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At least 991 records · Page 55

Reverse order-disorder transition of Janus particles confined in two dimensions

In this study Janus particles with different patch sizes, confined to two dimensions, generate a series of patterns of interest to the field of nanoscience. Here we observe reverse melting, where for some densities the system melts under cooling. For a broad range of hydrophobic patch sizes ( 60° < θ 0 < 90°), a reentrant transition from solid to liquid and then to an ordered phase emerges as temperature (T) decreases due to the formation of rhombus chains at low T. This reentrant phase has pseudo long-range orientational order but short-range translational order, similar to a hexatic phase. Our work provides guidelines to study the melting and assembly of Janus particles in two dimensions, as well as mechanisms to generate phases with specific symmetry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Microstructural pattern formation during liquid metal dealloying: Phase-field simulations and theoretical analyses

In recent years, liquid metal dealloying has emerged as a promising material processing method to generate micro- and nanoscale bicontinuous or porous structures. Most previous studies focused on the experimental characterization of the dealloying process and on the properties of the dealloyed materials, leaving the theoretical study incomplete to fully understand the fundamental mechanisms of the liquid metal dealloying process. In this paper, we use theoretical models and phase-field simulations to clarify the kinetics and pattern formation during liquid metal dealloying. Our investigation starts from a theoretical analysis of the 1D dissolution of a binary precursor alloy, which reveals that the 1D dissolution process involves two regimes. In the first regime, due to the low solubility of one of the elements in the melt, it accumulates at the solid-liquid interface, which reduces the dissolution kinetics. In the second regime, the interface kinetics reaches a stationary regime where both elements of the precursor alloy dissolve into the melt. Previous works revealed that in the early dealloying stage, the dealloying front is destabilized by an interfacial spinodal decomposition, which triggers the formation of interconnected ligaments. Here we extend this line of work by proposing a linear stability analysis able to predict the initial length scale of the ligaments formed in the initial stage of the dealloying. Combining this analysis with the 1D dissolution model proposed here enables us to better understand the initial conditions (composition of the precursor alloy and the melt) leading to a planar dissolution without interface destabilization. Finally, we report a strong influence of solid-state diffusion on dealloying. Although the solid-state diffusivity is four to five orders of magnitude smaller than in the liquid phase, it is found to affect both dissolution kinetics and ligament morphologies.

36 MATERIALS SCIENCE↗

High-resolution in-situ characterization of laser powder bed fusion via transmission X-ray microscopy at X-ray free electron lasers

In this work, we describe the instrumentation used to perform the first operando transmission X-ray microscopy (TXM) and simultaneous X-ray diffraction of laser melting simulating laser powder bed fusion on the XCS instrument at the Linac Coherent Light Source (LCLS) X-ray free-electron laser (XFEL). Our TXM with 40× magnification in the X-ray regime at 11 keV gave spatial resolutions down to 940 nm per line pair, with effective pixel sizes down to 206 nm, image integration times of <100 fs, and frame rates tunable between 2.1 and 119 ns for two probe frames (0.48 GHz to 8.4 MHz). Images were recorded on Zyla and Icarus (UXI) detectors to trade off between spatial resolution and time dynamics. A 1 kW CW IR laser was coupled into the interaction point to conduct pump–probe studies of laser melting and solidification dynamics. Our temporal and spatial resolution with attenuation-based contrast exceeds that currently possible with synchrotron-based high-speed radiography. This system was sensitive to feature velocities of 10–12000 m s −1 but we did not observe any motion in this range in the laser melting of Al6061 alloy. Shockwaves were not observed and hot cracking proceeded at velocities below the detection limits. Pore accumulation was observed between successive shots, indicating that bubble escape mechanisms were not active. With proper experimental design, the spatial resolution, contrast and field of view could be further improved or modified. The increased brightness and narrower bandwidth of the XFEL allowed for this imaging technique and it lays the groundwork for a wide range of operando techniques to study additive manufacturing.

