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At least 145 records · Page 8

Structural Phase Transitions of NbO 2 : Bulk versus Surface

The metal to insulator transition of NbO 2 has been predicted to be a result of a structural phase transition (SPT) governed by Peierls physics. However, direct observation of the SPT using experimental techniques is still restricted by the extremely high transition temperature (810 °C) and the proclivity for NbO 2 to oxidize into Nb 2 O 5 above 400 °C when exposed to air. In this work, we address these issues and employ temperature-dependent X-ray spectroscopy to describe the SPT of NbO 2 from the bulk to surface. Temperature-dependent extended X-ray absorption fine structure spectroscopy (T-EXAFS) reveals a gradual weakening of the bulk Nb dimers over a large temperature range, which is indicative of a second-order Peierls mechanism. From these measurements, we determine the critical dimer distance to be 2.77 Å. Our T-EXAFS observations are supported by density functional theory of the phonon dispersion and the electronic density of states of NbO 2 , which conclude that the dimerization is responsible for the insulating phase. The dimerization does not extend to the topmost layers, where an oxygen rich surface reconstruction is preferred irrespective of temperature even in extremely reducing environments; changes in the low-energy electron diffraction patterns are attributed to oxygen concentration and are independent of the underlying bulk phase transitions of NbO 2 .

36 MATERIALS SCIENCE↗

Discovery of Gold Nanoparticles in Marcellus Shale

A high density of gold (Au) nanoparticles has been observed on the surfaces of the coexisting opal nanospheres in kerogen-bearing shales from the Marcellus Formation. Our analyses of the Au nanoparticles and associated minerals indicate that this represents a new formation type of colloidal gold nanoparticles. Additionally, the opal nanospheres are a new kind of natural opal-A that is characteristic of the mesoporous texture formed through oil-in-water emulsion processes. High-resolution transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy analysis directly reveals spherical gold nanoparticles and gold nanorods associated with mesoporous opal nanospheres. Our newly found textures indicate that opal nanospheres may have facilitated the co-precipitation of pure gold nanoparticles in organic-bearing, reduced environments. Furthermore, our TEM observations provide distinct images of the initial phase of colloidal gold and silica, which may contribute to the formation of Au deposits involving "invisible" gold, secondary supergene enrichments, or high-grade gold accumulations. Finally, the discovery of Au nanoparticles in hydrocarbon-rich shale formations such as Marcellus (which contains 0.6-4.1 wt % gold/opal) suggests a potential for co-production of both gas/oil and gold-two valuable commodities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Facile One-Pot Block Copolymer-Mediated Solvothermal Approach for Synthesis of High-Entropy Alloy with Enhanced OER Activity

Herein, we introduce a straightforward synthesis approach for highly active dendritic multimetallic high-entropy alloy (DMHEA@PtIrPdAgRu) nanoparticles with sufficient entropic mixing, featuring uniform distribution of five noble group metals (Pt, Ir, Pd, Ag, and Ru) via a block copolymer-mediated one-pot solvothermal reduction method for oxygen evolution reaction (OER). In this synthesis, N,N -dimethylformamide (DMF) is used as a reductant as well as solvent and core–shell-corona-type (poly(styrene)- block -poly(vinylpyridine)- block -poly(ethylene oxide)) (PS-PVP-PEO) block copolymer as a structure directing agent. The cooperative effect between the copolymer architecture and the reducing environment of DMF promoted a confined nucleation mechanism for forming a single-phase dendritic structure HEA with high compositional uniformity, thereby mitigating phase segregation, a common challenge in the synthesis of multimetallic nanoparticles. This prepared DMHEA@PtIrPdAgRu catalyst exhibits a low overpotential of 490 mV to attain a high current density of 100 mA cm –2 with a Tafel slope of 442 mV dec –1 for oxygen evolution. The superior OER performance is attributed to the synergistic cooperation among its active and coordinated metal centers as well as the incorporation of corrosion-resistant metal like platinum.

block copolymer↗

Lithium metal-mediated electrochemical reduction of per- and poly-fluoroalkyl substances

Per- and poly-fluoroalkyl substances (PFAS) have substantial environmental and health hazards. Unfortunately, current degradation routes require high temperatures or corrosive conditions and/or lead to incomplete defluorination and the generation of shorter alkyl chains. Inspired by the lithium-metal battery literature, here we develop an electrochemical degradation process that leverages reactive metals and highly reducing environments. Here, we show that electrodeposited lithium metal can enable 95% degradation and 94% defluorination of perfluorooctanoic acid to LiF without forming any shorter C 2 –C 6 PFAS as end products. Using computational simulations, we find that electron transfer from lithium to perfluorooctanoic acid leads to rapid C–F bond cleavage, fluoride formation and carbon chain fragmentation. We expand the scope to other PFAS compounds and demonstrate substantial degrees of degradation on over 22 different PFAS, plus complete mineralization to inorganic fluorides. Finally, we use the mineralized F − as a fluorine source for the synthesis of fluorinated non-PFAS compounds to complete a circular fluorine loop from waste to valuable product.

