Liquid Metal Marbles

Liquid metal marbles that are droplets of liquid metal encapsulated by micro‐ or nanoparticles are introduced. Droplets of galinstan liquid metal are coated with insulators (including Teflon and silica) and semiconductors (including WO₃, TiO_2, MoO₃, In₂O₃ and carbon nanotubes) by rolling over a powder bed and also by submerging in colloidal suspensions. It is shown that these marbles can be split and merged, can be suspended on water, and are even stable when moving under the force of gravity and impacting a flat solid surface. Furthermore, the marble coating can operate as an active electronic junction and the nanomaterial coated liquid metal marble can act as a highly sensitive electrochemical based heavy metal ion sensor. This new element thus represents a significant platform for the advancement of research into soft electronics.     

Liquid Metal/Metal Oxide Frameworks

A new platform described as the liquid metal/metal oxide (LM/MO) framework is introduced. The constituent spherical structures of these frameworks are made of micro‐ to nanosized liquid metal spheres and nanosized metal oxides, combining the advantages of both materials. It is shown that the diameters of the spheres and the stoichiometry of the structures can be actively controlled. Additionally, the liquid suspension of these spheres demonstrates tuneable plasmon resonances. These spherical structures are assembled to form LM/MO frameworks which are capable of demonstrating high sensitivity towards low concentrations of heavy metal ions, and enhanced solar light driven photocalalytic activities. These demonstrations imply that the LM/MO frameworks are a suitable candidate for the development of future high performance electronic and optical devices.     

铜基金属粉末选区激光烧结的工艺研究

优化工艺参数（激光功率275～1125W，扫描速率0．04～0．06m／s，扫描间距0．15～0．30mm），对多组份铜基金属粉末（组份包括纯Cu，预合金CuSn和预合金CuP）进行了选区激光烧结（SLS）实验，其成形机制为粉末部分熔化状态下的液相烧结机制。在保证适宜的成形机制的前提下，研究了激光功率、扫描速率、扫描间距、铺粉厚度等工艺参数对烧结组织及性能的影响。结果表明，适当增加激光功率或减小扫描速率能改善烧结致密度及组织连续性。减小扫描间距致使烧结线从断续分布连续转变为较为平整的结合状态，组织致密性及均匀性显著提高。减小铺粉厚度有利于改善层问结合性；但最小铺粉厚度需适当选择，否则会因凝固收缩效应及铺粉不均匀性而降低烧结致密度。     

Ultrasoft Liquid Metal Elastomer Foams with Positive and Negative Piezopermittivity for Tactile Sensing

Soft, capacitive tactile (pressure) sensors are important for applications including human–machine interfaces, soft robots, and electronic skins. Such capacitors consist of two electrodes separated by a soft dielectric. Pressing the capacitor brings the electrodes closer together and thereby increases capacitance. Thus, sensitivity to a given force is maximized by using dielectric materials that are soft and have a high dielectric constant, yet such properties are often in conflict with each other. Here, a liquid metal elastomer foam (LMEF) is introduced that is extremely soft (elastic modulus 7.8 kPa), highly compressible (70% strain), and has a high permittivity. Compressing the LMEF displaces the air in the foam structure, increasing the permittivity over a large range (5.6–11.7). This is called “positive piezopermittivity.” Interestingly, it is discovered that the permittivity of such materials decreases (“negative piezopermittivity”) when compressed to large strain due to the geometric deformation of the liquid metal droplets. This mechanism is theoretically confirmed via electromagnetic theory, and finite element simulation. Using these materials, a soft tactile sensor with high sensitivity, high initial capacitance, and large capacitance change is demonstrated. In addition, a tactile sensor powered wirelessly (from 3 m away) with high power conversion efficiency (84%) is demonstrated.     

A Substrate‐Selective Nanoreactor Made of Molecularly Imprinted Polymer Containing Catalytic Silver Nanoparticles

An original, substrate‐selective nanoreactor is designed and characterized. The nanoreactor made of a 4‐nitrophonel (NP)‐imprinted polymer and Ag nanoparticles, can specifically recognize NP compared with its analogues 4‐nitrophenyl acetate (NPA) and 2,6‐dimethyl‐4‐nitrophenol (DNP). Under comparable conditions, this nanoreactor significantly accelerated the reduction of NP; however, much less acceleration is shown for its analogues. Unlike traditional Ag nanoreactors, which lack molecular recognition abilities, this unique nanoreactor is composed of molecularly imprinted networks, making substrate‐selective catalysis feasible.     

