Bulk Liquid Metal Research Articles

Surface-Enhanced Raman Scattering Sensors Employing a Nanoparticle-On-Liquid-Mirror (NPoLM) Architecture.

Surface-enhanced Raman scattering (SERS) sensors typically employ nanophotonic structures that support high-field confinement and enhancement in hotspots to increase the Raman scattering from target molecules by orders of magnitude. In general, high field and SERS enhancement can be achieved by reducing the critical dimensions and mode volumes of the hotspots to nanoscale. To this end, a multitude of SERS sensors employing photonic structures with nanometric hotspots have been demonstrated. However, delivering analyte molecules into nanometric hotspots is challenging, and the trade-off between field confinement/enhancement and analyte delivery efficiency is a critical limiting factor for the performance of many nanophotonic SERS sensors. Here, a new type of SERS sensor employing solid-metal nanoparticles and bulk liquid metal is demonstrated to form nanophotonic resonators with a nanoparticle-on-liquid-mirror (NPoLM) architecture, which effectively resolves this trade-off. In particular, this unconventional sensor architecture allows for the convenient formation of nanometric hotspots by introducing liquid metal after analyte molecules are efficiently delivered to the surface of gold nanoparticles. In addition, a cost-effective and reliable process is developed to produce gold nanoparticles on a substrate suitable for forming NPoLM structures. These NPoLM structures achieve two orders of magnitude higher SERS signals than the gold nanoparticles alone.

Mechanism behind the Controlled Generation of Liquid Metal Nanoparticles by Mechanical Agitation.

The size-controlled synthesis of liquid metal nanoparticles is necessary in a variety of applications. Sonication is a common method for breaking down bulk liquid metals into small particles, yet the influence of critical factors such as liquid metal composition has remained elusive. Our study employs high-speed imaging to unravel the mechanism of liquid metal particle formation during mechanical agitation. Gallium-based liquid metals, with and without secondary metals of bismuth, indium, and tin, are analyzed to observe the effect of cavitation and surface eruption during sonication and particle release. The impact of the secondary metal inclusion is investigated on liquid metals' surface tension, solution turbidity, and size distribution of the generated particles. Our work evidences that there is an inverse relationship between the surface tension and the ability of liquid metals to be broken down by sonication. We show that even for 0.22 at. % of bismuth in gallium, the surface tension is significantly decreased from 558 to 417 mN/m (measured in Milli-Q water), resulting in an enhanced particle generation rate: 3.6 times increase in turbidity and ∼43% reduction in the size of particles for bismuth in gallium liquid alloy compared to liquid gallium for the same sonication duration. The effect of particles' size on the photocatalysis of the annealed particles is also presented to show the applicability of the process in a proof-of-concept demonstration. This work contributes to a broader understanding of the synthesis of nanoparticles, with controlled size and characteristics, via mechanical agitation of liquid metals for diverse applications.

Divide and Conquer: Design of Gallium‐Based Liquid Metal Particles for Soft and Stretchable Electronics

AbstractGallium‐based liquid metal (LM) has attracted considerable attention as a promising material for stretchable conductors due to its remarkable combination of deformability and metallic conductivity. However, LM inherently faces challenges such as high surface tension, resistance increase, electrical failure due to leakage, and limited mechanical stability. Recently, researchers have explored the concept of “dividing” bulk LM into microparticles (LMP) as a means of addressing these limitations. Nonetheless, the fabrication of LMP results in inherent electrical insulation, requiring additional activation steps to enable their use as stretchable conductors. In this review, the potential of LMP is discussed as an alternative to bulk LM and explore various methods to generate stable LMP‐based conductors and electrically activate LMP for their implementation in soft and stretchable electronics.

