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At least 19 records

Melting of Magnesium Borohydride under High Hydrogen Pressure: Thermodynamic Stability and Effects of Nanoconfinement

The thermodynamic stability and melting point of magnesium borohydride were probed under hydrogen pressures up to 1000 bar (100 MPa) and temperatures up to 400 °C. At 400 °C, Mg(BH4)2 was found to be chemically stable between 700 and 1000 bar H2, whereas under 350 bar H2 or lower pressures, the bulk material partially decomposed into MgH2 and MgB12H12. The melting point of solvent-free Mg(BH4)2 was estimated to be 367-375 °C, which was above previously reported values by 40-90 °C. Our results indicated that a high hydrogen backpressure is needed to prevent the decomposition of Mg(BH4)2 before measuring the melting point and that molten Mg(BH4)2 can exist as a stable liquid phase between 367 and 400 °C under hydrogen overpressures of 700 bar or above. The occurrence of a pure molten Mg(BH4)2 phase enabled efficient melt-infiltration of Mg(BH4)2 into the pores of porous templated carbons (CMK-3 and CMK-8) and graphene aerogels. Both transmission electron microscopy and small-angle X-ray scattering confirmed efficient incorporation of the borohydride into the carbon pores. The Mg(BH4)2@carbon samples exhibited comparable hydrogen capacities to bulk Mg(BH4)2 upon desorption up to 390 °C based on the mass of the active component; the onset of hydrogen release was reduced by 15-25 °C compared to the bulk. Importantly, melt-infiltration under hydrogen pressure was shown to be an efficient way to introduce metal borohydrides into the pores of carbon-based materials, helping to prevent particle agglomeration and formation of stable closo-polyborate byproducts.

White, James L.↗

Sound velocity and compressibility of melts along the hedenbergite (CaFeSi2O6)-diopside (CaMgSi2O6) join at high pressure : Implications for stability and seismic signature of Fe-rich melts in the mantle

Iron-rich silicate melts play an important role in the magmatic history of the Earth and the 16 Moon. However, their elastic properties at high pressures, especially the sound velocity, are poorly 17 understood. Here we determined the ultrasonic sound velocity for the first time of a hedenbergite 18 (Hd, CaFeSi2O6) melt and a melt mixture of 50 mol% hedenbergite + 50 mol% diopside (Hd50Di50) 19 at high pressure and temperature conditions up to 6 GPa and 2329 K, using high-pressure ultrasonic 20 technique combined with synchrotron radiation in a multi-anvil apparatus. Our results show that 21 Fe can significantly reduce the sound velocity while increase the density of silicate melts. 22 Comparing the Di, Hd, and Hd50Di50 melts, we find that the sound velocity does not mix linearly 23 2 for melts in the Hd-Di join, whereas the density for Hd-Di melts at high pressures can be well-24 described by linear mixing. Combined with melt geometry and melt compaction models, we 25 applied our results to study the stability and seismic signature of Fe-rich silicate melts in the Earth’s 26 upper mantle. For the low-velocity zone (LVZ) in mantle asthenosphere, although the degree of 27 seismic velocity reduction can be explained by the presence of a small amount of partial melt 28 distributed in film/band geometry along grain boundaries, Fe-rich melts formed at this depth are 29 unlikely to be gravitationally stable, but may be dynamically unextractable if the melt supply is 30 continuous. For the low-velocity layer (LVL) above the mantle transition zone, the presence of Fe-31 rich melts (with FeO>~10 wt%) distributed in textural equilibrium with the ambient mantle is a 32 plausible explanation.

diopside↗

Testing the Recycled Gabbro Hypothesis for the Origin of “Ghost Plagioclase” Melt Signatures Using 87 Sr/ 86 Sr of Individual Olivine-Hosted Melt Inclusions From Hawai'i

