Alloy Droplets Research Articles

Controlled Nanopore Sizes in Supraparticle Supports for Enhanced Propane Dehydrogenation with GaPt SCALMS Catalysts.

The efficient immobilization of GaPt liquid metal alloy droplets onto tailored supports improves catalytic performance by preventing coalescence and subsequent loss of active surface area. Herein, we use tailored supraparticle (SP) supports with controlled nanopores to systematically study the influence of pore sizes on the catalytic stability of GaPt supported catalytically active liquid metal solution (SCALMS) in propane dehydrogenation (PDH). Initially, GaPt droplets were prepared via an atom-efficient and scalable ultrasonication method with recycling loops to yield droplets <300 nm. Subsequently, these droplets were immobilized onto SiO2-based SPs with controlled pore sizes ranging from 45 to 320 nm. Catalytic evaluations in PDH revealed that GaPt immobilized on SPs with larger pores demonstrated superior stability over 15 h time-on-stream evidenced by reduced deactivation rates from 0.046 to 0.026 h-1. Nanocomputed tomography and identical location SEM confirmed the successful immobilization of GaPt droplets within the interstitial sites formed by the primary particles constituting the SPs. These remained unchanged before and after the catalytic reaction, demonstrating efficient coalescence prevention. Our findings underscore the importance of support pore size engineering for improving the stability of GaPt SCALMS catalysts and highlight, particularly, the high potential of using SPs in this context.

Dendrite growth kinetics and microstructure evolution mechanism of Ni2TiAl intermetallic compound within substantially undercooled liquid Ni64Al19Ti17 alloy

The dendrite growth kinetics and microstructure evolution mechanism of the Ni2TiAl intermetallic compound within substantially undercooled liquid Ni64Al19Ti17 alloy were investigated using electrostatic levitation (ESL) and drop tube (DT) techniques. The growth velocity of primary Ni2TiAl dendrites displayed a power-law relation with liquid undercooling, achieving a maximum of 80 mm/s at the undercooling of 254 K (0.16 TL). The solidification pathway transformed from primary Ni2TiAl growth plus subsequent (Ni3Ti+Ni2TiAl) eutectic growth into the successive growth of Ni2TiAl and Ni3Ti phases as the alloy undercooling increased sufficiently. The high cooling rates of freely falling alloy droplets effectively suppressed the martensitic transformation observed for primary Ni2TiAl intermetallic compound under typical ESL radiative cooling condition. Both nanoindentation and Vickers hardness performances of the Ni2TiAl phase formed under these two conditions exhibited conspicuous enhancement due to grain refinement effects. The microstructures with martensitic transformation under ESL condition showed higher hardness than those under DT condition despite their larger grain size.

Wrinkled Shrinkage on Surface Monophasic Structure of Floating Refractory Alloy Droplets Solidified in Space Environment

AbstractThe surface‐wrinkled shrinkage structure of spheres is very common and also quite intriguing to explore and reveal the analogous droplet solidification kinetics in the space environment. Here, a liquid‐to‐solid phase transition experiment of floating refractory alloy droplets is designed to study the surface wrinkled shrinkage structures aboard China Space Station with a 10−5 gravity level. The experimental Ti‐Ni‐V alloy droplets undergo an extremely high overheating temperature beyond 1800 K and then achieve a supercooling of 307 K, displaying a strong thermodynamic metastability. The spherical surface deformation structures of this alloy under microgravity coupled with extreme metastable solidification are explored. Moreover, through the active control of metastable rapid solidification, a surface monophasic structure and a B2 structure capable of stress‐induced martensitic transformation are facilitated by wrinkled shrinkage dynamics under microgravity. Their findings shed further light on the surface deformation structures during the microgravity solidification process.

