Liquid Metal Research Articles

Surface-Enriched Room-Temperature Liquid Bismuth for Catalytic CO2 Reduction.

Bismuth-based electrocatalysts are effective for carbon dioxide (CO2) reduction to formate. However, at room temperature, these materials are only available in solid state, which inevitably suffers from surface deactivation, declining current densities, and Faradaic efficiencies. Here, the formation of a liquid bismuth catalyst on the liquid gallium surface at ambient conditions is shown as its exceptional performance in the electrochemical reduction of CO2 (i.e., CO2RR). By doping a trace amount of bismuth (740ppm atomic) in gallium liquid metal, a surface enrichment of bismuth by over 400 times (30 at%) in liquid state is obtained without atomic aggregation, achieving 98% Faradic efficiency for CO2 conversion to formate over 80 h. Ab initio molecular simulations and density functional theory calculations reveal that bismuth atoms in the liquid state are the most energetically favorable sites for the CO2RR intermediates, superior to solid Bi-sites, as well as joint GaBi-sites. This study opens an avenue for fabricating high-performing liquid-state metallic catalysts that cannot be reached by elementary metals under electrocatalytic conditions.

Electrodeposition behaviour of samarium in 1,3-dimethyl-2-imidazolidone solvent

Abstract The present study investigates the electrochemistry spectroscopy of Sm(III), and electrodeposition of samarium metal in neutral ligand-based ionic liquid (solvate ionic liquid). Mixture consisted of a samarium precursor (either samarium triflate or samarium nitrate hexahydrate) in the solvate ionic liquid, 1.3-dimethyl-2-imidazolidone (DMI). FT-IR analysis of Sm(III)-DMI electrolytes indicates that Sm3+ ion coordinates with DMI through carbonyl group (C=O); the band splits into two with emergence of new peak at 1630 cm−1 and 1649 cm−1 for the triflate and nitrate solutions, respectively. Raman spectroscopy also confirms the solvation of Sm(III) with DMI through oxygen atom of the carbonyl group. Voltametric behaviour of Sm(III) ion indicates two-step reduction mechanism via Sm(III)/Sm(II) at ca. −2.0 V and Sm(II)/Sm(0) at ca. −3.0 V vs. Ag/Ag+ for both samarium(III)-containing electrolytes. Diffusion coefficient value of Sm(III) was determined to be 2.185 × 10−6 cm2/s and 2.418 × 10−8 cm2/s for triflate and nitrate electrolytes, respectively. Electrodeposition of samarium was achieved through constant potential electrolysis using copper substrate as the working electrode which yielded compact deposits from triflate-DMI and non-uniform granular deposit from nitrate-DMI electrolyte. Ex situ X-ray photoelectron spectroscopy analysis of the as-deposited samples revealed the presence of metallic Sm (1081 eV) co-existing with its oxide form (1083 eV).

Thiol Coordination Softens Liquid Metal Particles To Improve On-Demand Conductivity.

Achieving tunable rupturing of eutectic gallium indium (EGaIn) particles holds great significance in flexible electronic applications, particularly pressure sensors. We tune the mechanosensitivity of EGaIn particles by preparing them in toluene with thiol surfactants and demonstrate an improvement over typical preparations in ethanol. We observe, across multiple length scales, that thiol surfactants and the nonpolar solvent synergistically reduce the applied stress requirements for electromechanical actuation. At the nanoscale, dodecanethiol and propanethiol in toluene suppress gallium oxide growth, as characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. Quantitative AFM imaging produces force-indentation curves and height images, while conductive AFM measures current while probing individual EGaIn particles. As the applied force increases, thiolated particles demonstrate intensified softening, rupturing, and stress-induced electrical activation at forces 40% lower than those for bare particles in ethanol. To confirm that thiolation facilitates rupturing at the macroscale, a laser is used to ablate samples of EGaIn particles. Scanning electron microscopy and resistance measurements across macroscopic samples confirm that thiolated EGaIn particles coalesce to exhibit electrical activation at 0.1 W. Particles prepared in ethanol, however, require 3 times higher laser power to demonstrate a similar behavior. This unique collection of advanced techniques demonstrates that our particle synthesis conditions can facilitate on-demand functionality to benefit electronic applications.