Melt inclusions with large, positive Sr anomalies have been described in multiple tectonic settings, and the origins of this unusual geochemical feature are debated. Three origins have been proposed, all involving plagioclase as the source of the elevated Sr: (i) direct assimilation of plagioclase-rich lithologies, (ii) recycled lower oceanic gabbro in the mantle source, and (iii) shallow-level diffusive interaction between present day lower oceanic crust (i.e., plagioclase-bearing lithologies) and the percolating melt. A “ghost plagioclase” signature (i.e., a large, positive Sr anomaly without associated high Al 2 O 3 ) is present in melt inclusions from Mauna Loa. Here, we present new 87 Sr/ 86 Sr measurements of individual olivine-hosted melt inclusions from three Hawaiian volcanoes, Mauna Loa, Loihi, and Koolau. The data set includes a Mauna Loa melt inclusion with the highest reported Sr anomaly (or highest (Sr/Ce) N , which is 7.2) for Hawai'i. All melt inclusions have 87 Sr/ 86 Sr values within the range reported previously for the lavas from each volcano. Critically, the 87 Sr/ 86 Sr of the high (Sr/Ce) N melt inclusion lies within the narrow range of 87 Sr/ 86 Sr for Mauna Loa melts that lack high (Sr/Ce) N signatures. Therefore, to explain the high (Sr/Ce) N ratio of the ghost plagioclase signature using an ancient recycled gabbro, the gabbro-infused mantle source would have had to evolve, by chance, to have the same 87 Sr/ 86 Sr as the source of the Mauna Loa melts that lack a recycled gabbro (ghost plagioclase) signature. Alternatively, shallow-level diffusive interactions between Mauna Loa plagioclase-rich cumulates and a percolating mantle-derived melt provides a simpler explanation for the presence of the high (Sr/Ce) N Mauna Loa melts.

58 GEOSCIENCES↗

Solvent-Free Melt-Processed Cathode Mitigates Li Anode Instability in Polymer-Based Solid-State Batteries

Solvent-free manufacturing of battery components is a promising alternative to traditional slurry processing for reducing the cost and environmental impact. In this work, we used twin-screw melt extrusion to fabricate a polymer-based high voltage composite cathode. The melt-processed cathode is dense (near zero porosity) and thick (65 μm) and has high active material loading (80 wt %). The active particles are distributed uniformly throughout the melt-processed cathode, unlike the traditional slurry-cast cathode, which exhibits inhomogeneous particle distribution. In the melt-processed cathode, polymer and carbon form separate phases, whereas in the slurry-cast cathode they blend into a single phase. Due to these structural differences, the melt-processed cathode shows smooth charge–discharge profiles, while the slurry-cast cathode shows noisy charging and soft-shorting behavior. In conclusion, this work highlights that twin-screw extrusion as a scalable, solvent-free manufacturing method is advantageous in producing uniform cathodes, which mitigates anode instability.

25 ENERGY STORAGE↗

Melting rate correlation with batch properties and melter operating conditions during conversion of nuclear waste melter feeds to glasses

The rate of conversion of nuclear waste melter feed to glass is affected by the selection of melter feed materials and by melter design and operation. The melting rate correlation (MRC) is an equation that relates the glass production rate with two types of variables: (1) feed and melt properties: conversion heat, cold-cap bottom temperature, and glass melt viscosity; and (2) melter design and operation parameters: melter geometry, melter operating temperature, and gas bubbling rate. The MRC shows good agreement for an extended melting-rate data set of high-level waste (HLW) melter feeds and a data set generated for low-activity waste (LAW) melter feeds. Laboratory observation of heated melter feed samples is often used to assess the cold-cap bottom temperature of HLW melter feeds (moderately foaming feeds), but this technique appears inadequate for LAW melter feeds (vigorously foaming feeds). For LAW feeds, an adequate assessment of the cold-cap bottom temperature was achieved using evolved gas analysis, which allows identification of the collapse of primary foam for oxidized feeds. This assessment shows that the cold-cap bottom temperature for vigorously foaming LAW feeds is higher than that for moderately foaming HLW feeds. When the results of MRC are compared, LAW feeds are generally less sensitive to the bubbling rate and melt viscosity, and more sensitive to the cold-cap bottom temperature than HLW feeds. The MRC qualifies as a promising tool to support the selection of melter feed materials and melter operating conditions, which is determined from expensive independent scaled melter experiments, and sophisticated mathematical models.

Lee, Seung Min↗

High-pressure elastic properties of dolomite melt supporting carbonate-induced melting in deep upper mantle

Deeply subducted carbonates likely cause low-degree melting of the upper mantle and thus play an important role in the deep carbon cycle. However, direct seismic detection of carbonate-induced partial melts in the Earth’s interior is hindered by our poor knowledge on the elastic properties of carbonate melts. Here we report the first experimentally determined sound velocity and density data on dolomite melt up to 5.9 GPa and 2046 K by in-situ ultrasonic and sink-float techniques, respectively, as well as first-principles molecular dynamics simulations of dolomite melt up to 16 GPa and 3000 K. Using our new elasticity data, the calculated V P /V S ratio of the deep upper mantle (~180–330 km) with a small amount of carbonate-rich melt provides a natural explanation for the elevated V P /V S ratio of the upper mantle from global seismic observations, supporting the pervasive presence of a low-degree carbonate-rich partial melt (~0.05%) that is consistent with the volatile-induced or redox-regulated initial melting in the upper mantle as argued by petrologic studies. This carbonate-rich partial melt region implies a global average carbon (C) concentration of 80–140 ppm. by weight in the deep upper mantle source region, consistent with the mantle carbon content determined from geochemical studies.