Electromagnetic effects on the solidification of a metallic alloy droplet impacting onto a surface

The effect of magnetic fields on the solidification of a droplet impacting a substrate, and its potential for controlling the topology and properties of the final solidified splat, has not been explored thus far. In this research, we conduct a computational study on the solidification of a metallic alloy droplet impacting onto a substrate under the influence of a magnetic field, for the first time. Our model undergoes rigorous assessments through a systematic procedure to avoid error-hiding of different sub-models. We investigate the effects of applying direct and alternating magnetic fields with different Strouhal numbers (or dimensionless frequencies). Our findings demonstrate that MagnetoHydroDynamics (MHD) can effectively control the shape of the frozen splat upon impact. Depending on the interplay between the inertia and capillary forces as well as the MHD braking and shaking effects (damping and oscillating Lorentz forces), we achieve a hemispherical, oblate, prolate, or cupcake solidified splat topology. Additionally, we identify a critical Strouhal number at which the solidified splat-shape parameters reach an extremum. Our analyses reveal two distinct causes underlying this phenomenon at low or moderate Weber numbers. At low Weber numbers, the resonance triggered by the proximity of the MHD actuation frequency and the capillary natural frequency of the splat is the determining factor. On the other hand, at the higher Weber numbers, the severe droplet regime changes and instability play a key role.

Numerical method determining the time-dependent position of a minority phase sphere in the Fe-Cu alloy droplet

Abstract A numerical method was developed to track the dynamic positions of the L2 phase sphere inside the Fe-Cu alloy droplet. Firstly, the temperature field distribution within alloy droplet was calculated, and the variation in thermal gradient was analyzed. Secondly, the migration behavior of the sphere was analyzed based on Marangoni convection. Finally, the theoretical position of the 10 μm sphere was determined. The results demonstrated that there is a little difference in temperature between the center and the surface of the droplet, but its gradient is very different. Moreover, the maximum migration times for the L2 phase sphere were determined to be ~0.02 s, 0.07 s, and 0.14 s within 300μm, 600μm, and 900μm alloy droplets, respectively. In addition, it was also found that the same-sized spheres can reach the same relative position, i.e., 0.485R. This means the final position of the sphere within the different alloy droplets is independent of the droplet size.

The coalescence and oscillation of eutectic gallium indium alloy droplets

Gallium-based liquid metal droplets have excellent deformation performance, and their oscillation has huge potential in oscillator and organ-on-chip research. At present, the oscillation of gallium-based liquid metal droplets controlled by external energy (such as the application of electric fields and chemical reactions) has been thoroughly studied, while there are vacancies in the study of the oscillation due to coalescence of droplets without external energy input. A numerical simulation study on the oscillation process after the coalescence of two and three eutectic gallium indium alloy droplets is conducted. The degree of deformation of the droplet is described by the dimensionless length change in the symmetry axis direction of the line connecting the centers of the initial droplets in the top view, that is, in the y direction. The oscillation curve of the droplet is obtained by the fitting method. The results show that the oscillation of coalesced droplets has obvious periodicity and damping attenuation characteristics, and increasing the number of droplets or reducing the droplet radius will increase the damping coefficient. Furthermore, the ratio of droplet sizes and their initial distribution have an impact on the variations in kinetic energy of the three droplets in the y direction, thereby influencing the deformation of the droplets. This research enriches the theory of gallium-based liquid metal droplet deformation and plays a significant role in guiding the application of droplet oscillation in the fields of micromixers and measuring the physical parameters of solutions.

Low-loss liquid metal interconnects for superconducting quantum circuits

Building a modular architecture with superconducting quantum computing chips is one of the means to achieve qubit scalability, allowing the screening, selection, replacement, and integration of individual qubit modules into large quantum systems. However, the nondestructive replacement of modules within a compact architecture remains a challenge. Liquid metals, specifically gallium alloys, can be alternatives to solid-state galvanic interconnects. This is motivated by their self-healing, self-aligning, and other desirable fluidic properties, potentially enabling the nondestructive replacement of modules at room temperatures, even after operating the entire system at millikelvin regimes. In this study, we present coplanar waveguide resonators (CPWRs) interconnected by gallium alloy droplets, achieving high internal quality factors up to nearly one million and demonstrating performance on par with the continuous solid-state CPWRs. Leveraging the desirable fluidic properties of gallium alloys at room temperature and their compact design, we envision a modular quantum system enabled by liquid metals.