Flame emission spectroscopy of single droplet micro explosions.

Nanoparticles exhibit superior physical and chemical properties, making them highly desirable for various applications. Flame spray pyrolysis (FSP) is a versatile technique for synthesizing size and composition-controlled metal oxide/sulfide nanoparticles through a gas-phase reaction. To understand the fundamental mechanisms governing nanoparticle formation in FSP, simplified single-droplet experiments have proven to unravel the physicochemical mechanisms of liquid metal precursor combustions. This work introduces a novel method using flame emission spectroscopy and high-speed imaging to analyze combustion species and metal release during metalorganic single droplet combustions, with the example of the 2-ethylhexanoci acid (EHA)-tetrahydrothiophene (THT)-mesitylcopper (MiCu) precursor system. The method enables the tracing of precursor components released from droplet into the flame by spatial and temporal resolved emission tracking from combustion species (OH*, CH*, C2*, CS*, CS2*) and atomic spectral lines (Cu I). The tracking of metal emission enables the direct observation of the particle formation route, offering novel insights into the metalorganic precursor combustions. The findings of this work show a direct correlation between micro-explosions and nanoparticle formation through the gas-to-particle route. The release of copper emissions is observed with the micro-explosion event, marking the micro-explosions as the critical mechanism for the metal release and subsequent nanoparticle formation during the combustion process. The results indicate a metalorganic viscous shell formation (THT + MiCu) leading to the micro explosion. The EHA/THT ratio significantly affects the combustion behavior. Lower ratios lead to a gradual copper release before the micro explosion; higher ratios shorten the copper release and delay the micro explosion - the highest ratio results in two distinct burning stages.

Structural Evolution of Liquid Metals and Alloys.

Low-melting liquid metals are emerging as a new group of highly functional solvents due to their capability to dissolve and alloy various metals in their elemental state to form solutions as well as colloidal systems. Furthermore, these liquid metals can facilitate and catalyze multiple unique chemical reactions. Despite the intriguing science behind liquid metals and alloys, very little is known about their fundamental structures in the nanometric regime. To bridge this gap, this work employs small angle neutron scattering and molecular dynamics simulations, revealing that the most commonly used liquid metal solvents, EGaIn and Galinstan, are surprisingly structured with the formation of clusters ranging from 157Å to 15.7Å. Conversely, non-eutectic liquid metal alloys of GaSn or GaIn at low solute concentrations of 1, 2, and 5wt%, as well as pure Ga, do not exhibit these structures. Importantly, the eutectic alloys retain their structure even at elevated temperatures of 60 and 90°C, highlighting that they are not just simple homogeneous fluids consisting of individual atoms. Understanding the complex soft structure of liquid alloys will assist in comprehending complex phenomena occurring within these fluids and contribute to deriving reaction mechanisms in the realm of synthesis and liquid metal-based catalysis. This article is protected by copyright. All rights reserved.

Liquid‐Metal‐Loaded Hydrogel with Antibacterial Effect and Sustained Release of Growth Factor for Wound Healing

AbstractMultifunctional medical hydrogels play an important role in wound healing because of their excellent biocompatibility, convenient operation, and drug release capacity. So far, many efforts have been exploited to developing new‐generation hydrogels with distinctive capabilities in promoting wound healing. Herein, the liquid‐metal (LM)‐loaded hydrogels are reported with antibacterial effect under an 808 nm near‐infrared laser irradiation for wound healing therapeutic strategies. The addition of LM droplets enables the hydrogel to control the temperature rise and plays an antibacterial effect with the release of gallium3+ under laser irradiation. Benefiting from the porous network structure of hydrogels, the encapsulated growth factors can be released stably at the wound site. Under the synergistic effect of LM and growth factors in the wound tissue, the hydrogel displays antibacterial features and promotes the regeneration of epithelial tissue and neovascularization, thereby further accelerating wound healing. This hydrogel has proven biosafety and low toxicity in vitro and in vivo. With these advantages, such hydrogel is a promising candidate to be developed as a new medical product for future clinical medicine.