47 OTHER INSTRUMENTATION↗

Effect of water vapor and thermal history on nuclear waste feed conversion to glass

Water affects the glass melting process by interacting with the foam layer at the glass melt surface and by influencing the batch conversion reactions. Water vapor from the nuclear waste slurry feed maintains a high water vapor pressure in the melter atmosphere. To investigate to what extent water vapor affects the vitrification of nuclear waste in joule-heated, cold-top melters, a series of feed expansion experiments were performed under humid and dry atmospheres using samples of low-activity waste (LAW) melter feed simulants. Melting of feed pellets in the presence of water vapor slightly decreased the temperature of primary foam onset, but did not significantly affect the feed volume expansion by foaming or the foam-collapse temperature. Sets of feed expansion experiments and evolved gas analyses were also performed to check the effect of thermal history on LAW feed samples tested as direct slurry, loose powder, and slow- and fast-dried pellets.

Marcial, Jose↗

A comparison of ceramic and carbon-based reductants for vitrification of low-activity waste

Sucrose is the current baseline additive at the Hanford Waste Treatment and Immobilization Plant in Washington, USA to control foaming during waste feed to glass transitions and the redox state of the glass melt. Alternative reductants are being investigated to alleviate strain on effluent treatment from toxic acetonitrile production from incomplete combustion of sucrose. This study evaluates ceramic additive options including B4C, B6Si, SiC and VB2 in simulated low-activity waste feed, as well as coke dust, probing the feed volume expansion during melting as well as the gas evolution. All alternative reductant options examined significantly reduced acetonitrile production, however there was variability in their effectiveness as foam-reducing agents. VB2 and coke at the appropriate ratios were similarly effective as sucrose in controlling both foam volume and glass redox state, but with considerably less acetonitrile production. B4C, B6Si and SiC showed more promising foam control and very little acetonitrile production, however all of the final glasses were over reduced, i.e., Fe2+/FeT = 0.5. These alternative reductant studies provide operational flexibility to the operation of the vitrification plant, as well as options for alternative raw materials in industrial glass melting.

Rigby, Jessica C. (ORCID:0000000235719977)↗

Structure and stability of alkali gallates structurally reminiscent of hollandite

Abstract Single crystals of CsGa 7 O 11 , RbGa 7 O 11 , and RbGa 4 In 5 O 14 were grown from alkali halide melts and their structures were characterized by single crystal and powder X‐ray diffraction. CsGa 7 O 11 and RbGa 7 O 11 adopt the same structure type, reminiscent of the hollandite structure type, as it contains nearly rectangular channels made up of two dimers of edge‐sharing GaO 6 octahedra, and two corner‐sharing octahedron/tetrahedron pairs. The structure of RbGa 4 In 5 O 14 is more complex and is comprised of indium octahedra, gallium trigonal bipyramids, and gallium tetrahedra, and contains similar sized tunnels as CsGa 7 O 11 and RbGa 7 O 11 . CsGa 7 O 11 and RbGa 4 In 5 O 14 were further characterized by TGA, ion exchange experiments, and DFT studies revealing that both structures are thermodynamically stable up to 850°C; however, CsGa 7 O 11 decomposes to GaO(OH) xH 2 O when heated in warm aqueous solutions. CsGa 7 O 11 undergoes ion exchange in both an aqueous solution of RbCl and a RbNO 3 melt, as predicted by DFT studies, where the ion exchange is more extensive in the RbNO 3 melt.

Juillerat, Christian A.↗

Controllable Solar Flux Heating for Freeze Recovery in Molten Salt Parabolic Trough Collectors

In molten-salt parabolic trough plants, the melting process is particularly important for freeze recovery of salt that is solidified in a collector loop, should such an event occur. Currently impedance heating is expected for freeze recovery of the collector loops, but this method can be expensive. Here, a lower-cost alternative is proposed to use controllable concentrated solar flux directly from the parabolic mirrors to thaw salt that is frozen in the collector. A computational fluid dynamics model was developed to explore the solidification and melting processes of molten salt in a parabolic trough receiver and to assess the viability of this concept. Results indicate that concentrated solar heating has the potential to melt frozen salt in 5.6 h, compared to that in 8.8 h for a 300 W m –1 impedance heating system. At the same time, controllable solar flux heating introduces nonuniform solar fluxes on the receiver surface, which can induce significant thermal stress on the receiver tube. A preliminary stress analysis indicates that the temperature difference across the receiver tube should be maintained below about 70 °C for heating up to 300 °C at internal pressures ≤10 bar. At these conditions, freeze recovery using solar flux heating will not significantly affect receiver lifetime. These results suggest that controllable solar flux heating could effectively supplement or replace impedance heating in the freeze recovery system. Incorporating this methodology in future parabolic trough concentrating solar power plants is an opportunity for capital and operational cost-savings.

