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 2265 K 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.

In-situ observation of phase separation dynamics for immiscible aqueous solution within ultrasonic field.

A high-speed imaging technique was used to observe the phase separation process of water (H2O)-20 %succinonitrile (SCN) immiscible solution within ultrasound field. Combining with numerical simulation, the effects of ultrasonic cavitation and acoustic streaming on the fragmentation and migration of secondary droplets were revealed. It was found that the previously spherical or near-spherical secondary H2O-rich droplets formed under static condition were dynamically transformed into several novel forms, such as tadpole-like, string-beads, gourd-like, and threadlike patterns. The calculated results showed that the cavitation could fragment micron-scale H2O-rich droplets because of the produced higher shock wave pressure than the droplets' Laplace pressure, and the subsequent droplet morphology evolution mainly depended on the liquid ejection volume determined by the distance between the droplets and the collapsing bubbles. Meanwhile, acoustic streaming, which generated shear force exceeding the surface tension of H2O-rich phase, stretched, split and finally fractured millimeter-sized or even larger secondary droplets into several smaller spherical sub-droplets. In comparison, the observed secondary droplet distribution characteristics in H2O-20 %SCN solution were similar to the Bi-rich particles in the ultrasonic solidification microstructures of Al-30 %Bi immiscible alloy, confirming that this work provided a deep understanding of the liquid phase separation mechanism within ultrasonic field.

Evaporation kinetics during containerless chemical synthesis of ZIF-8 in levitated droplets.

Zeolitic imidazolate framework-8 was synthesized in a containerless state via acoustic levitation. The cavitation effect of ultrasound affected the coordination connection of organic ligands in acoustically levitated droplets and they exhibited a conspicuous difference in the particle size distribution as compared with those under normal conditions. Herein, methanol was chosen as the solvent to investigate the influence of droplet evaporation on acoustic levitation synthesis. The kinetic parameters of droplet evaporation such as geometrical morphology transformation, concentration change and temperature evolution were measured for the levitation state. Surface evaporation resulted in the drastic deformation of the droplet during ZIF-8 synthesis and caused its vertical vibration and shape oscillation. The abrupt change of the levitation state aggravated the sound field effect on the containerless synthesis and caused a decrease of particle size distribution. A two-dimensional axis-symmetry model was used to visually simulate the sound field distribution during acoustic levitation synthesis based on the finite element method. The fabricated ZIF-8 was able to remove phthalic acid in wastewater through adsorption, and its kinetic features followed a pseudo second-order rate model.

A high-temperature acoustic field measurement and analysis system for determining cavitation intensity in ultrasonically solidified metallic alloys.

A high-temperature acoustic field measurement and analysis system (HTAFS) was self-designed and developed to achieve real-time acoustic field analysis and quantitative cavitation characterization within high-temperature liquids. The acoustic signal was acquired by a high-temperature resistant waveguide and calibrated by separate compensation of line and continuous spectra to eliminate frequency offsets. Moreover, a new method was proposed to derive from the continuous-spectrum sound intensity and line-spectrum sound intensity in the frequency band above 1.5 times the fundamental frequency to characterize the intensity of transient cavitation and stable cavitation. The acoustic field characteristics within solidifying liquid Al-7 %Si alloy were successfully determined by this system. With the increase of ultrasound amplitude, the acoustic pressure in the alloy melt increased to be stable, the transient cavitation intensity first rose and then declined, and the stable cavitation intensity remained unchanged. Combined with the structural evolution of the primary α(Al) phase, the transient cavitation intensity was determined to be the dominant factor for the ultrasound-induced grain refinement effect.

Extraordinary Solidification Mechanism of Liquid Alloys Under Acoustic Levitation State.