Metal Species–Encapsulated Mesoporous Silica Nanoparticles: Current Advancements and Latest Breakthroughs

Despite their advantageous morphological attributes and attractive physicochemical properties, mesoporous silica nanoparticles (MSNs) are merely supported as carriers or vectors for a reason. Incorporating various metal species in the confined nanospaces of MSNs (M‐MSNs) significantly enriches their mesoporous architecture and diverse functionalities, bringing exciting potentials to this burgeoning field of research. These incorporated guest species offer enormous benefits to the MSN hosts concerning the reduction of their eventual size and the enhancement of their performance and stability, among other benefits. Substantially, the guest species act through contributing to reduced aggregation, augmented durability, ease of long‐term storage, and reduced toxicity, attributes that are of particular interest in diverse fields of biomedicine. In this review, the first aim is to discuss the current advancements and latest breakthroughs in the fabrication of M‐MSNs, emphasizing the pros and cons, the confinement of various metal species in the nanospaces of MSNs, and various factors influencing the encapsulation of metal species in MSNs. Further, an emphasis on potential applications of M‐MSNs in various fields, including in adsorption, catalysis, photoluminescence, and biomedicine, among others, along with a set of examples is provided. Finally, the advances in M‐MSNs with perspectives are summarized.     

In Situ Monitoring the Role of Working Metal Catalyst Nanoparticles for Ultrahigh Purity Single‐Walled Carbon Nanotubes

The high‐end applications of single‐walled carbon nanotubes (SWCNTs) are hindered by the existence of large amount of impurities, especially the graphene layers encapsulating metal nanoparticles (metal@C NPs). The role of working metal catalysts during chemical vapor deposition (CVD) growth and post purifications by oxidation are not yet fully understood. Herein, the in situ monitoring the role of working metal catalyst NPs for ultrahigh purity SWCNTs by CVD growth and CO₂ purifications is carried out in an online thermogravimetric reactor attached with a mass spectrometer. The growth of SWCNTs almost stops after the initial 2 min, then, the mass increase of the samples mainly originates from the metal@CNP formation. Therefore, high‐purity SWCNTs (98.5 wt%) with few metal@CNPs can be available by 2 min CVD growth. Furthermore, CO₂ oxidation of the SWCNTs is also investigated in a thermogravimetric reactor. The oxidation of graphene layers surrounding the metal NPs and the SWCNTs occurs during distinct temperature ranges, which is further demonstrated by the significant differences among their oxidation activation energies. Ultrahigh purity of SWNCT with a carbon content of 99.5 wt% can be available by a CO₂‐assited purification method. The in situ study of the CVD growth and CO₂ oxidation of SWCNTs provides the real time information on the working catalyst during reaction and the reactivity information of metal@CNPs and SWCNTs under an oxidizing atmosphere. The success for the preparation of high‐purity SWCNT lies in the efficient growth of SWCNTs with a low amount of nanocarbon impurities and partial oxidation of metal@CNPs by catalytic CO₂ oxidation with proper operation parameters.     

飞秒激光在金属纳米材料制备和材料微结构加工中的应用

介绍了飞秒激光在高纯度金属纳米颗粒的制备及纳米颗粒的尺寸和形状的改变,玻璃内部形成基于金属纳米粒子的“三维空间选择性”析出的彩色图案的制备,有机聚合物微光子器件的制备以及光存储、光波导和光开关器件的制备等方面的应用。     

Thermoelectric Performance Enhancement in BiSbTe Alloy by Microstructure Modulation via Cyclic Spark Plasma Sintering with Liquid Phase

The widespread application of thermoelectric (TE) technology demands high-performance materials, which has stimulated unceasing efforts devoted to the performance enhancement of Bi₂Te₃-based commercialized thermoelectric materials. This study highlights the importance of the synthesis process for high-performance achievement and demonstrates that the enhancement of the thermoelectric performance of (Bi,Sb)₂Te₃ can be achieved by applying cyclic spark plasma sintering to Bi_xSb_2–xTe₃-Te above its eutectic temperature. This facile process results in a unique microstructure characterized by the growth of grains and plentiful nanostructures. The enlarged grains lead to high charge carrier mobility that boosts the power factor. The abundant dislocations originating from the plastic deformation during cyclic liquid phase sintering and the pinning effect by the Sb-rich nano-precipitates result in low lattice thermal conductivity. Therefore, a high ZT value of over 1.46 is achieved, which is 50% higher than conventionally spark-plasma-sintered (Bi,Sb)₂Te₃. The proposed cyclic spark plasma liquid phase sintering process for TE performance enhancement is validated by the representative (Bi,Sb)₂Te₃ thermoelectric alloy and is applicable for other telluride-based materials.     