Printing Completely Conformal Liquid Metal Circuits on Arbitrary Curved Surfaces via Customized Conformal Mask

Printing Completely Conformal Liquid Metal Circuits on Arbitrary Curved Surfaces via Customized Conformal Mask

Model-Based input energy control for reproducible AISI 316L laser deposited tracks

In the Directed Energy Deposition (DED) process, when the mass flow of metal particles is relatively high, the thickness of the layers increases, leading to a more productive process. The higher the mass flow is, the more difficult it becomes to get a stable melt pool. The accumulation of residual heat in the previously consolidated material constitutes a thermal input affecting the balance at the laser-material interaction zone. An accurate control of the temperature of the laser-material interaction zone is critical to maintain the dynamic viscosity of the liquid metal within the narrow margin in which it can be managed in a stable way. The present work introduces a thermal model in which domains with tunable properties are considered to reproduce the growing of the manufactured sample. Concurrently, a virtual closed-loop PID regulator has been implemented in order to calculate suitable values of laser power to compensate the heat accumulated in the material, offering the results from the model as input process parameters to be directly applied in the real process. The levels of laser power proposed by the model have been experimentally applied, leading to a stable process capable of carrying out in reality the desired component.

A liquid metal-embedded 3D interconnected-porous TPU/MXene composite with improved capacitive sensitivity and pressure detection range.

Flexible capacitive sensors are widely deployed in wearable smart electronics. Substantial studies have been devoted to constructing characteristic material architectures to improve their electromechanical sensing performance by facilitating the change of the electrode layer spacing. However, the air gaps introduced by the designed material architectures are easily squeezed when subjected to high-pressure loads, resulting in a limited increase in sensitivity over a wide range. To overcome this limitation, in this work, we embed the liquid metal (LM) in the internally interconnected porous structure of a flexible composite foam to fabricate a flexible and high-performance capacitive sensor. Different from the conventional conductive elements filled composite, the incompressible feature of the embedded fluidic LM leads to significantly improved mechanical stability of the composite foam to withstand high pressure loadings, resulting in a wider pressure sensing range from 10 Pa to 260 kPa for our capacitive composite sensor. Simultaneously, the metal conductivity and liquid ductility of the embedded LM endow the as-fabricated capacitive sensor with outstanding mechanical flexibility and pressure sensitivity (up to 1.91 kPa-1). Meanwhile, the LM-embedded interconnected-porous thermoplastic polyurethane/MXene composite sensor also shows excellent reliability over 4000 long-period load cycles, and the response times are merely 60 ms and 110 ms for the loading and unloading processes, respectively. To highlight their advantages in various applications, the as-proposed capacitive sensors are demonstrated to detect human movements and monitor biophysical heart-rate signals. It is believed that our finding could extend the material framework of flexible capacitive sensors and offer new possibilities and solutions in the development of the next-generation wearable electronics.