14 SOLAR ENERGY↗

Accelerating Large-Format Metal Additive Manufacturing: How Controls R&D is Driving Speed, Scale, and Efficiency

This article highlights work at Oak Ridge National Laboratory’s Manufacturing Demonstration Facility to develop closed-loop, feedback control for laser-wire based Directed Energy Deposition, a form of metal Big Area Additive Manufacturing (m-BAAM), a process being developed in partnership with GKN Aerospace specifically for the production of Ti-6Al-4V pre-forms for aerospace components. A large-scale structural demonstrator component is presented as a case-study in which not just control, but the entire 3D printing workflow for m-BAAM is discussed in detail, including design principles for large-format metal AM, toolpath generation, parameter development, process control, and system operation, as well as post-print net-shape geometric analysis and finish machining. In terms of control, a multi-sensor approach has been utilized to measure both layer height and melt pool size, and multiple modes of closed-loop control have been developed to manipulate process parameters (laser power, print speed, deposition rate) to control these variables. Layer height control and melt pool size control have yielded excellent local (intralayer) and global (component-level) geometry control, and the impact of melt pool size control in particular on thermal gradients and material properties is the subject of continuing research. Further, these modes of control have allowed the process to advance to higher deposition rates (exceeding 7.5 lb/hr), larger parts (1-meter scale), shorter build times, and higher overall efficiency. The control modes are examined individually, highlighting their development, demonstration, and lessons learned, and it is shown how they operate concurrently to enable the printing of a large-scale, near net shape Ti-6Al-4V component.

Gibson, Brian↗

In-Cu alloy substrates for low-temperature chemical vapor deposition of Mo2C

Two-dimensional transition metal carbides are promising materials because of their potential for combining the favorable properties of transition metal carbides with the high aspect ratio of two-dimensional materials. Though commonly produced by top-down wet-chemical synthesis methods, synthesis by chemical vapor deposition is being considered because of its ability to achieve large areas, controlled layer thickness, and reduced defect density. Typically, liquid Cu is used as a synthesis substrate, though the high melting temperature of Cu (1085 °C) requires high synthesis temperatures. Thus, alternative substrates have been studied in order to reduce the necessary melting temperature. This work systematically studies the impact of synthesis parameters and substrate composition on the growth of ultrathin Mo2C (∼4–120 nm thick) by chemical vapor deposition on an In-Cu alloy. Mo2C flake size increases, and graphene/Mo2C heterostructures form with an increase in the methane flow rates. Increasing the In composition slightly decreases surface coverage and coalescence but does not appreciably impact the Mo2C flake size. Increasing In content also decreases the alloy substrate melting temperature so that a lower temperature synthesis (800 °C) can be performed. However, the necessary high temperatures for pyrolysis of methane lead to a lower limit for the synthesis temperature, similar to graphene.

Young, Katherine T. (ORCID:0000000285845576)↗

Electrochemical Recovery of Iron from Spent Pickle Liquor by Chloride-Based Molten Salt Electrolysis

Spent pickle liquor (SPL) is a waste stream generated in the steel industry that presents both a disposal challenge and a potential resource for metal recovery. This study investigates the electrochemical extraction of high-purity iron metal from SPL using chloride-based molten salt electrolysis (CMSE). Electrochemical characterization of diluted SPL confirmed Fe 2+ as the dominant species. Thermal dehydration of SPL under inert atmosphere yielded FeCl 2 -rich solids, which were directly employed as feedstock for electrolysis in LiCl–KCl eutectic melts at 500 °C. Cyclic voltammetry of FeCl 2 in this melt revealed well-defined Fe 2+ /Fe 0 redox behavior within the electrochemical stability window of the supporting electrolyte. High coulombic efficiency (>85%) electrodeposition was achieved demonstrating that iron metal can be produced from dehydrated SPL by CMSE. The electrodeposited iron exhibited >98 wt% purity, which was further enhanced to 99.9 wt% via arc melting. The resulting iron powder was ferromagnetic, and its size distribution was found to be suitable for powder metallurgy applications. This work demonstrates a scalable, energy-efficient pathway for valorizing SPL into high-purity iron metal, advancing circular economy strategies in the steel industry.