A Novel Strategy for Preparing Stretchable and Reliable Biphasic Liquid Metal

Low‐melting liquid metal is a hugely promising material for flexible conductive patterns due to its excellent conductivity and supercompliance, especially low‐cost and environmental liquid processing technology. However, the ever‐present fluidity characteristic greatly limits the stable shape and reliability of prepared liquid metal conductive electronics. Herein, a novel solidification strategy of liquid GaIn alloys by Ni doping and heat treatment is first reported, which can efficiently create a solid phase in the liquid metal and provide an effective solution for practical applications. Particularly, the liquid characteristic is preserved for conveniently fabricating different flexible electronic circuits, and then the solidification is carried out on prepared conductive patterns by heat treatment. The solidification mechanism is revealed by the interface chemical reaction between Ni and GaIn, creating the solid phase of intermetallic compound (Ga₄Ni₃ and InNi₃) during heat treatment. Moreover, a biphasic GaInNi can be obtained by regulating the atomic ratio of gallium, indium, and nickel. As a result, the obtained GaInNi possesses extremely low sheet resistance (15 ± 4.5 to 135 ± 2.5 mΩ sq^?1) and the variation of ΔR/R₀ exhibits low level (0–2) when strained up to 100%, which offers a promising strategy to prepare stretchable and reliable liquid metal electronics.     

Motility of Metal Nanoparticles in Silicon and Induced Anisotropic Silicon Etching

The autonomous motion behavior of metal particles in Si, and the consequential anisotropic etching of silicon and production of Si nanostructures, in particular, Si nanowire arrays in oxidizing hydrofluoric acid solution, has been systematically investigated. It is found that the autonomous motion of metal particles (Ag and Au) in Si is highly uniform, yet directional and preferential along the [100] crystallographic orientation of Si, rather than always being normal to the silicon surface. An electrokinetic model has been formulated, which, for the first time, satisfactorily explains the microscopic dynamic origin of motility of metal particles in Si. According to this model, the power generated in the bipolar electrochemical reaction at a metal particle's surface can be directly converted into mechanical work to propel the tunneling motion of metal particles in Si. The mechanism of pore and wire formation and their dependence on the crystal orientation are discussed. These models not only provide fundamental interpretation of metal‐induced formation of pits, porous silicon, and silicon nanowires and nanopores, they also reveal that metal particles in the metal/Si system could work as a self‐propelled nanomotor. Significantly, it provides a facile approach to produce various Si nanostructures, especially ordered Si nanowire arrays from Si wafers of desired properties.     

激光直接烧结FGH95合金的微观组织与性能

基于直接激光金属烧结成形技术,以FGH95镍基高温合金粉末为研究对象,讨论了烧结工艺参数对制件微观组织、体积密度及显微硬度的影响。制件微观组织结构由等轴晶和枝状晶组成,在较高的激光功率、较低的扫描速度和较小的扫描间距时,等轴晶数量减少,尺寸增加,而枝状晶数量多且晶粒细微。制件的体积密度随着激光功率的提高而增大,随着扫描速率和扫描间距的增大而减小;随着激光功率和扫描速度的提高,制件的显微硬度呈先降后升趋势;随着扫描间距的增大,制件的显微硬度呈递增趋势,在到达最大值时有明显的回落。采用激光功率为900 W,扫描速度为0.8 m/min,扫描间距为0.6 mm以及粉层厚度为0.9 mm的参数组合,可获得表面平整、体积密度高、晶粒均匀细小和无明显微观缺陷的制件,其显微硬度可达到477 HV。     

Recapillarity: Electrochemically Controlled Capillary Withdrawal of a Liquid Metal Alloy from Microchannels

This paper describes the mechanistic details of an electrochemical method to control the withdrawal of a liquid metal alloy, eutectic gallium indium (EGaIn), from microfluidic channels. EGaIn is one of several alloys of gallium that are liquid at room temperature and form a thin (nm scale) surface oxide that stabilizes the shape of the metal in microchannels. Applying a reductive potential to the metal removes the oxide in the presence of electrolyte and induces capillary behavior; we call this behavior “recapillarity” because of the importance of electrochemical reduction to the process. Recapillarity can repeatably toggle on and off capillary behavior by applying voltage, which is useful for controlling the withdrawal of metal from microchannels. This paper explores the mechanism of withdrawal and identifies the applied current as the key factor dictating the withdrawal velocity. Experimental observations suggest that this current may be necessary to reduce the oxide on the leading interface of the metal as well as the oxide sandwiched between the wall of the microchannel and the bulk liquid metal. The ability to control the shape and position of a metal using an applied voltage may prove useful for shape reconfigurable electronics, optics, transient circuits, and microfluidic components.     