Sarkar, Bidushi [Univ. of Chicago, IL (United Stat↗

Land-based wind plant wake characterization using dual-Doppler radar measurements at AWAKEN

Wind plant wakes have been shown to persist for tens of kilometers downstream in offshore environments, reducing the power output of neighboring plants, but their behavior on land remains relatively unexplored through observation. This study capitalizes on the unique and extensive field data collected for the American WAKE ExperimeNt (AWAKEN) project underway in northern Oklahoma. X-band dual-Doppler radars deployed at this site measure wind speed and direction at 25-m and 2-min resolution within a 30-km range, capturing the interactions between three neighboring wind plants. These measurements show that the wake of one wind plant extends at least 15 km downstream under easterly wind and stable atmospheric conditions. Though the wake wind speed increases within the first 10 km, it plateaus at 90% of the freestream wind speed. The spanwise velocity distribution within the wake initially shows the clear signature of the wind plant layout, which is smoothed as it propagates downstream, indicating spanwise momentum transfer is a key mechanism in wind plant wake development and recovery. These findings have important implications for wind plant siting decisions and resource assessments, and provide insights into atmospheric interactions at the wind plant scale.

17 WIND ENERGY↗

Structure transition and zigzag magnetic order in Ir/Rh-substituted honeycomb lattice α - RuCl 3

Here, we report magnetization and neutron diffraction studies on crystal and magnetic structures of Ir- and Rh-substituted honeycomb lattice α-RuCl 3 . The iridium or rhodium atoms are distributed at the Ru site with little structural modification. Both systems undergo a room-temperature monoclinic C2/m to low-temperature trigonal $R\bar{3}$ phase transformation with a large recoverable hysteresis. At low temperature, a zigzag spin order is observed with the same characteristic wave vector (0,0.5,1) as in the parent α-RuCl 3 . Detailed magnetic structure refinement reveals an ordered moment of 0.32(5)µB/Ru and an upper boundary of canting angle of 15(4)º away from the basal plane at 5 K for the 10% Ir-substituted α-RuCl 3 , which is different from the 0.45–0.73 µB/Ru and 32°–48° canting angle reported in the parent compound α-RuCl 3 . The observation of unchanged RuCl 6 local octahedral environment, reduced ordered magnetic moment size and canting angle compared to previously reported highlights the potential to study quantum spin-liquid behavior through nonmagnetic ion doping.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of Ba 3 Nb 0.75 Mn 2.25 O 9 -6H during thermochemical reduction of Ba 4 NbMn 3 O 12 -12R

The resurgence of interest in hydrogen-related technologies has stimulated new studies aimed at advancing lesser-developed water-splitting processes, such as solar thermochemical hydrogen production (STCH). Progress in STCH has been largely hindered by a lack of new materials able to efficiently split water at a rate comparable to ceria under identical experimental conditions. BaCe 0.25 Mn 0.75 O 3 (BCM) recently demonstrated enhanced hydrogen production over ceria and has the potential to further our understanding of two-step thermochemical cycles. A significant feature of the 12R hexagonal perovskite structure of BCM is the tendency to, in part, form a 6H polytype at high temperatures and reducing environments ( i.e. , during the first step of the thermochemical cycle), which may serve to mitigate degradation of the complex oxide. An analogous compound, namely BaNb 0.25 Mn 0.75 O 3 (BNM) with a 12R structure was synthesized and displays nearly complete conversion to the 6H structure under identical reaction conditions as BCM. The structure of the BNM-6H polytype was determined from Rietveld refinement of synchrotron powder X-ray diffraction data and is presented within the context of the previously established BCM-6H structure.