Materials science↗

Polarimetric Signatures in Landfalling Tropical Cyclones

Polarimetric radar observations from the NEXRAD WSR-88D operational radar network in the contiguous United States, routinely available since 2013, are used to reveal three prominent microphysical signatures in landfalling tropical cyclones: 1) hydrometeor size sorting within the eyewall convection, 2) vertical displacement of the melting layer within the inner core, and 3) dendritic growth layers within stratiform regions of the inner core. Size sorting signatures within eyewall convection are observed with greater frequency and prominence in more intense hurricanes, and are observed predominantly within the deep-layer environmental wind shear vector-relative quadrants that harbor the greatest frequency of deep convection (i.e., downshear and left-of-shear). Melting-layer displacements are shown that exceed 1 km in altitude compared to melting-layer altitudes in outer rainbands and are complemented by analyses of archived dropsonde data. Dendritic growth and attendant snow aggregation signatures in the inner core are found to occur more often when echo-top altitudes are low (≤10 km MSL), nearer the -15°C isotherm commonly associated with dendritic growth. These signatures, uniquely observed by polarimetric radar, provide greater insight into the physical structure and thermodynamic characteristics of tropical cyclones, which are important for improving rainfall estimation and the representation of tropical cyclones in numerical models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fluorescent amplification for next generation sequencing (FA-NGS) library preparation

BACKGROUND: Next generation sequencing (NGS) has become a universal practice in modern molecular biology. As the throughput of sequencing experiments increases, the preparation of conventional multiplexed libraries becomes more labor intensive. Conventional library preparation typically requires quality control (QC) testing for individual libraries such as amplification success evaluation and quantification, none of which occur until the end of the library preparation process. RESULTS: In this study, we address the need for a more streamlined high-throughput NGS workflow by tethering real-time quantitative PCR (qPCR) to conventional workflows to save time and implement single tube and single reagent QC. We modified two distinct library preparation workflows by replacing PCR and quantification with qPCR using SYBR Green I. qPCR enabled individual library quantification for pooling in a single tube without the need for additional reagents. Additionally, a melting curve analysis was implemented as an intermediate QC test to confirm successful amplification. Sequencing analysis showed comparable percent reads for each indexed library, demonstrating that pooling calculations based on qPCR allow for an even representation of sequencing reads. To aid the modified workflow, a software toolkit was developed and used to generate pooling instructions and analyze qPCR and melting curve data. CONCLUSIONS: We successfully applied fluorescent amplification for next generation sequencing (FA-NGS) library preparation to both plasmids and bacterial genomes. As a result of using qPCR for quantification and proceeding directly to library pooling, the modified library preparation workflow has fewer overall steps. Therefore, we speculate that the FA-NGS workflow has less risk of user error. The melting curve analysis provides the necessary QC test to identify and troubleshoot library failures prior to sequencing. While this study demonstrates the value of FA-NGS for plasmid or gDNA libraries, we speculate that its versatility could lead to successful application across other library types.

59 BASIC BIOLOGICAL SCIENCES↗

Spatiotemporally Registered In-Situ and Ex-Situ Datasets for Laser-based Blown Powder Directed Energy Deposition

This dataset is comprised of in situ sensing data collected during laser-based, blown powder directed energy deposition (DED) of Inconel 718 representing eight different printing conditions: (1) nominal, (2) +15% scan speed, (3) +12% laser power, (4) +42% powder feed rate, (5) +100% jerk limit, (6) +10% layer height, (7) +20% hatch spacing, (8) +20% carrier gas flow. All eight DED builds constructed an identical test coupon geometry consisting of geometric features representative of industrial print requirements (e.g., bulk deposition, thin walls, overhangs). In situ data consists of xyz-coordinates (100 Hz) and on-axis melt pool camera video (60 Hz), both of which have been temporally synchronized to spatially map the melt pool camera data. In addition, post-build X-ray computed tomography (XCT) data for each of the eight test geometries have been spatially registered to the recorded xyz-coordinates, allowing for comparisons between melt pool camera data and flaws identified in the XCT data.