Synthesis,Structure, Properties,and Applications of Bimetallic Nanoparticles of Noble Metals

Bimetallic nanoparticles of noble metals are of high interest in imaging, biomedical devices, including nanomedicine, and heterogeneous catalysis. Synthesis, properties, characterization, biological properties, and practical applicability of nanoparticles on the basis of platinum group metals and the coin metals Ag and Au are discussed, also in comparison with the corresponding monometallic nanoparticles. In addition to the parameters that are required to characterize monometallic nanoparticles (mainly size, size distribution, shape, crystallographic nature, surface functionalization, charge), further information is required for a full characterization of bimetallic nanoparticles. This concerns the overall elemental composition of a bimetallic nanoparticle population (ratio of the two metals) and the internal distribution of the elements in individual nanoparticles (e.g., the presence of homogeneous alloys, core–shell systems, and possible intermediate stages). It is also important to ensure that all particles are identical in terms of elemental composition, that is, that the homogeneity of the particle population is given. Macroscopic properties like light absorption, antibacterial effects, and catalytic activity depend on these properties. The currently available methods for a full characterization of bimetallic nanoparticles are discussed, and future developments in this field are outlined.     

Liquid Metal Welding to Suppress Li Dendrite by Equalized Heat Distribution

It is important to understand the growth mechanism of Li dendrites for the protection of Li metal anodes. Herein, joule heat as another inducing mechanism for Li dendrites is proposed and demonstrated by experiments and theoretical simulations. A nonuniform interface structure can lead to disordered surface thermal distribution based on joule heat theory, which may induce chaotic nucleation and growth of dendrites. Based on this concept, a new strategy of liquid metal welding is explored to overcome such joule heat distribution issue. This strategy is universally compatible with other traditional protection routes such as solid electrode interphase films, charging protocols, and electrolytes. Multistrategy synergetic protection strategies result in remarkable performance.     

Creation of Liquid Metal 3D Microstructures Using Dielectrophoresis

Patterning customized arrays of microscale Galinstan or EGaIn liquid metals enables the creation of a variety of microfabricated systems. Current techniques for creating microsized 3D structures of liquid metals are limited by the large dimension or low aspect ratio of such structures, and time‐consuming processes. Here, a novel technique for creating 3D microstructures of Galinstan using dielectrophoresis is introduced. The presented technique enables the rapid creation of Galinstan microstructures with various dimensions and aspect ratios. Two series of proof‐of‐concept experiments are conducted to demonstrate the capabilities of this technique. First, the 3D Galinstan microstructures are utilized as 3D microelectrodes to enhance the trapping of tungsten trioxide (WO₃) nanoparticles flowing through a microfluidic channel. Second, the patterned Galinstan microstructures are utilized as microfins to improve the dissipation of heat within a microfluidic channel that is located onto a hot spot. The presented technique can be readily used for creating customized arrays of 3D Galinstan microstructures for a wide range of applications.     

Size Effect on Properties of Varistors Made From Zinc Oxide Nanoparticles Through Low Temperature Spark Plasma Sintering

Conditions for the elaboration of nanostructured varistors by spark plasma sintering (SPS) are investigated, using 8‐nm zinc oxide nanoparticles synthesized following an organometallic approach. A binary system constituted of zinc oxide and bismuth oxide nanoparticles is used for this purpose. It is synthesized at room temperature in an organic solution through the hydrolysis of dicyclohexylzinc and bismuth acetate precursors. Sintering of this material is performed by SPS at various temperatures and dwell times. The determination of the microstructure and the chemical composition of the as‐prepared ceramics are based on scanning electron microscopy and X‐ray diffraction analysis. The nonlinear electrical characteristics are evidenced by current–voltage measurements. The breakdown voltage of these nanostructured varistors strongly depends on grain sizes. The results show that nanostructured varistors are obtained by SPS at sintering temperatures ranging from 550 to 600 °C.     

Multifunctional Liquid-Free Ionic Conductive Elastomer Fabricated by Liquid Metal Induced Polymerization

Novel liquid-free ionic conductive elastomers are fabricated by the polymerization of acrylic acid (AA) in polymerizable deep eutectic solvent (PDES). Liquid metal (LM) nanodroplets are used to initiate and further cross-link polyacrylic acid (PAA) chains into a liquid-free polymeric network without any extra initiators and cross-linkers. The resulting liquid-free ionic conductive elastomers exhibit high transparency (94.1%), ultra-stretchability (2600%), and autonomous self-healing. Spin trapping electron paramagnetic resonance and dye fading experiments reveal the generation of free radicals. UV–visible spectrometry and viscosity tests demonstrate the cross-linking effect of Ga³⁺. The gelation time is much shorter than that of the conventional ammonium persulfate thermal initiation process. Furthermore, this liquid-free polymer material is intrinsically resistant to freezing and drying, enabling it to operate under harsh conditions. In consideration of transparency, self-healing, ultra-stretchability, moldability, and sensory features, the resulting elastomeric conductor may hold promise for industrial applications in wearable devices, force mapping, and flexible electroluminescent devices.