Implantable Wet‐Adhesive Flexible Electronics with Ultrathin Gelatin Film

AbstractImplantable flexible electronic has attracted significant research interest in various fields. However, it still faces the challenge of simultaneously achieving tight adhesion to tissues in a mildly wet environment and possessing excellent biocompatibility to reduce immune rejection reactions after implantation. Here, a degradable wet‐adhesive flexible electronic device based on liquid metal and ultrathin gelatin film is developed. The ultrathin gelatin film forms numerous hydrogen bonds with tissue in a slightly humid environment, rapidly constructing a wet‐adhesive interface without damaging tissue structure. Inkjet printing is utilized to pattern the mixture of liquid metal and PVP on the surface of the ultrathin gelatin to create flexible patch. With the excellent conductivity of liquid metal, low toxicity, and similarity to natural tissue components of gelatin, flexible patch exhibits outstanding biocompatibility and fatigue resistance. It can be implanted in the body for up to 6 weeks, retaining monitoring capabilities and resisting 1 000 000 cycles of bending fatigue. This study provides a novel strategy for the future development of implantable flexible electronics.

Biphasic Liquid Metal Composite for Strain Sensor with High Stretchability and Sensitivity

Strain measurement is crucial for the safety and stability of engineering activities. With the increasing demand for sensors and large strain measurement in engineering monitoring, the study on the large strain measurement is deepening. However, the conventional strain sensors based on rigid conductive materials have limited flexibility and low stretchability, and the research of large strain and flexible sensors in engineering still lacks. In this work, a highly stretchable and sensitive flexible strain sensor based on liquid metal‐Nickle microparticles (LMN) composite is developed to detect large strain. The LMN composite, featuring uniformly dispersed Nickle microparticles within the liquid metal matrix, is deposited onto the elastomer Ecoflex base material.The LMN composite based‐sensor exhibits high sensitivity (GF = 16.14644 at strain of 200%), large stretchability (up to 200%) and low hysteresis. The theoretical relationship between the relative resistance changes and strain is derived, and the theoretical derivation is compared with experimental data to verify the accuracy of theoretical derivation. Additionally, the LMN composite based‐sensors can be used to detect pressure and bending signals in engineering. This work highlights the potential of LMN composite in broad applications and can facilitate the application of flexible sensing devices in engineering.

LES of the upper plenum of the liquid metal fast reactor under the forced flow conditions

A Large Eddy Simulation (LES) of the upper plenum of the E-SCAPE (European SCAled Pool Experiment) facility under the normal operations has been conducted to gain deeper insights into the thermal hydraulics phenomena in liquid metal fast reactors (LMFRs). The results unravel the overall flow features in the upper plenum, the thermal instability in the above core structure region and the impact of the jets from the barrel holes on the large flow circulation and thermal mixing.The above core structure region is represented using a homogeneous porous model. It is shown that during the normal operations, most of the hot stream of the lead bismuth eutectic (LBE) from the core center rises to the top and disperses from the upper barrel holes. Conversely, the cold LBE spread out from the lower barrel holes. Mixing between the two streams only affect the fluids leaving from the middle heights demonstrating limited mixing. These jets help to create a large circulation in the upper plenum region which prevents any thermal stratification. At the interface between the hotter and colder streams, there are unsteady large-scale structures resulting in a mixing layer in the thermal field. This strong mixing is not conventional turbulence and potentially cannot be captured by Reynolds Averaged Navier Stokes average (RANS) modelling.The flow in the upper plenum is dominated by the influences of the different types of jets, which include some free jets issued horizontally or angled upwards and some jets impinging onto the structures in the plenum. The jets overall behave similar to ‘standard’ jets, though significant interactions between the top and bottom jets and the background circulations have strong influences at later stages of the jets, typically after four jet diameters leading to the jets not reaching self-similarity. In addition, the turbulence that is observed in the upper plenum is largely generated by the jet flows and hence the distribution of turbulence is very non-uniform. Away from the jets, turbulence is minimal with the mixing largely driven by the large-scale circulation.