Supramolecular gelator functionalized liquid metal nanodroplets as lubricant additive for friction reduction and anti-wear

In this work, dopamine n-butenylamide (DBA) modified GLM nanodroplets were prepared via directional ultrasound of bulk liquid metal in ethanol aqueous solution as well as DBA self-assembly, followed by grafting with urea-based gelators via radical polymerization to obtain GLM-based supramolecular gelators (Gelator@GLM). The grafting gelators can impart their good compatibility between the GLM nanodroplets and the base oil, so that the Gelator@GLM nanodroplets can be dispersed in the base oil uniformly and stably for more than 3 weeks. Meanwhile, the tribological properties of Gelator@GLM nanodroplets was significantly enhanced, with a reduction of coefficient of friction (COF) and the wear volume of 41.18% and 92.13%, respectively, when compared with the base oil. Furthermore, Gelator@GLM additives exhibited stable lubrication performance even under variable temperature and frequency conditions. The synergistic effect of GLM nanodroplets and the gels generating a physical adsorption film and a chemically protective film (containing iron and chromium oxides, nitrides and carbides) can be credited with the improved tribological performance.

A Numerical Study of Scenarios for the Substitution of Pulverized Coal Injection by Blast Furnace Gas Enriched by Hydrogen and Oxygen Aiming at a Reduction in CO2 Emissions in the Blast Furnace Process

A numerical simulation procedure is proposed for analyzing the partial replacement of pulverized coal injection by hydrogen, oxygen, and blast furnace gas (BFG) injections mixed with pulverized coal (PCI) within the tuyeres of large blast furnaces. The massive use of hydrogen-rich gas is extremely interesting for ironmaking blast furnaces in the context of net-zero carbon hot metal production. Likewise, this new approach allows for increasing productivity and for reducing the specific emissions of carbon dioxide toward a net-zero carbon ironmaking technology. Nevertheless, the mixture of pulverized coal injection and gas injection is a complex technology. In addition to the impact on chemical reactions and energy exchange, the internal temperature and gas flow patterns can also change drastically. With a view to assessing the state of the furnace in this complex operation, a comprehensive mathematical model utilizing multiphase theory was developed. The model simultaneously handles bulk solids (sinter, pellets, small coke, granular coke, and also iron ore), gas, liquid metal and slag, and coal powder phases. The associated conservation equations take into account momentum, mass, chemical species, and energy while being discretized and solved using finite volume techniques. The numerical model was validated against the reference operating conditions using 220 kg per ton of pig iron (kg/tHM) of pulverized coal. Therefore, the combined injection of different concentrations of fuel hydrogen, blast furnace gas, and oxygen was simulated for replacing 40, 60, and 80 kg/tHM of coal injection. Theoretical analysis showed that the best scenario with stable operation conditions could be achieved with a productivity increase of 20% corresponding to a CO2 reduction of 15% and 60 kg/tHM of PCI replacement.

Stretchable Liquid Metal Films with High Surface Area and Strain Invariant Resistance

AbstractThis paper reports soft and stretchable films of liquid metal particles (LMPs) that offer high surface area and high conductivity. Liquid metals (LM) based on gallium are compelling conductors for soft and stretchable devices, yet it is difficult to make electrodes of LM with high surface area due to the tendency of liquids to minimize their surface area. To form films of percolated particles with high surface area, LMPs are first created by sonicating LM in isopropanol with trace amounts of hydrochloric acid and 1,6‐hexane dithiol to decrease the amount of surface oxide on the LMPs. A film of these particles placed on a tacky substrate is initially insulating but percolate into conductive paths by straining the substrate. The resulting electrode has high conductivity (1.64 × 105 S m−1) and high surface area (1257% greater than a bulk LM film with the same areal footprint). Interestingly, these electrodes have nearly strain‐invariant resistance (R/R0 = 1.23 at 600% strain). The ability to create high surface area electrodes in such a simple manner may find use in sensing, capacitive storage, batteries, and energy‐harvesting devices.

Self-Standing, Photothermal-Actuating, and Motion-Monitoring Janus Films One-Pot Synthesized by Green Carboxymethyl Glucomannan/Liquid Metal Nanoinks.