Decoupling effect stimulated independent dendrite growth of eutectic phases under microgravity and containerless states

Eutectic growth process is usually characterized by the simultaneous coupled growth of two different solids within one uniform liquid phase, while fluid dynamics normally predicts the equiaxed shrinkage for floating viscous droplets on freezing. Here a decoupling effect was induced by the microgravity and containerless states aboard space station, which led to the independent dendrite growth of two eutectic phases within extremely undercooled liquid Nb-Si refractory alloy. The confronting fluid flow pattern driven by polar heterogeneous nucleation was found to stimulate the elongated surface deformation of alloy droplet at a high dendrite growth velocity.

Primary dendrite growth within binary Fe71Ge29 eutectic alloy under duplex levitation states

The primary β-Fe3Ge2 dendrite growth kinetics within liquid Fe71Ge29 eutectic alloy was studied by both acoustic levitation and electrostatic levitation techniques, with maximum experimental undercoolings of 130 and 143 K, respectively. At small undercoolings, (α1 + β-Fe3Ge2) eutectic growth proceeded and then transformed to lamellar (ε-Fe3Ge + β-Fe3Ge2) microstructure by peritectoid reaction. Once liquid undercooling reached 56 K, β primary phase started to nucleate preferentially and its maximum growth velocity attained 13.5 mm/s at 143 K undercooling. By acoustic levitation processing, β dendrites were distributed inside the alloy droplet. Under electrostatic levitation state, β dendrites were distributed both at the periphery and within the interior of alloy droplet, and their volume fraction was significantly higher than that under acoustic levitation. Numerical simulation results indicated that a duplex flow was induced by alloy droplet shape oscillation and acoustic streaming. The flow exhibited maximum intensity near the alloy surface, which inhibited the achievement of larger undercoolings during acoustic levitation.

An improved preparation method of core-shell Al@Sn-Bi microspheres and its microstructure formation mechanism

This paper presents an improved method for achieving controllable preparation of the composition and size of the monotectic alloy core-shell structure microspheres. This advancement is expected to enhance the commercial application of monotectic alloy core-shell structure microspheres. By installing a heating device at the top of the drop tube in the pulsated orifice ejection method setup, we achieved in-situ heat treatment of falling droplets, resulting in the successful preparation of Al45(Sn42Bi58)55 core-shell structure microspheres. Furthermore, we investigated the formation mechanism of the Al@Sn-Bi core-shell structure. Nine sets of Al-Sn-Bi microspheres with varying in-situ heat treatment temperatures were prepared. Analysis via X-ray diffraction and transmission electron microscopy revealed that the microspheres consisted of Al-rich, Sn-rich, and Bi-rich phases, without any intermetallic compounds. Scanning electron microscopy results indicated that as the in-situ heat treatment temperature increased, the structure of the Al-Sn-Bi microspheres transitioned from irregular to regular core-shell configurations. This suggests that higher heat treatment temperatures prolong liquid phase separation time, leading to increased repetition of Marangoni motion within the droplet, Ostwald ripening of the minor phase droplets, and Soret effect of the matrix phase. However, at temperatures exceeding 700 °C, the solidification rate of alloy droplets decreased, causing the Al-rich phase core to deviate from the center and form a crescent structure due to Stokes motion.

Investigation of the spreading of a liquid metal droplet under a vertical magnetic field

In the liquid metal divertor of a magnetic confinement fusion device, the spreading characteristics of the liquid metal are crucial for ensuring the stable operation of the divertor. This study has experimentally investigated the spreading characteristics of a GaInSn alloy droplet on a solid substrate under a strong vertical magnetic field, with the magnetic field intensity ranging from 0 to 2.5 T. First, several parameters of the droplet, such as droplet shape, spreading factor, dynamic contact angle, spreading velocity, and rebound behavior after impacting, were studied without a magnetic field. The fitting relationship between maximum spreading factor βmax and Weber number We was obtained and has been compared with the scaling laws from the literature. Furthermore, the effect of the vertical magnetic field on those parameters has been investigated systematically. Quantitative results on βmax and the maximum spreading time tDmax, varied with the Hartmann number (Ha) and the We number, provide a comprehensive understanding of the spreading dynamics. The specific relationship between βmax and We number under different magnetic field intensities (B) shows that a vertical magnetic field has a great inhibiting effect on liquid metal droplet spreading. Finally, the influence of oxidation on droplet spreading characteristics also has been studied. These basic findings are important for the application of liquid metal on a divertor/limiter in a fusion reactor, offering a theoretical reference engineering design.