Mechanically programmable substrate enable highly stretchable solar cell arrays for self-powered electronic skin

Development of stretchable solar cells to accommodate large strain without sacrificing the power conversion efficiency is challenging. This study presents a novel approach to manufacture highly stretchable solar cell arrays, which can be integrated into wearable medical devices to operate under challenging environments. Overcoming the limitations of rigid metal wires, liquid metal wires are employed to connect single crystal silicon solar cells, ensuring both high conversion efficiency and exceptional stretchability (up to 100%). The manufacturing process introduces embedding electrospinning films into elastic silicone substrates to create a tight bond between rigid solar cells and stretchable substrates with programmable strain capabilities. Notably, a stretchable interconnect wire is efficiently fabricated using the semi-liquid metal template printing technique and demonstrates remarkable conductivity (up to 6 × 106 S/m). Individual structural unit of solar cell presents an impressive tensile rate of 200%, and endures up to 5000 cycles of tensile testing. The overall solar cell array exhibits outstanding adaptability to extensive bending and twisting, with a mere 0.1% short-circuit current reduction in its maximum stretched state. The stretchable photovoltaic device is successfully employed in creating self-powered electronic skin for continuous real-time monitoring of parameters, showcasing its valuable potential in wearable medical electronic devices and comprehensive sports health monitoring.

A review on optimum substrate surface roughness to create better wetting

Surface roughness or texture is one of the key parameters for liquid fluids or liquid metals to achieve good or poor wetting. In certain applications surface roughness of a smooth surface [mirror finish] is treated as a slippery surface for poor wettability however in a few applications’ roughness surfaces are considered as better wetting, especially for liquid metals. In this regard, to understand the parameters for the optimum surface roughness of the substrates to achieve good wetting is essential. In the present review paper, an attempt has been made to find the ideal roughness value of the substrate for better wetting of liquid metals or alloys based on substrates and fluids.

Bioinspired Liquid Metal based Soft Humanoid Robots.

The pursuit of constructing humanoid robots to replicate the anatomical structures and capabilities of human beings has been a long-standing significant undertaking and especially garnered tremendous attention in recent years. However, despite the progress made over recent decades, humanoid robots have predominantly been confined to those rigid metallic structures, which however starkly contrast with the inherent flexibility observed in biological systems. To better innovate this area, the present article systematically explores the value and potential of liquid metals and their derivatives in facilitating a crucial transition towards soft humanoid robots. Through a comprehensive interpretation of bionics, we present an overview of liquid metals' multifaceted roles as essential components in constructing advanced humanoid robots - functioning as soft actuators, sensors, power sources, logical devices, circuit systems, and even transformable skeletal structures. We conceived that the integration of these components with flexible structures, facilitated by the unique properties of liquid metals, can create unexpected versatile functionalities and behaviors to better fulfill human needs. Finally, we envision a revolution in humanoid robots, transitioning from metallic frameworks to hybrid soft-rigid structures resembling that of biological tissues. This article is expected to provide fundamental guidance for the coming research, thereby advancing the area. This article is protected by copyright. All rights reserved.

Multifunctional Nanocomposite Yield-Stress Fluids for Printable and Stretchable Electronics

Multifunctional Nanocomposite Yield-Stress Fluids for Printable and Stretchable Electronics

On Spontaneous Dispersion as a Cause of Microstratification of Metal Melts

The phenomenon of spontaneous dispersion is considered as the cause of the microstratification of metal melts. In a microstratification melt, a violation of long-range order in the arrangement of atoms (LRO) is observed, which corresponds to a dispersed particle size of more than 2 nm. Microseparation occurs due to spontaneous dispersion upon contact of liquid and solid metal or the mixing of two liquid metals. The possibility of spontaneous dispersion was assessed using three different criteria: Volmer’s criterion, Rehbinder’s criterion and the diffusion rate criterion. The diffusion rate criterion was obtained on the basis of the theory of rate processes, which describes how diffusing atoms overcome the interphase boundary. It has been established that Al–Sn melts contain colloidal-scale particles (4 nm), and Al–Si and Al–Ge melts contain atomic-scale particles (0.1 nm). For a system with a continuous series of Cu–Ni solid solutions in dispersion (Cu10Ni90—Cu20Ni80), the particle size is 2 nm. The particle size of the ternary eutectic GaInSn in the dispersion (Ga50In50—Ga50Sn50) is 5.6 nm, and the size of immiscible Cu–Fe melts in the dispersion (Cu80Fe20—Cu60Fe40) is 4.8 nm. Long-range order violations (LRO) and the presence of microlayering with colloidal particles larger than 20 nm were observed in the GaInSn ternary eutectic, in the Al–Sn simple eutectic with the preferential interaction of similar atoms, and in Cu–Fe melts with a monotectic phase diagram.

