the delta (associated with word- and phrase-level properties), theta (syllable-level properties), and alpha bands (attention-related properties). CTenv estimates were used to predict aphasia severity, performance in rhythmic perception and production tasks, and treatment response in a sentence-level rhythm-based intervention. Results: CTenv in delta and theta, but not alpha, predicted aphasia severity. Neither CTenv in delta, alpha, or theta bands predicted performance in rhythmic perception or production tasks. Some evidence supported that CTenv in theta could predict sentence-level learning in aphasia, but alpha and delta did not. Conclusion: CTenv of the syllable-level properties was relatively preserved in individuals with less language impairment. In contrast, higher encoding of word- and phrase-level properties was relatively impaired and was predictive of more severe language impairments. CTenv and treatment response to sentence-level rhythm-based interventions need to be further investigated.

Enhanced Triboelectric Charge Stability by Air-Stable Radicals.

This paper demonstrates that air-stable radicals enhance the stability of triboelectric charge on surfaces. While charge on surfaces is often undesirable (e.g., static discharge), improved charge retention can benefit specific applications such as air filtration. Here, it is shown that self-assembled monolayers (SAMs) containing air-stable radicals, 2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), hold the charge longer than those without TEMPO. Charging and retention are monitored by Kelvin Probe Force Microscopy (KPFM) as a function of time. Without the radicals on the surface, charge retention increases with the water contact angle (hydrophobicity), consistent with the understanding that surface water molecules can accelerate charge dissipation. Yet, the most prolonged charge retention is observed in surfaces treated with TEMPO, which are more hydrophilic than untreated control surfaces. The charge retention decreases with reducing radical density by etching the TEMPO-silane with tetrabutylammonium fluoride (TBAF) or scavenging the radicals with ascorbic acid. These results suggest a pathway toward increasing the lifetime of triboelectric charges, which may enhance air filtration, improve tribocharging for patterning charges on surfaces, or boost triboelectric energy harvesting.

Novel participant-level meta-analytic evidence for AbSANT efficacy.

The current study employed interrupted time series (ITS) models to analyze all available (published and unpublished) Abstract Semantic Associative Network Training (AbSANT) data. AbSANT is a semantically focused anomia treatment that targets not only concrete but abstract words, unique among existing anomia treatments. However, evidence to date for the positive effects of AbSANT comes only from small-sample, single-subject design studies, limiting the strength of this evidence and the inferences that can be drawn from it. The statistical power and greater representativeness afforded by this larger aggregated sample enabled us to look for group-level efficacy evidence for AbSANT, examine specific questions about AbSANT's direct training and generalization effects, and identify potential predictors and mechanisms of AbSANT treatment response. We found that across 33 participants from four different data sources, AbSANT appears to be a robust word retrieval therapy protocol, with overall direct training and generalization effects that were more meaningful than exposure effects. Similar to previous smaller-sample study conclusions, we found that in this large sample, training abstract words results not only in larger direct training effects than training concrete words, but also larger generalization effects, suggesting that while AbSANT successfully improves both abstract and concrete word retrieval, it may be better suited for training abstract words. In general, direct training effects were more persistent after treatment ended than generalization effects and effects for concrete words were more persistent than for abstract words. Additionally, the effects of generalization appear to be distinct from the effects of simple exposure to words, and generalization effects are consistent with AbSANT's hypothesized mechanism of action: spreading activation from directly trained concepts to related concepts. Also consistent with this mechanism, we found that milder aphasia and both conceptual and lexical semantic processing ability predicted both direct training and generalization gains, and that executive function was predictive of generalization effects. These factors are thus important to consider when evaluating the appropriateness of AbSANT for individual clients.

Gallium Liquid Metal: Nanotoolbox for Antimicrobial Applications.