58 GEOSCIENCES↗

In-situ X-ray and visual observation of foam morphology and behavior at the batch-melt interface during melting of simulated waste glass

We report to attain a basic understanding of the primary foam structure and behavior, which affects the heat and mass transfer and the efficiency of the glass melting process, we investigated the primary foam layer under the glass batch floating on molten glass. The primary foam affects mass transfer during batch melting, in turn affecting the melting process. The recently performed direct in-situ three-dimensional X-ray computed tomography of the batch melting in a laboratory-scale melter vessel allowed us to visualize the features of the reacting batch layer and the foam that develops at its bottom, though with an insufficient resolution of images. In this study, we obtained better temporal and spatial resolution using the two-dimensional X-ray radiography and visual observation of the structure and behavior of transient primary foam as it formed and decayed. As soon as the batch was charged onto the melt surface, foam bubbles began to evolve, grow, and coalesce, forming a primary foam layer, 5-10 mm thick, within tens of seconds. This foam layer was sustained by ongoing gas evolving reactions counterbalanced by bubble coalescence into cavities that moved sideways and escaped to the atmosphere. Eventually, the entire remaining batch turned into foam that gradually decayed at the melt surface. The decay rate agreed with literature observations of surface foam produced by secondary foaming.

36 MATERIALS SCIENCE↗

Structural disorder, sublattice melting, and thermo-elastic properties of anti-perovskite Li 3 OBr under high pressure and temperature

Here, in situ synchrotron x-ray diffraction experiments were conducted in the system Li-O-Br at pressures up to 6.5 GPa and temperatures up to the melting points. The thermal equation of state determined from the P–V–T measurements indicates that crystalline anti-perovskite Li 3 OBr exhibits similar thermo-elastic properties to common salts. At temperatures that are 50–75 °C below the crystal melting, a pre-melting behavior was inferred based on weakened Bragg intensity and a substantial increase in the diffuse scattering. Concurrent with the onset of pre-melting, an anomalous increase in the lattice volume was observed and is interpreted as anion sublattice disorder. These findings support previous ab initio molecular dynamics simulations based on a simple anion interchange mechanism, indicating that structural disorder below crystal melting temperature can be a main driving force for Li-sublattice melting and superionic transition in the Li 3 OBr anti-perovskite.

36 MATERIALS SCIENCE↗

Direct observations of shock-induced melting in a porous solid using time-resolved x-ray diffraction

Here in this work we provide direct evidence of shock-induced melting and associated kinetics in a porous solid (aluminum powder) using time-resolved x-ray diffraction. Unambiguous evidence of melting in 50% porous aluminum (Al) powder samples, shocked to peak pressures between ~13 - 19 GPa, was provided by the broadening of the Debye-Scherrer ring corresponding to the (111) peak. Shocked Al powder did not melt completely in any of our experiments within the durations of measurement. Incomplete (partial) melting of the powder, even after several hundreds of nanoseconds of shock loading, provides insights into thermal transport with Al powder particles under high-pressure dynamic loading. Such insights are quite valuable for developing well-constrained melting models and thermodynamic equations of state for porous Al and other porous solids relevant to planetary and materials science.

36 MATERIALS SCIENCE↗

Bubble explosion induced melt pool instabilities in electron beam melting of aluminum alloy

Electron beam melting (EBM) is an additive manufacturing technology that can process materials and manufacture components otherwise impossible or uneconomical. However, defects, including porosity and surface irregularities, are widely reported in EBM-built components, and their formation mechanisms are not fully understood. Here, using in-situ high-speed synchrotron X-ray imaging, we reveal that bubble explosions in Al6061 during EBM induce melt pool instabilities contributing to defect formation. The melt pool and keyhole evolve through three stages: (1) initial formation of a melt pool, (2) subsurface bubble formation and explosion, and (3) periodic keyhole oscillation. During scanning, periodic bubble explosions can eject molten liquid as spatters and disturb the vapor depression and melt pool, contributing to surface humping, that may trigger lack-of-fusion defects in subsequent layers. The physical insights we report could provide guidance for EBM machine development, process innovation, alloy design and model development.