Composition and optical properties of (In, Ga)As nanowires grown by group-III-assisted molecular beam epitaxy.

(In, Ga) alloy droplets are used to catalyse the growth of (In, Ga)As nanowires by molecular beam epitaxy on Si(111) substrates. The composition, morphology and optical properties of these nanowires can be tuned by the employed elemental fluxes. To incorporate more than 10% of In, a high In/(In+Ga) flux ratio above 0.7 is required. We report a maximum In content of almost 30% in bulk (In, Ga)As nanowires for an In/(In+Ga) flux ratio of 0.8. However, with increasing In/(In+Ga) flux ratio, the nanowire length and diameter are notably reduced. Using photoluminescence and cathodoluminescence spectroscopy on nanowires covered by a passivating (In, Al)As shell, two luminescence bands are observed. A significant segment of the nanowires shows homogeneous emission, with a wavelength corresponding to the In content in this segment, while the consumption of the catalyst droplet leads to a spectrally-shifted emission band at the top of the nanowires. The (In,Ga)As nanowires studied in this work provide a new approach for the integration of infrared emitters on Si platforms.

Freezing Shrinkage Dynamics and Surface Dendritic Growth of Floating Refractory Alloy Droplets in Outer Space.

The freezing shrinkage and dendritic growth are of great importance for various alloys solidified from high-temperature liquids to solids since they dominate microstructure patterns and follow-up processing. However, the microgravity freezing shrinkage dynamics is scarcely explored on the ground as it is hard to suppress the strong natural convection inside liquid alloys. Here, a series of in-orbit solidification experiments is conducted aboard the China Space Station with a long-term stable 10-5 g0 microgravity condition. The highest temperature up to 2265K together with substantial liquid undercoolings far from a thermodynamically stable state are attained for both Nb82.7Si17.3 and Zr64V36 refractory alloys. Furthermore, the solidification under microgravity of a droplet is simulated to reveal the liquid-solid interface migration, temperature gradient, and flow field. The microgravity solidification process leads to freezing shrinkage cavities and distinctive surface dendritic microstructure patterns. The combined effects of shrinkage dynamics and liquid surface flow in outer space result in the dendrites growing not only along the tangential direction but also along the normal direction to the droplet surface. These space experimental results contribute to a further understanding of the solidification behavior of liquid alloys under a weaker convection condition, which is often masked by gravity on the ground.

Metastable Liquid Properties and Surface Flow Patterns of Ultrahigh Temperature Alloys Explored in Outer Space.

The metastable liquid properties and chemical bonds beyond 2000 K remain a huge challenge for ground-based research on liquid materials chemistry. We show the strong undercooling capability, metastable liquid properties and surface wave patterns of refractory Nb-Si and Zr-V binary alloys explored in space environment. The floating droplet of Nb82.7Si17.3 eutectic alloy superheated up to 2338 K exhibited an extreme undercooling of 437 K, approaching the 0.2TE threshold for homogeneous nucleation of liquid-solid reaction. The microgravity state endowed alloy droplets with nearly perfect sphericity and thus ensured the high accuracy to determine metastable undercooled liquid properties. A special kind of swirling flow was induced for liquid alloy owing to Marangoni convection, which resulted in the spiral microstructures on Zr64V36 alloy surface during liquid-solid phase transition. The coupled impacts of surface nucleation and surface flow brought in a novel olivary shape for these binary alloys. Furthermore, the chemical bonds and atomic structures of high temperature liquids were revealed to understand the liquid properties in outer space circumstances.