The proliferation of drug resistance in microbial pathogens poses a significant threat to human health. Hence, treatment measures are essential to surmount this growing problem. In this context, liquid metal nanoparticles are promising. Gallium, a post-transition metal notable for being a liquid at physiological temperature, has drawn attention for its distinctive properties, high antimicrobial efficacy, and low toxicity. Moreover, gallium nanoparticles demonstrate anti-inflammatory properties in immune cells. Gallium can alloy with other metals and be prepared in various composites to modify and tailor its characteristics and functionality. More importantly, the bactericidal mechanism of gallium liquid metal could sidestep the threat of emerging drug resistance mechanisms. Building on this rationale, gallium-based liquid metal nanoparticles can enable impactful and innovative strategic pathways in the battle against antimicrobial resistance. This review outlines the characteristics of gallium-based liquid metals at the nanoscale and their corresponding antimicrobial mechanisms to provide a comprehensive yet succinct overview of their current antimicrobial applications. In addition, challenges and opportunities that require further research efforts have been identified and discussed.

An atomically smooth container: Can the native oxide promote supercooling of liquid gallium?

Metals tend to supercool-that is, they freeze at temperatures below their melting points. In general, supercooling is less favorable when liquids are in contact with nucleation sites such as rough surfaces. Interestingly, bulk gallium (Ga) can significantly supercool, even when it is in contact with heterogeneous surfaces that could provide nucleation sites. We hypothesized that the native oxide on Ga provides an atomically smooth interface that prevents Ga from directly contacting surfaces, and thereby promotes supercooling. Although many metals form surface oxides, Ga is a convenient metal for studying supercooling because its melting point of 29.8°C is near room temperature. Using differential scanning calorimetry (DSC), we show that freezing of Ga with the oxide occurs at a lower temperature (-15.6 ± 3.5°C) than without the oxide (6.9 ± 2.0°C when the oxide is removed by HCl). We also demonstrate that the oxide enhances supercooling via macroscopic observations of freezing. These findings explain why Ga supercools and have implications for emerging applications of Ga that rely on it staying in the liquid state.

Item Response Theory Modeling of the Verb Naming Test.

PURPOSE: Item response theory (IRT) is a modern psychometric framework with several advantageous properties as compared with classical test theory. IRT has been successfully used to model performance on anomia tests in individuals with aphasia; however, all efforts to date have focused on noun production accuracy. The purpose of this study is to evaluate whether the Verb Naming Test (VNT), a prominent test of action naming, can be successfully modeled under IRT and evaluate its reliability. METHOD: We used responses on the VNT from 107 individuals with chronic aphasia from AphasiaBank. Unidimensionality and local independence, two assumptions prerequisite to IRT modeling, were evaluated using factor analysis and Yen's Q 3 statistic (Yen, 1984), respectively. The assumption of equal discrimination among test items was evaluated statistically via nested model comparisons and practically by using correlations of resulting IRT-derived scores. Finally, internal consistency, marginal and empirical reliability, and conditional reliability were evaluated. RESULTS: The VNT was found to be sufficiently unidimensional with the majority of item pairs demonstrating adequate local independence. An IRT model in which item discriminations are constrained to be equal demonstrated fit equivalent to a model in which unique discrimination parameters were estimated for each item. All forms of reliability were strong across the majority of IRT ability estimates. CONCLUSIONS: Modeling the VNT using IRT is feasible, yielding ability estimates that are both informative and reliable. Future efforts are needed to quantify the validity of the VNT under IRT and determine the extent to which it measures the same construct as other anomia tests. SUPPLEMENTAL MATERIAL: https://doi.org/10.23641/asha.22329235.

Technology Roadmap for Flexible Sensors.