The acoustic levitation of various materials can be realized by highly intensive ultrasound, which provides a free surface and containerless state for materials processing under space simulation conditions. The nonlinear effects such as acoustic radiation pressure, acoustic streaming, and ultrasonic cavitation open up special access to modulate the fluid dynamics and solidification mechanisms of liquid materials. Here, the physical characteristics of liquid flow, undercooling capability, phase separation, and crystal nucleation and growth within acoustically levitated droplets are explored comprehensively to reveal the extraordinary solidification kinetics of liquid alloys. The sectorial shape oscillations of the 2nd to 10th order modes accompanying internal potential flow are observed for water droplets with modulated ultrasound amplitudes, while the enhanced ultrasound intensity promotes ice nucleation and thus reduces water undercooling. The migration of Sn-rich globules during phase separation of immiscible Al-Cu-Sn alloy is dominated by the droplet deformation and rotation related to acoustic levitation. The high undercooling states of liquid Ag-Cu-Ge and Ni-Sn alloys during acoustic levitation result in the refinement of (Ag) dendrites and the formation of anomalous (Ni+Ni3 Sn) eutectics. The ultrasound-liquid interaction also induces surface waves during the containerless solidification of Ag-Cu and Ni-Sn eutectic alloys.

Floating synthesis with enhanced catalytic performance via acoustic levitation processing.

Acoustic levitation supplies a containerless state to eliminate natural convection and heterogeneous crystal nucleation and thus provides a highly uniform and ultra clean condition in the confined levitating area. Herein, we attempt to make full use of these advantages to fabricate well dispersed metal nanoparticles. The gold nanoparticles, synthesized in an acoustically levitated droplet, exhibited a smaller size and improved catalytic performance in 4-nitrophenol reduction were synthesized in an acoustically levitated droplet. The sound field was simulated to understand the impact of acoustic levitation on gold nanoparticle growth with the aid of crystal growth theory. Chemical reducing reactions in the acoustic levitated space trend to occur in a better dispersed state because the sound field supplies continuous vibration energy. The bubble movement and the cavitation effect accelerate the nucleation, decrease the size, and the internal flow inside levitated droplet probably inhibit the particle fusion in the growth stage. These factors lead to a reduction in particle size compared with the normal wet chemical synthetic condition. The resultant higher surface area and more numerous active catalytic sites contribute to the improvement of the catalytic performance.

Ultrasonic polymerization of CuO@PNIPAM and its temperature tuning glucose sensing behavior.

The extraordinary high pressure and temperature produced during cavitation is crucial for ultrasonic sonochemistry. However, the cavitation effect is usually confined to a small zone nearby the ultrasonic horn, outside of which ultrasound produces much less effects on chemical reaction. In present work, in order to expand the range of effective zone and intensify the cavitation effect, N2 aeration was introduced to an ultrasonic polymerization process of CuO@PNIPAM in aqueous solution. By increasing the number of bubble nucleus gathered on the CuO surface and lowering the surface tension of the aqueous solution, the cavitation effect is intensified on the CuO surface within the whole reaction vessel, which benefits the covalently bonding between PNIPAM and CuO to a large degree and results in the formation of CuO@PNIPAM hybrid composite with excellent interfacial bonding. It is promising that the hybrid composite can be applied as temperature responsive glucose sensing platform with ON and OFF states due to the wettability change of PNIPAM versus temperature.

Shearing particle monolayers: strain-rate frequency superposition.

We report surface shear rheological measurements on monolayers of silica nanoparticles at the air-water interface. We have used the method of strain-rate frequency superposition (SRFS) to characterize the structural relaxation. We show that the rheological properties of the layers have the same universal linear and nonlinear behavior as three-dimensional soft materials. We also discuss the original healing properties of these monolayers.

An ellipsometry study of silica nanoparticle layers at the water surface.

We have studied silica nanoparticle layers spread at the air/water interface. The surface pressure of the layers has been determined in a Langmuir trough via two orthogonal Wilhelmy plates. We observed significant differences in surface pressure according to the preparation protocol: layers spread then compressed or layers obtained after successive spreading steps. We also studied the two types of layers by multiple angle of incidence ellipsometry. We introduce a two-layer model which enables us to evaluate the radius of interfacial aggregates and their contact angle with the air/water interface.