Metastable Liquid Properties and Surface Flow Patterns of Ultrahigh Temperature Alloys Explored in Outer Space

AbstractThe metastable liquid properties and chemical bonds beyond 2000 K remain a huge challenge for ground‐based research on liquid materials chemistry. We show the strong undercooling capability, metastable liquid properties and surface wave patterns of refractory Nb−Si and Zr−V binary alloys explored in space environment. The floating droplet of Nb82.7Si17.3 eutectic alloy superheated up to 2338 K exhibited an extreme undercooling of 437 K, approaching the 0.2TE threshold for homogeneous nucleation of liquid‐solid reaction. The microgravity state endowed alloy droplets with nearly perfect sphericity and thus ensured the high accuracy to determine metastable undercooled liquid properties. A special kind of swirling flow was induced for liquid alloy owing to Marangoni convection, which resulted in the spiral microstructures on Zr64V36 alloy surface during liquid‐solid phase transition. The coupled impacts of surface nucleation and surface flow brought in a novel olivary shape for these binary alloys. Furthermore, the chemical bonds and atomic structures of high temperature liquids were revealed to understand the liquid properties in outer space circumstances.

Evaluation of the segregation in printed mono-sized Al-In alloy droplets

Monotectic alloys, with a focus on lightweight and multifaceted aluminum-indium alloys, possess extensive applications and considerable potential for growth within high-tech sectors. This study addresses a crucial gap within additive manufacturing research pertaining to monotectic alloys, a matter of significance in the context of Industry 4.0. We investigate the application of Uniform Metal Droplet Printing Technology (UMDPT) to address the segregation issue prevalent during the solidification process of these alloys, an impediment compromising their resilience and longevity. The research not only advocates for the use of UMDPT in producing monotectic alloys, but also offers valuable insights into the mechanisms of segregation inhibition, thereby broadening the understanding of additive manufacturing technology. Experimental results indicate that this technology can efficaciously inhibit the segregation of the indium-rich secondary phase during the solidification of the aluminum-indium alloy. The conducted experiments utilized droplets at 1073 K with a nozzle diameter of 500 μm and demonstrated a uniform dispersion of the secondary phase, with a size of 0.5 μm and a variation coefficient of 0.375. This groundbreaking research outcome bears considerable implications for further advancements in this domain and fosters the evolution of more efficient manufacturing methodologies.

A systematic study on self-catalyzed growth of InAs/GaSb axial heterostructured nanowires by MOCVD

Traditional Au-catalyzed growth method of nanowires will mix Au atoms into Si substrates and InAs/GaSb axial heterojunction materials to introduce deep energy levels, which will seriously degrade the electrical and photoelectric properties of nanodevices. In this work, we studied in detail the effects of multiple growth parameters on self-catalyzed growth of InAs/GaSb axial heterostructured NWs on Si substrate by MOCVD. It is found that in the switching process from InAs material precursor to GaSb material precursor, if growth temperature of GaSb is not appropriate and switching time is too long, it will cause the decomposition and disappearance of InAs NWs, and directly terminate the realization of InAs/GaSb axial heterojunction NWs. Both the parameter windows of the growth temperature and V/III ratio are very narrow, which directly affects the growth trend of GaSb material in axial or radial deposition. It provides an important and meaningful method for self-catalyzed high-quality nanowires by MOCVD that up high pure GaSb nanowires requires the catalyzed guidance of alloy droplets and buffer seed nanowire and bottom InAs nanowires just meet both requirements.

Liquid state properties and rapid solidification mechanism of Fe-Nd-B alloy investigated under space simulation conditions

The thermophysical properties of liquid Fe84Nd10B6 alloy from superheated to undercooled state were investigated by space simulation technology combined with ab initio molecular dynamics (AIMD) simulations. The liquid density at liquidus temperature and its temperature coefficient were determined as 7.17 g·cm−3 and 5.51 × 10−4 g·cm−3·K−1, while its liquid thermal expansion coefficient was measured as 7.69 × 10−5 K−1. The ratio of specific heat to emissivity decayed as a quadratic power function. Under electrostatic levitation (ESL) condition, even though the cooling rate of liquid alloy was only 23.6–35.3 K/s, a maximum 131 K undercooling was realized. As alloy undercooling rose, the grain size of primary α(Fe) dendrite was refined, whose volume fraction decreased from 26.2% to 22.0%. Meanwhile, the volume fraction of major peritectic τ1(Nd2Fe14B) phase was increased from 68.6% to 76.8%, which was accompanied by the reduction of peri-eutectoid τ2(Nd1.1Fe4B4) phase down to 1.2%. In the case of microgravity processing by drop tube, liquid undercooling and cooling rate respectively reached up to 260 K (0.16 TL) and 3.9 × 104 K/s for the falling alloy droplets. Instead of τ1 phase, the primary α(Fe) phase occupied the largest volume fraction of 49.7% in large alloy droplets. At enhanced undercooling and cooling rate, the peritectic τ1 phase only increased from 26.2% up to 43.5%, whereas those of α(Fe) and τ2 phases declined to 44.0% and 12.5%, respectively. It was found that the increase of liquid alloy undercooling promoted the peritectic transformation to some extent, but high cooling rate greatly restricted peritectic reaction by reducing reaction time. The coupled effect of liquid undercooling and cooling rate controlled the volume fraction of each phase in rapidly solidified microstructures.