Humans rely increasingly on sensors to address grand challenges and to improve quality of life in the era of digitalization and big data. For ubiquitous sensing, flexible sensors are developed to overcome the limitations of conventional rigid counterparts. Despite rapid advancement in bench-side research over the last decade, the market adoption of flexible sensors remains limited. To ease and to expedite their deployment, here, we identify bottlenecks hindering the maturation of flexible sensors and propose promising solutions. We first analyze challenges in achieving satisfactory sensing performance for real-world applications and then summarize issues in compatible sensor-biology interfaces, followed by brief discussions on powering and connecting sensor networks. Issues en route to commercialization and for sustainable growth of the sector are also analyzed, highlighting environmental concerns and emphasizing nontechnical issues such as business, regulatory, and ethical considerations. Additionally, we look at future intelligent flexible sensors. In proposing a comprehensive roadmap, we hope to steer research efforts towards common goals and to guide coordinated development strategies from disparate communities. Through such collaborative efforts, scientific breakthroughs can be made sooner and capitalized for the betterment of humanity.

Liquid metal-based soft, hermetic, and wireless-communicable seals for stretchable systems.

Soft materials tend to be highly permeable to gases, making it difficult to create stretchable hermetic seals. With the integration of spacers, we demonstrate the use of liquid metals, which show both metallic and fluidic properties, as stretchable hermetic seals. Such soft seals are used in both a stretchable battery and a stretchable heat transfer system that involve volatile fluids, including water and organic fluids. The capacity retention of the battery was ~72.5% after 500 cycles, and the sealed heat transfer system showed an increased thermal conductivity of approximately 309 watts per meter-kelvin while strained and heated. Furthermore, with the incorporation of a signal transmission window, we demonstrated wireless communication through such seals. This work provides a route to create stretchable yet hermetic packaging design solutions for soft devices.

Flexible-to-Stretchable Mechanical and Electrical Interconnects.

Stretchable electronic devices that maintain electrical function when subjected to stress or strain are useful for enabling new applications for electronics, such as wearable devices, human-machine interfaces, and components for soft robotics. Powering and communicating with these devices is a challenge. NFC (near-field communication) coils solve this challenge but only work efficiently when they are in close proximity to the device. Alternatively, electrical signals and power can arrive via physical connections between the stretchable device and an external source, such as a battery. The ability to create a robust physical and electrical connection between mechanically disparate components may enable new types of hybrid devices in which at least a portion is stretchable or deformable, such as hinges. This paper presents a simple method to make mechanical and electrical connections between elastomeric conductors and flexible (or rigid) conductors. The adhesion at the interface between these disparate materials arises from surface chemistry that forms strong covalent bonds. The utilization of liquid metals as the conductor provides stretchable interconnects between stretchable and non-stretchable electrical traces. The liquid metal can be printed or injected into vias to create interconnects. We characterized the mechanical and electrical properties of these hybrid devices to demonstrate the concept and identify geometric design criteria to maximize mechanical strength. The work here provides a simple and general strategy for creating mechanical and electrical connections that may find use in a variety of stretchable and soft electronic devices.

Comparing the Reliability of Virtual and In-Person Post-Stroke Neuropsychological Assessment with Language Tasks.

OBJECTIVE: Neuropsychological testing is essential for both clinical and basic stroke research; however, the in-person nature of this testing is a limitation. Virtual testing overcomes the hurdles of geographic location, mobility issues and permits social distancing, yet its validity has received relatively little investigation, particularly in comparison with in-person testing. METHOD: We expand on our prior findings of virtual testing feasibility by assessing virtual versus in-person administration of language and communication tasks with 48 left-hemisphere stroke patients (21 F, 27 M; mean age = 63.4 ± 12; mean years of education = 15.3 ± 3.5) in a quasi-test-retest paradigm. Each participant completed two testing sessions: one in their home and one in the research lab. Participants were assigned to one of the eight groups, with the testing condition (fully in-person, partially virtual), order of home session (first, second) and technology (iPad, Windows tablet) varied across groups. RESULTS: Across six speech-language tasks that utilized varying response modalities and interfaces, we found no significant difference in performance between virtual and in-person testing. However, our results reveal key considerations for successful virtual administration of neuropsychological tests, including technology complications and disparities in internet access. CONCLUSIONS: Virtual administration of neuropsychological assessments demonstrates comparable reliability with in-person data collection involving stroke survivors, though technology issues must be taken into account.