additive manufacturing↗

Real-time single-element-detection structured illumination optical metrology for laser powder bed fusion

Laser powder bed fusion (LPBF) is a type of metal additive manufacturing which could benefit from improved process monitoring to improve quality control. We demonstrate, for the first time to our knowledge, the coaxial monitoring of melt track formation in steel powder with spatial frequency modulation imaging (SPIFI), an enhanced-resolution imaging technique which uses a photodiode to record one-dimensional images. Using a custom live-display software and a high-speed SPIFI geometry, we offset the SPIFI field of view from the fusing beam to monitor different regions of the LPBF melt pool and surrounding area. This demonstrates the potential of SPIFI to monitor spatial features within the melt pool in real-time with increased data efficiency.

Hunter, Scott (ORCID:0009000886150312)↗

Comparing Pr 3+ and Nd 3+ for deactivating the Er 3+ : 4 I 13/2 level in lanthanum titanate glass

Erbium lanthanum titanate glasses were prepared by levitation melting for the spectroscopic study of ways to promote the mid-infrared fluorescence. Two series of heavily erbium doped glasses (15 wt%) were prepared with the addition of either Pr 3+ or Nd 3+ in amounts relative to Er 3+ of 0.05, 0.1, and 0.2. Both ions quench the lower Er 3+ laser level with the Pr 3+ doing so more rapidly. Although high co-dopant concentrations result in higher energy transfer, as clearly evidenced in upconversion and downconversion fluorescence measurements, the mid-infrared lifetime also suffers a reduction and, therefore, a balance must be struck in the co-dopant concentration. Lifetime and spectral measurements indicate that, at a fixed relative co-dopant amount, Pr 3+ is more effective than Nd 3+ at removing the bottleneck of the Er 3+ 4 I 13/2 level. Moreover, consideration of the lifetimes alongside the absorption data of the individual ions indicates that despite the large absorption cross-section of Nd 3+ at 808 nm, the concentration needed to yield more absorbed power than utilizing direct 976 nm excitation of Er 3+ results in unfavorable lifetimes of the mid-infrared transition. In the end, Pr 3+ prevails as the superior co-dopant in terms of the effects on fluorescence lifetimes as well as potential laser system design considerations. In a unique self-doping approach, a reducing melt atmosphere of Ar instead of O 2 creates a small fraction of Ti 3+ . In 5Er 2 O 3 -12La 2 O 3 -83TiO 2 glass, the presence of Ti 3+ quenches the 4 I 13/2 emission about 2.6 times more than the 4 I 11/2 when lifetimes are compared to an O 2 melt environment. As an additional means of increasing the mid-infrared emission, the effect of temperature on the mid- and near- infrared lifetimes of a lightly doped lanthanum titanate composition is investigated between 77-300 K. The mid-infrared lifetime increases by ∼30% while the near-infrared lifetime increases by ∼10%, which suggests in addition to co-doping, active cooling of the gain media will further enhance performance.

Materials Science↗

Sea ice heat and mass balance measurements from four autonomous buoys during the MOSAiC drift campaign

As part of the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC), four autonomous seasonal ice mass balance buoys were deployed in first- and second-year ice. These buoys measured position, barometric pressure, snow depth, ice thickness, ice growth, surface melt, bottom melt, and vertical profiles of temperature from the air, through the snow and ice, and into the upper ocean. Observed air temperatures were similar at all four sites; however, snow–ice interface temperatures varied by as much as 10°C, primarily due to differences in snow depth. Observed winter ice growth rates (November to May) were <1 cm day -1 , with summer melt rates (June to July) as large as 5 cm day -1 . Air temperatures changed as much as 2°C hour -1 but were dampened to <0.3°C hour -1 at the snow–ice interface. Initial October ice thicknesses ranged from 0.3 m in first-year ice to 1.2 m in second-year ice. By February, this range was only 1.20–1.46 m, due in part to differences in the onset of basal freezing. In second-year ice, this delay was due to large brine-filled voids in the ice; propagating the cold front through this ice required freezing the brine. Mass balance results were similar to those measured by autonomous buoys deployed at the North Pole from 2000 to 2013. Winter average estimates of the ocean heat flux ranged from 0 to 3 W m -2 , with a large increase in June 2020 as the floe moved into warmer water. Estimates of average snow thermal conductivity measured at two buoys during periods of linear temperature profiles were 0.41 and 0.42 W m -1 °C -1 , higher than previously published estimates. Results from these ice mass balance buoys can contribute to efforts to close the MOSAiC heat budget.