08 HYDROGEN↗

Engineering Evaluation of Barium Buildup in a Decayed CsCl Sealed Source and Potential Impact for Cesium Release from a Breached Source

For more than 50 years, radioactive 137 Cs has been a major source material for radioactive sealed sources, usually constructed as cesium chloride (CsCl) salt loaded into double-walled, stainless-steel capsules. A complication develops as 137 Cs decays to 137 Ba since this process creates a strongly reducing environment inside the capsule. A potential hazard exists if the capsule is breached and air ingress induces rapid exothermic oxidation, and this mechanism is suspected to be responsible for the well-known contamination incident at the Harbor View facility in Washington state. For this study, many thermodynamic evaluations were performed to assess the internal state of capsules after several decades of decay and to describe the potential oxidation if the capsule contents were to suddenly be exposed to air. Results suggest that reduction of impurities such as Cu, Fe, Pb, and Cr to metal will occur. If these impurities are lacking, it is possible that even Ba metal will form. In most cases, rapid oxidation can occur, and the exothermic reactions are sufficient to vaporize portions of the contents, which would include the remaining 137 Cs.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

PDV Methods and Analysis for Surveillance of Explosive Components

The Weapons Evaluation Test Laboratory (WETL) at Sandia is collaborating with Lawrence Livermore National Laboratory (LLNL) to enhance explosive surveillance testing by integrating Photon Doppler Velocimetry (PDV) data. This project has streamlined the testing environment, reducing hardware costs and training needs while improving data collection efficiency and usability for lab technicians.

Kress, Matthew Kip [Sandia National Laboratories (↗

Stability of Polyethylene Glycol-Coated Copper Nanoparticles and Their Optical Properties

Oxidation is a corrosion reaction where the corroded metal forms an oxide. Prevention of oxidation at the nanoscale is critically important to retain the physicochemical properties of metal nanoparticles. In this work, we studied the stability of polyethylene glycol (PEG) coated copper nanoparticles (PEGylated CuNPs) against oxidation. The freshly-prepared PEGylated CuNPs mainly consist of metallic Cu which are quite stable in air although their surfaces are typically covered with a few monolayers of cuprous oxide. However, they are quickly oxidized in water due to the presence of protons that facilitate oxidation of the cuprous oxide to cupric oxide. PEG with carboxylic acid terminus could slightly delay the oxidation process compared to that with thiol terminus. It was found that a solvent with reducing power such as ethanol could greatly enhance the stability of PEGylated CuNPs by preventing further oxidation of the cuprous oxide to cupric oxide and thus retain the optical properties of CuNPs. The reducing environment also assists the galvanic replacement of these PEGylated CuNPs to form hollow nanoshells; however, they consist of ultra-small particle assemblies due to the co-reduction of gold precursor during the replacement reaction. As a result, these nanoshells do not exhibit strong optical properties in the near-infrared region. This study highlights the importance of solvent effects on PEGylated nonprecious metal nanoparticles against oxidation corrosion and its applications in preserving physicochemical properties of metallic nanostructures.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Magnetic studies on Apollo 15 and 16 lunar samples

The magnetic properties of lunar samples are almost exclusively due to rather pure metallic iron. The mare basalt contains about 0.06 wt.% Fe, the soils 0.5-0.6 wt.%, and the breccias 0.3-1.0 wt.%. Most of the additional iron in the soils and breccias is believed to be the result of reduction processes operating on the lunar surface. Whereas the total metallic iron content of the soils from all landing sites is rather constant, the Fe(0)/Fe(++) ratio and the average iron grain size increase with the age of the landing site, reflecting increasing maturity. The crystalline rocks studied from Apollo 16 have highly variable, but generally, very high metallic Fe content (up to 1.7 wt.% Fe). It is suggested that these rocks are either breccias or igneous samples which have been severely thermally metamorphosed in a highly reducing environment.

Pearce, G. W.↗

High temperature electrically conducting ceramic heating element and control system

Improvements were made in both electrode technology and ceramic conductor quality to increase significantly the lifetime and thermal cycling capability of electrically conducting ceramic heater elements. These elements were operated in vacuum, inert and reducing environments as well as oxidizing atmospheres adding to the versatility of the conducting ceramic as an ohmic heater. Using stabilized zirconia conducting ceramic heater elements, a furnace was fabricated and demonstrated to have excellent thermal response and cycling capability. The furnace was used to melt platinum-20% rhodium alloy (melting point 1904 C) with an isothermal ceramic heating element having a nominal working cavity size of 2.5 cm diameter by 10.0 cm long. The furnace was operated to 1940 C with the isothermal ceramic heating element. The same furnace structure was fitted with a pair of main heater elements to provide axial gradient temperature control over a working cavity length of 17.8 cm.