Downsizing bulk liquid metals (LM) at the nanometer scale with biocompatibility and multifunction is a key process for electronic or medical applications. Here, we report a stable and green LM aqueous colloidal ink by wrapping eutectic gallium-indium alloys (EGaIn) with carboxymethyl glucomannan (CGM) derived from radiata pine chip, which is capable of being prepared into a free-standing, photothermal-actuating, and motion-monitoring Janus film. With the assistance of CGM, the bulk EGaIn was ultrasonicated into stable nanodroplets (∼500 nm) with a typical "core-shell" structure, in which the colloidal inks can be stored for more than 1 week under room temperature. The stable CGM/EGaIn inks can be patterned on different substrates to form coating layers or self-assembled into free-standing Janus films with high mechanical strength and modulus (∼94 MPa and ∼3.8 GPa) by density deposition. Such a Janus film with anisotropic thermal conductivity made it a potential photothermal actuator. In addition, the biocompatible film demonstrated both high conductivity and large resistance variation in response to strain change (gauge factor >500), allowing for human motion monitoring. This work provides a new prospect for the development of biocompatible and high-performance nano-LM materials.

Tailorable, Lightweight and Superelastic Liquid Metal Monoliths for Multifunctional Electromagnetic Interference Shielding

HighlightsA confined thermal expansion strategy to fabricate liquid metal (LM)-based monoliths with continuous LM network at ultra-low content.The results show a strong integration advantage of LM-based monoliths in density, mechanical strength, electromagnetic interference shielding effectiveness, and near field shielding effectiveness, as well as multi-functions such as magnetic actuation.Liquid metal (LM) has become an emerging material paradigm in the electromagnetic interference shielding field owing to its excellent electrical conductivity. However, the processing of lightweight bulk LM composites with finite package without leakage is still a great challenge, due to high surface tension and pump-out issues of LM. Here, a novel confined thermal expansion strategy based on expandable microsphere (EM) is proposed to develop a new class of LM-based monoliths with 3D continuous conductive network. The EM/LM monolith (EM/LMm) presents outstanding performance of lightweight like metallic aerogel (0.104 g cm−1), high strength (3.43 MPa), super elasticity (90% strain), as well as excellent tailor ability and recyclability, rely on its unique gas-filled closed-cellular structure and refined LM network. Moreover, the assembled highly conducting EM/LMm exhibits a recorded shielding effectiveness (98.7 dB) over a broad frequency range of 8.2–40 GHz among reported LM-based composites at an ultra-low content of LM, and demonstrates excellent electromagnetic sealing capacity in practical electronics. The ternary EM/LM/Ni monoliths fabricated by the same approach could be promising universal design principles for multifunctional LM composites, and applicable in magnetic responsive actuator.

Improving tribological behaviors of gallium-based liquid metal by h-BN nano-additive

Gallium-based liquid metal is a potential lubricant on account of its high load capacity and thermal stability. However, the lubrication performance of gallium-based liquid metal (LM) is limited by its metallic characteristics. In this work, hexagonal boron nitride (h-BN) nanosheet with good lubricity is utilized as additive to enhance lubrication behaviors of LM. The bonding between LM and h-BN particles is reversible. In alkaline solution, LM is able to be separated from h-BN particles and agglomerate to bulk liquid metal. Moreover, our frictional tests demonstrate that when using h-BN as additive in LM, it holds enhanced tribological performance including reduction of the friction coefficient and wear rate in contrast to the pure LM. Moreover, the study of the lubrication mechanisms suggests that the adhesion of LM and deposition of h-BN are the critical factors for improving lubricity. This work proposed a facile method to improve the tribological behaviours of LM and promoted the understanding of the lubricating principles of LM and h-BN.

Sustainable existence of solid mercury (Hg) nanoparticles at room temperature and their applications.

Although liquid mercury (Hg) has been known since antiquity, the formation of stable solid nano forms of Hg at room temperature has not been reported so far. Here, for the first time, we report a simple sonochemical route to obtain solid mercury nanoparticles, stabilized by reduced graphene oxide at ambient conditions. The as-formed solid Hg nanoparticles were found to exhibit remarkable rhombohedral morphology and crystallinity at room temperature. Extensive characterization using various physicochemical techniques revealed the unique properties of the solid nanoparticles of Hg compared to its bulk liquid metal phase. Furthermore, the solid nature of the Hg nanoparticles was studied electrochemically, revealing distinctive properties. We believe that solid Hg nanoparticles have the potential for important applications in the fields of electroanalytical chemistry and electrocatalysis.