54 ENVIRONMENTAL SCIENCES↗

Marine aerosol generation experiments in the High Arctic during summertime

The rapidly warming Arctic has transitioned to thinner sea ice which fractures, producing leads. Few studies have investigated Arctic sea spray aerosol (SSA) produced from open ocean, leads, and melt ponds, which vary in salinity and organic and microbial community composition. A marine aerosol reference tank was deployed aboard an icebreaker to the Arctic Ocean during August–September 2018 to study SSA generated from locally collected surface waters. Aerosol generation experiments were carried out using water collected from the marginal ice zone, a human-made hole in sea ice near the North Pole, and both lead and melt pond water during an ice floe drift period. Salinity, chlorophyll a, organic carbon, nitrogen, and microbial community composition were measured. Eukaryotic plankton and bacterial abundance were elevated in experimental water from the marginal ice zone, but the relative contributions from major eukaryotic taxonomic groups varied little across the experiments. The chemical composition of individual SSA particles was analyzed using Raman microspectroscopy and computer-controlled scanning electron microscopy with energy-dispersive X-ray spectroscopy. Individual sea salt aerosol, primary organic aerosol, and mineral dust particles were observed. Sea salt aerosol constituted 44–95% of individual submicrometer and 68–100% of supermicrometer particles, by number, generated during each experiment. Carbon was detected in 85%, by number, of the individual sea salt particles, with visible organic coatings. Carbohydrates were detected in 72% of particles, by number, with smaller contributions from long-chain fatty acids (13%) and siliceous material (15%). SSA generated from melt pond water contained only long-chain fatty acids and siliceous material. Quantification of the ice-nucleating activity showed that locally produced SSA may define the High Arctic background ice-nucleating particle population, but cannot account for the peak atmospheric concentrations observed. As the Arctic warms, the increasing SSA emissions have a complex dependence on changing biological and physical processes.

54 ENVIRONMENTAL SCIENCES↗

Experimental calibration of an Fe3+/Fe2+-in-amphibole oxybarometer and its application to shallow magmatic processes at Shiveluch Volcano, Kamchatka

Abstract Oxygen fugacity is an important but difficult parameter to constrain for primitive arc magmas. In this study, the partitioning behavior of Fe3+/Fe2+ between amphibole and glass synthesized in piston-cylinder and cold-seal apparatus experiments is developed as an oxybarometer, applicable to magmas ranging from basaltic to dacitic composition. The partitioning of Fe2+ is strongly dependent on melt polymerization; the relative compatibility of Fe2+ in amphibole decreases with increasing polymerization. The Fe2+/Mg distribution coefficient between amphibole and melt is a relatively constant value across all compositions and is, on average, 0.27. The amphibole oxybarometer is applied to amphibole in mafic enclaves, cumulates, and basaltic tephra erupted from Shiveluch volcano in Kamchatka with measured Fe3+/FeTotal. An average Fe3+/Fe2+ amphibole-glass distribution coefficient for basalt is used to convert the Fe3+/FeTotal of amphibole in samples from Shiveluch to magmatic oxygen fugacity relative to NNO. The fO2 of primitive melts at the volcano is approximately NNO+2 and is faithfully recorded in amphibole from an amphibole-rich cumulate and the basaltic tephra. Apparently, higher fO2 recorded by amphibole in mafic enclaves likely results from partial dehydrogenation of amphibole during residence in a shallow andesite storage region. We identify three pulses of mafic magma recharge within two weeks of, a month before, and two to three months before the eruption and find that, at each of these times, the host andesite was recharged by at least two magmas at varying stages of differentiation. Application of the amphibole oxybarometer not only gives insight into magmatic fO2 but also potentially details of shallow magmatic processes.

Geochemistry & Geophysics↗