Halbach, C. R.↗

Exobiology and the origin of life

Research supported wholly or in part by NASA is summarized, Topics covered include the molecular analysis of ultraviolet-photoproduced organic solids synthesized under simulated Jovian conditions; the molecular analysis of organic solids produced by electrical discharge in reducing atmospheres; the organic chemistry of interstellar grains; the spectra of possible organic solids present as aerosols in planetary atmospheres; far infrared studies of organic polymers of possible astrophysical interest; organic dust synthesized in reducing environments by ultraviolet radiation or electric discharge; the diffusion of galactic civilizations; eavesdropping on galactic civilizations; Lander imaging as a detector of life on Mars; and continuing puzzles about Mars. Bibliographic data is included for four additional publications not supported by NASA grant, but related to the objectives of the program.

Sagan, C.↗

The Tucson iron and its relationship to enstatite meteorites

The Tucson meteorite was studied in order to search for the origin of its silicates and to explore a possible relationship between Tucson and the enstatite meteorites. All samples were analyzed with an electron microprobe. The silicate inclusions are described in terms of size and texture, and the silicate mineralogy, which is that of a highly reduced assemblage, is described. The bulk composition of the silicate inclusions is discussed. The results provide evidence of fast cooling. The textural and mineralogical data all point to the presence of a high temperature melt followed by rapid cooling and quenching. Several hypotheses for the origin of the Tucson are discussed, and it is concluded that the preferred hypothesis is that the meteorite formed by the high temperature impact mixing of a forsterite-enstatite silicate assemblage with Si-bearing metal, both having formed in a highly reduced environment.

Nehru, C. E.↗

The rheology of icy satellites

High-temperature creep in orthoenstatite under conditions of controlled oxygen fugacity was studied. It was found that creep was conttrolled by the extremely thin layer of SiO2 which wetted the grain boundaries. Slight reduction of the (Mg, Fe)SiO3 enstatite during hot pressing produced microscopic particles of Fe and the thin film of intergranular SiO2. This result highlights another complication in determining the flow properties of iron bearing silicates which constitute the bulk of terrestrial planets and moons. The Phenomenon may be important in the ductile formation of any extraterrestrial body which is formed in a reducing environment. The rheology of dirty ice was studied. This involves micromechanical modeling of hardening phenomena due to contamination by a cosmic distribution of silicate particles. The larger particles are modeled by suspension theory. In order to handle the distribution of particles sizes, the hardening is readed as a critical phenomenon, and real space renormalization group techniques are used. Smaller particles interact directly with the dislocations. The particulate hardening effect was studied in metals. The magnitude of such hardening in ice and the defect chemistry of ice are studied to assess the effects of chemical contamination by methane, ammonia, or other likely contaminants.

Sammis, C. G.↗

Experimental geochemistry of Pu and Sm and the thermodynamics of trace element partitioning

An experimental study of the partitioning of Pu and Sm between diopside/liquid and whitlockite/liquid supports the hypothesis that Pu behaves as a light rare earth element during igneous processes in reducing environments. D-Pu/D-Sm is found to be about 2 for both diopsidic pyroxene and whitlockite, and the amount of fractionation would be decreased further if Pu were compared to Ce or Nd. Data indicate that temperature, rather than melt composition, is the most important control on elemental partitioning, and that P2O5 in aluminosilicate melts serves as a complexing agent for the actinides and lanthanides.

Jones, John H.↗

Estimation of duration and mental workload at differing times of day by males and females

Two experiments are reported which investigated whether male and female operator duration estimation and subjective workload followed conventional circadian fluctuation. In the first experiment, twenty-four subjects performed a filled time-estimation task in a constant blacked-out, noise-reduced environment at 0800, 1200, 1600, and 2000 h. In the second experiment, twelve subjects performed an unfilled time estimation task in similar conditions at 0900, 1400, and 1900 h. At the termination of all experimental sessions, participants completed the NASA TLX workload assessment questionnaire as a measure of perceived mental workload. Results indicated that while physiological response followed an expected pattern, estimations of duration and subjective perception of workload showed no significant effects for time-of-day. In each of the experiments, however, there were significant differences in durational estimates and mental workload response depending upon the gender of the participant. Results are taken to support the assertion that subjective workload is responsive largely to task-related factors and indicates the important differences that may be expected due to operator gender.

Hancock, P. A.↗

Reducing Run-In Wear Of Ceramic-Based Coatings

Silver surface layer helps rough ceramic slide smoothly. Thin film is magnetron-sputtered onto PS200, self-lubricating composite coating containing mixture of chromium carbide, silver, and barium fluoride/calcium fluoride eutectic. Carbide provides wear resistance, while silver and fluorides provide lubrication. Because both silver top coat and PS200 thermally and chemically stable oxidizing and reducing environments to 900 degrees C, combination appropriate as lubrication for cylinder-wall/piston-ring contacts in Stirling engines and for backup lubrication for gas lubricated journal bearings.

Dellacorte, Christopher↗