Surface modification of liquid metal as an effective approach for deformable electronics and energy devices.

The fields of flexible or stretchable electronics and energy devices, reconfigurable and compliant soft robotics, wearable e-textiles or health-care devices have paid significant attention to the need of deformable conductive electrodes due to its critical role in device performances. Gallium-based liquid metals, such as the eutectic gallium–indium (EGaIn) being an electrically conductive liquid phase at room temperature, have attracted immense interests as a promising candidate for deformable conductor. However, in the case of bulk liquid metal, there are several limitations such as the need of encapsulation, dispersion in a polymer matrix, or accurate patterning. For these reasons, the preparation of liquid metal particles in harnessing the properties in a non-bulk form and surface modification is crucial for the success of incorporating liquid metal into functional devices. Herein, we discuss the current progress in chemical surface modification and interfacial manipulations of liquid metal particles. The physical and chemical properties of the surface modification-assisted liquid metal polymer composite are also reviewed. Lastly, the applications of the surface-modified liquid metal particles such as flexible electrode, soft robotics, energy storage or harvester, thermal conductor, dielectric sensor, and bioelectronics are discussed, and the corresponding perspectives of deformable electronics and energy devices are provided. In particular, we focus on the functionalization method or requirement of liquid metal particles in each application. The challenging issues and outlook on the applications of surface-modified liquid metal particles are also discussed.

Liquid Metals in Catalysis for Energy Applications

Summary To keep up with the fast-paced transitioning of the global energy sector, which is constantly thriving to enable reliable, economic, and sustainable energy production, catalysis research has been required to continuously evolve in response. The challenges in the existing systems are predominantly due to dependencies on heterogeneous solid catalysts that are susceptible to coking. In this respect, liquid-metal (LM) catalysts have been demonstrated to have a critical advantage over conventional catalysts. Recently, LMs acquired a place in catalysis, with a reputation often synonymous with interesting properties and a remarkable ability to break trade-offs between homogeneous and heterogeneous catalysis. This review bridges the fundamental principles of LM research and the recent advances in LM-based thermal and electrochemical catalysis for energy applications. Moreover, emerging approaches for the improved utilization of LMs are outlined, and the concepts requiring greater research attention that could enable the development of exciting energy solutions are highlighted.

Printable Liquid Metal Microparticle Ink for Ultrastretchable Electronics.

Liquid metal confined in the elastomer represents an ideal platform for stretchable electronics with ultimate deformability. To enable facile and scalable patterning of conductive features, bulk liquid metal is typically dispersed into fine particles to formulate printable inks. The presence of native oxide or organic ligands stabilizing these liquid metal particles unfortunately inhibits their direct coalescence to recover the metallic conductivity and liquid-state deformability. Here, we report a chemical sintering process that converts printed liquid metal microparticles into a highly deformable conductor. The process involves the removal of surface passivating oxide by a short exposure to acid fume and subsequent selective wetting of liquid metal microparticles onto copper nanoplates present in the ink formulation. The chemical reaction provides the basis for a facile and scalable procedure to print conductive features over a large area with exceptional conductivity (>104 S cm-1) and ultrahigh stretchability (∼1000% strain). Their practical suitability is demonstrated by the fabrication of an ultrastretchable ribbon cable and an epidermal heater.