Interfacial self-assembled of covalent organic framework onto MXenes for efficient enrichment and recovery of Au(III) and Pd(II) from aqueous solution

Recovery of precious metal ions in wastewater could not only improve resource utilization, but also could reduce environmental pollution. Herein, a composite of TpPa@Nb2C was constructed by an interfacial self-assembled method and explored the synergistic adsorption effects for precious metals. The structure and morphology of the composites were analyzed by advanced characterization techniques, followed by parametric analysis of Au(III)/Pd(II) adsorption from the simulated wastewater. The results showed that the grafting of COFs with abundant reducing active sites on the MXenes could significantly improve the selectivity and adsorption capacity. Meanwhile, the interaction was found as monolayer way and controlled by chemistry process, and the maximum equilibrium Au(III) and Pd(II) uptake reached up to 910.1 and 386.2 mg/g, respectively. The competitive adsorption study showed that the co-existence of impurities had little effect on the removal rate. The mechanism analysis demonstrated that the precious metal ions were reduced to elemental gold/palladium on the network of TpPa@Nb2C, and they got three electrons or two electrons from the hydroxyl groups through redox reaction, respectively. Thus, this study provided an excellent material for enrichment and recovery of precious metals in waste liquid and the treatment of e-waste.

LM-Gel Plasticine Based on Binary Cooperative with Kneadable Shaping and Conductivity.

Liquid metal (LM)-based polymers have received growing interest for wearable health monitoring, electronic skins, and soft robotics. However, fabricating multifunctional LM-based polymers, in particular, featuring a convenient shaping ability while offering excellent deformability and conductivity remains a challenge. To overcome this obstacle, here, we propose a strategy to prepare LM-Gel "plasticine" (LGP) with great deformability, which is composed of a PVA (poly(vinyl alcohol)) soft network and an LM conductive phase. LGP can be easily constructed into different shapes such as plasticine and can be applied to different conditions (such as building a 3D circuit, circuit repair, and switch). Meanwhile, LGP has great conductivity (2.3 × 104 S/m) after surface annealing. Besides, LGP has a good electric heating performance, which shows the potential for application in wearable heating devices. Thus, this approach not only provides a way to prepare LM-polymer plasticine but also provides a novel perspective toward extending the applied range of LM-polymer composites.

Liquid-Metal-Based Spin-Coating Exfoliation for Atomically Thin Metal Oxide Synthesis.

Two-dimensional (2D) semiconductors possess exceptional electronic, optical, and magnetic properties, making them highly desirable for widespread applications. However, conventional mechanical exfoliation and epitaxial growth methods are insufficient in meeting the demand for atomically thin films covering large areas while maintaining high quality. Herein, leveraging liquid metal oxidation reaction, we propose a motorized spin-coating exfoliation strategy to efficiently produce large-area 2D metal oxide (2DMO) semiconductors with high crystallinity, atomically thin thickness, and flat surfaces on diverse substrates. Moreover, we realized a 2D gallium oxide-based deep ultraviolet solar-blind photodetector featuring a metal-semiconductor-metal structure, showcasing high responsivity (8.24 A W-1) at 254 nm and excellent sensitivity (4.3 × 1012 cm Hz1/2 W-1). This novel liquid-metal-based spin-coating exfoliation strategy offers great potential for synthesizing atomically thin 2D semiconductors, opening new avenues for future functional electronic and optical applications.