36 MATERIALS SCIENCE↗

Samarium: from a distorted-fcc phase to melting under dynamic compression using in-situ x-ray diffraction

Abstract Lattice and electronic structure interactions for f -electrons are fundamental challenges for lanthanide equation of state development. Difficulties in first-principles calculations, such as density functional theory (DFT), emphasize the need for well-characterized experimental data. Here, we measure in-situ x-ray diffraction of shocked samarium (Sm) and temperature along the Hugoniot for the first time, providing direct evidence for phase transitions. We report direct evidence of a distorted fcc (dfcc) phase at 23 GPa. Shocked samarium melts from the dfcc phase starting at 33 GPa (1333 K), with complete melt at 40 GPa (1468 K). Previous work indicated shock melt at 27 GPa (1200 K), underscoring the significance of x-ray measurements for detecting phase transitions. Interestingly, our observed melting is in sharp contrast with the melting reported by a diamond anvil cell study. These experimental data can tightly constrain first principles calculations and serve as key touchstones for equation of state modeling.

36 MATERIALS SCIENCE↗

Tuning the melting point and phase stability of rare-earth oxides to facilitate their crystal growth from the melt

The challenge of growing rare-earth (RE) sesquioxide crystals can be overcome by tailoring their structural stability and melting point via composition engineering. This work contributes to the advancement of the field of crystal growth of high-entropy oxides. A compound with only small REs (Lu,Y,Ho,Yb,Er) 2 O 3 maintains a cubic C-type structure upon cooling from the melt, as observed via in-situ high-temperature neutron diffraction on aerodynamically levitated samples. On the other hand, a compound with a mixture of small and large REs (Lu,Y,Ho,Nd,La) 2 O 3 crystallizes as a mixture of a primary C-type phase with an unstable secondary phase. Crystals of compositions (Lu,Y,Ho,Nd,La) 2 O 3 and (Lu,Y,Gd,Nd,La) 2 O 3 were grown by the micro-pulling-down (mPD) method with a single monoclinic B-type phase, while a powder of (Lu,Y,Ho,Yb,Er) 2 O 3 did not melt at the maximum operating temperature of an iridium-rhenium crucible. The minimization of the melting point of the two grown crystals is attributed to the mismatch in cation sizes. The electron probe microanalysis reveals that the general element segregation behavior in the crystals depends on the composition.

36 MATERIALS SCIENCE↗

DEM and MELT: A Modular and Compact In-Can Melting Technology Dedicated to D and D and Remediation Waste - 20033

The DEM and MELT In-Can vitrification process is designed to process intermediate and high level waste coming for D and D and remediation operations. It is developed to treat liquid and solid waste, to produce a small amount of secondary waste and to minimize investment and operating costs. This In-Can vitrification process is also developed with a compact and modular design and can be adapted regarding nuclear operators' needs and requirements. Furthermore, this robust and simple process is flexible enough to accommodate most uncertainties on waste composition. The DEM and MELT process is developed through the French consortium coordinated by CEA which gathers Orano, ECM technologies and Andra. In the frame of this project, Orano has designed a compact and modular layout of the process allowing an efficient in situ implementation, close to the waste to be treated. This paper presents the compact and modular design of the DEM and MELT process and the way it can be used for a short duration, as a decommissioning tool aimed to be dismantled just after the treatment operation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ability to Simulate Absorption and Melt Pool Dynamics for Laser Melting of Bare Aluminum Plate: Results and Insights from the 2022 Asynchronous AM-Bench Challenge

The 2022 Asynchronous AM-Bench challenge was designed to test the ability of simulations to accurately predict laser power absorption as well as various melt pool behaviors (width, depth, and solidification) during laser melting of solid metal during stationary and scanned laser illumination. In this challenge, participants were asked to predict a series of experimental outcomes. Experimental data were obtained from a series of experiments performed at the Advanced Photon Source at Argonne National Laboratories in 2019. These experiments combined integrating sphere radiometry with high-speed X-ray imaging, allowing for the simultaneous recording of absolute laser power absorption and two-dimensional, projected images of the melt pool. All challenge problems were based on experiments using bare aluminum solid metal. Participants were provided with pertinent experimental information like laser power, scan speed, laser spot size, and material composition. Additionally, participants were given absorptance and X-ray imaging data from stationary and scanned laser experiments on solid Ti–6Al–4V that could be used for testing their models before attempting challenge problems. In total, this challenge received 56 submissions from eight different research groups for eight individual challenge problems. The data for this challenge, and associated information, are available for download from the NIST Public Data Repository. This paper summarizes the results from the 2022 Asynchronous AM-Bench challenge as well as discusses the lessons learned to help inform future challenges.

36 MATERIALS SCIENCE↗