Effect of Stirring on the Quality of ADC 12 Cast Aluminium Alloy

Stirring is one the most utilized process in small foundry. It is used for homogenizing the temperature and mixing process during melting. However, stirring may cause undesirable effect to the quality of castings if it is not managed properly. Bifilm is one of the defects that can be detrimental to the quality of aluminium castings, and its formation can be related to the stirring during melting. The research aim is to investigate the effect of stirring during melting of cast aluminium alloys. The quality of castings is approached by the term of bifilm index and mechanical properties. ADC 12 cast aluminium alloys is used in the experiment. The ADC 12 ingots are melted at 720 °C, and then stirred for 0, 3 and 5 minutes. Reduced Pressure Test is used for determining the bifilm index. Samples for mechanical testing are also casted into specific geometry. Results indicate that prolonged stirring time increases the bifilm index, indicating that more porosity and bifilm oxide are formed. Extended stirring time instigates more turbulence in liquid metal, hence surface oxides are folded and trapped in the bulk liquid metal. Charpy impact test, hardness test and tensile test have also carried out. More Porosity and bifilm oxide are formed in the samples and tend to decrease the mechanical property.

Numerical Simulation and Experimental Validation of Liquid Metal Droplet Formation in a Co-Flowing Capillary Microfluidic Device.

A two-phase flow axisymmetric numerical model was proposed to understand liquid metal droplet formation in a co-flowing capillary microfluidics device based on a phase field model. The droplet detachment processes were observed in the experiment and are in good agreement with the simulation method. The effects of the viscosities and flowrates of the continuous phase fluid, interfacial tension as well as the wetting property of the metallic needle against the bulk liquid metal on the droplet formation and production rate were numerically investigated. It was found that the droplet diameter decreased with the increment of the viscosities and flowrates of the outer phase carrier fluid. The dispersed phase fluid with high interfacial tension tended to prolong the time for equilibrium between the viscous drag force and interfacial tension on the liquid–liquid fluid surface, delaying the droplet to be pinched off from the capillary orifice and causing large droplet diameter. Finally, the wetting performance of the metallic needle against the liquid metal was explored. The result indicate that the droplet diameter became less dependent on the contact angle while the size distribution of the liquid metal droplet was affected by their wetting performance. A more hydrophilic wetting performance were expected to prepare liquid metal droplet with more monodispersity. The numerical model and simulation results provide the feasibility of predicting the droplet formation with a high surface tension in a glass capillary microfluidic device.

Liquid Metal–Mediated Mechanochemical Polymerization

Mechanically controlled polymerization that employs the mechanical energy to fabricate novel synthetic materials has attracted considerable interest. However, only a few examples have been achieved so far, owing to the limited choices of materials and strategies. Herein, a versatile, liquid metal (LM)-mediated mechanochemical polymerization method (LMMMP) is developed for the air-compatible, robust preparation of polymers in an aqueous solution. This method involves the simultaneous disruption of bulk LMs into micro- and nanodroplets and the combination of monomers into polymers during ultrasonic irradiation. The pristine and reactive LM surface continuously generated by ultrasound endows this polymerization method with excellent oxygen tolerance, high reaction rate, and the ability to produce polymers with high molecular weight from a wide variety of water-soluble monomers. Besides, LM droplets are readily reclaimed and reused for polymerization. The authors envision that the LMMMP promotes the utilization of mechanical energy for the synthesis of functional polymers, constitutes a novel fabrication approach for polymer-LM nanocomposites, and provides new insight into the design of LM-based platforms for polymerization.

Liquid Metal-Mediated Mechanochemical Polymerization.

Mechanically controlled polymerization that employs the mechanical energy to fabricate novel synthetic materials has attracted considerable interest. However, only a few examples have been achieved so far, owing to the limited choices of materials and strategies. Herein, a versatile, liquid metal (LM)-mediated mechanochemical polymerization method (LMMMP) is developed for the air-compatible, robust preparation of polymers in an aqueous solution. This method involves the simultaneous disruption of bulk LMs into micro- and nanodroplets and the combination of monomers into polymers during ultrasonic irradiation. The pristine and reactive LM surface continuously generated by ultrasound endows this polymerization method with excellent oxygen tolerance, high reaction rate, and the ability to produce polymers with high molecular weight from a wide variety of water-soluble monomers. Besides, LM droplets are readily reclaimed and reused for polymerization. The authors envision that the LMMMP promotes the utilization of mechanical energy for the synthesis of functional polymers, constitutes a novel fabrication approach for polymer-LM nanocomposites, and provides new insight into the design of LM-based platforms for polymerization.