Combustion of micron-sized Al-Mg alloy wires in hot H2O/O2/N2 flows

The use of aluminum-magnesium (Al-Mg) alloy particle as energetic additive in solid propellants was previously shown to have many advantages over pure Al particle, such as relatively low ignition temperature, high reaction rate and low particle agglomeration rate. In this paper, the combustion of Al-Mg alloy in hot H2O/O2/N2 flows was experimentally studied using wires with a diameter of 200 µm. The employment of wires instead of particles provided a unique opportunity to obtain fundamental insights into the combustion process due to the spatial stabilization and large size of the sample. High-speed imaging showed that the combustion of Al-Mg alloy wire could be divided into three stages, namely pre-heating, ignition, and combustion. Spectral measurements suggested that the chemiluminescence emissions from Mg, MgO and MgOH dominated the collected spectra, in spite of only 3% Mg (by weight) existed in the alloy. Additionally, it was observed that moderate gaseous reactions could occur well before the breakup of the passive oxide coating, generating obvious fine oxide smokes. Moreover, consumption rates of the wire in different hot oxidizers were obtained and compared. It was shown that O2 featured more significant promotion of the reaction than H2O. Nevertheless, without O2, much less metal-oxide particles were generated. Temperature measurements indicated that the ignition temperature lied within 2160 ∼ 2220 K, which was lower than the melting points of Al2O3 (2350 K) and MgO (3125 K). Large single burning Al-Mg alloy droplets (∼200 µm diameter) were generated after the micro-explosion inside the wire. It was found that the combustion of Al-Mg alloy in both H2O/O2/N2 and H2O/N2 atmospheres were diffusion-controlled with a stand-off distance around 150 µm (stand-off ratios at ∼ 1.3). Finally, SEM and EDS measurements revealed that Al, Mg and O elements coexisted on the surface of the burnt wires. Nevertheless, it was observed that the oxidization of Mg started before Al, and the reaction of alloy was more intense when O2 existed. This led to the generation of much thicker oxide layers and larger number of nanoparticles.

From waste to wealth: Valuable metals recovered from waste tungsten leaching residue by a smelting reduction process using CaO-Fe capture agent

Tungsten leaching residue (W-residue), a hazardous waste generated from the industrial recovery of the spent tungsten carbides, poses a threat to the environment. The W-residue contains high grades of SiO2 and TiO2 oxides, and low grades of high-value metal oxides such as WO3, CoO, Ta2O5, and Nb2O5. Herein, a smelting reduction process was proposed to effectively recover the high-value metals from the W-residue and obtained a medium-entropy carbide (MEC) composite. During the smelting process, the valuable metals were recovered as alloy consisting of (Fe, Co)-rich silicide, (Fe, Cr, W)-rich silicide, and (W, Ta, Nb, Ti)C, respectively. The addition of flux CaO lowered the liquidus temperature of the molten slag, and effective alloy-slag phase separation was achieved by adding Fe as a metal collector to capture the alloy droplets entrapped in the slag. Under the optimal conditions, the total recovery rate reached 86.8%. Moreover, the obtained (W, Ta, Nb, Ti)C as MEC exhibited a Vickers hardness of over 19 GPa and can be used as a wear-resistant alloy. This study proposed a strategy for extracting high-value metals from hazardous tungsten residue, which could complement existing recycling processes towards a closed-loop process in the tungsten industry.