Novel Anticorrosion Property of Organic Coating Based on Liquid Metal

AbstractCompared with the traditional solid fillers, liquid metal can be easily treated into small particles similar to liquid capsule just by a sonication method. Epoxy‐based coatings containing liquid metal (EGaIn) particles are prepared easily via a straightforward method, and its corrosion performance and mechanical property of the coating are investigated. The results show that a small amount of liquid metal particles can improve the corrosion protection performance of the coatings via enhancing the barrier properties, which is completely different with the bulk liquid metal. It also improves the anticorrosion property of the coating containing zinc particles by increasing the contact area between zinc particles themselves and steel substrate, and inhibiting the corrosion process. Meanwhile, the mechanical properties are improved because particles fill the defects of coating well and dissipate stress concentration with its similarity to capsule.

Emergence of Liquid Metals in Nanotechnology.

Bulk liquid metals have prospective applications as soft and fluid electrical and thermal conductors in electronic and optical devices, composites, microfluidics, robotics, and metallurgy with unique opportunities for processing, chemistry, and function. Yet liquid metals' great potential in nanotechnology remains in its infancy. Although work to date focuses primarily on Ga, Hg, and their alloys, to expand the field, we define "liquid metals" as metals and alloys with melting points (mp) up to 330 °C, readily accessible and processable even using household kitchen appliances. Such a definition encompasses a family of metals-including the majority of post-transition metals and Zn group elements (excluding Zn itself)-with remarkable versatility in chemistry, physics, and engineering. These liquid alloys can create metallic compounds of different morphologies, compositions, and properties, thereby enabling control over nanoscale phenomena. In addition, the presence of electronic and ionic "pools" within the bulk of liquid metals, as well as deviation from classical metallurgy on the surfaces of liquid metals, provides opportunities for gaining new capabilities in nanotechnology. For example, the bulk and surfaces of liquid metals can be used as reaction media for creating and manipulating nanomaterials, promoting reactions, or controlling crystallization of dissolved species. Interestingly, liquid metals have enormous surface tensions, yet the tension can be tuned electrically over a wide range or modified via surface species, such as the native oxides. The ability to control the interfacial tension allows these liquids to be readily reduced in size to the nanoscale. The liquid nature of such nanoparticles enables shape-reconfigurable structures, the creation of soft metallic nanocomposites, and the dissolution or dispersion of other materials within (or on) the metal to produce multiphasic or heterostructure particles. This Perspective highlights the salient features of these materials and seeks to raise awareness of future opportunities to understand and to utilize liquid metals for nanotechnology.

Capillary-Based Microfluidic Fabrication of Liquid Metal Microspheres toward Functional Microelectrodes and Photothermal Medium

Liquid metals (LMs) possess tremendous potential applications in flexible electronic devices, heat flow management, and smart actuators. Splitting the bulk LMs into microspheres is of great significance to fabricate free-standing and microscale LM-based functional materials and devices. However, it is difficult to disperse the bulk LMs into microspheres because of their large surface tension and high density. In this work, the capillary-based microfluidic chip is employed to continuously and automatically generate LM microspheres in a large scale. The capillary-based microfluidic fabrication is universally applicable in ionic aqueous solution, hydrophobic solution, and the polymeric aqueous solution. The precise size control of LM microspheres can be easily realized by the co-flowing configuration in the microchannels. The coefficient of size variation of monodispersed LM microspheres can be controlled to as low as 0.47%. The free-standing LM microspheres can be used as functional microelectrodes within a wide temperature range from -19.8 to 20 °C and to fabricate tunable integrated circuits with different output powers. Most importantly, the LM microspheres exhibit photothermal property, which is used to make the optical sensor with linear response and to conduct the solar energy harvesting. The capillary-based microfluidic fabrication of LM microspheres provides a facile and templated methodology for processing bulk LMs into microscale units. The LM microspheres with excellent electrical conductivity and photothermal property hold great promise for the development of miniature soft electronics, light-driven actuators, and energy conversion medium.