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At least 73 records · Page 4

Laboratory Development of a Pot Calcination Process for Converting Liquid Wastes to Solids

Simulated Darex, Purex, Thorex, and TBP-25 wastes were batch-evaporated and calcined to solids. The weight of residue was decreased to ~ 8% of the original waste for Darex, to ~ 4% for Purex, to ~ 2% for Thorex, and ~ 7% for TBP-25 by calcination to 1200°C. Semicontinuous evaporation and calcination to solids at 900°C of Darex and Purex wastes gave volume reduction factors of ~ 8 and 7 to 10, respectively. The nitrate contents of the residues from batch calcination to 800°C were from ~ 0.07 to 0.5 wt % while the nitrate contents of the residues from semicontinuous calcination to 900°C were from ~ 0.1 to 0.7 wt %. Sodium, calcium, and magnesium additives to Purex waste decreased the percent of sulfate volatilized into the condensate from ~ 30% to <0.5%. Replacement of the atmosphere above the waste with nitric oxide decreased ruthenium volatility from 50 to 60% of that originally present in Purex waste to 0.5 to 3.5%. The thermal conductivities for the calcined wastes, measured in situ, were all >0.1 Btu/hr ft °F at ~ 400°F and increased almost linearly with increasing temperature to >0.3 Btu/hr ft °F at ~ 1600°F in all cases studied.

052001* -- Nuclear Fuels-- Waste Processing↗

Development of flame and smoke retardant thermoplastic molding compounds

Compositions of polypropylene and ethylene-acrylic acid resins filled with high levels of alumina trihydrate of magnesium hydroxide were examined for smoke generation and impact resistance. Best results were obtained using alumina trihydrate coated with a low modulus elastomer, and ethylene-acrylic acid resin. Addition of polyvinyl alcohol fibers to the filled resin improves impact resistance and causes somewhat of an increase in smoke evolution.

Mueller, W. A.↗

Molecular dynamics study on interface formation and bond strength of impact-welded Mg-steel joints

It was recently demonstrated that the vaporizing foil actuator welding (VFAW) method can directly join immiscible magnesium and steel alloys without coating or a third chemical element based intermetallic compound layer. The VFAW Mg/steel joint exhibits a mixed interface layer of up to 200μm thickness consisting of Mg matrix and Fe particles. Computer simulations have suggested the formation of the interlayer is from the high-velocity frictional shearing between the Mg/steel substrates during the oblique impact in the VFAW process. This paper investigates the formation of Mg-Fe interlayer under VFAW condition with different shearing velocities using molecular dynamics (MD) model, and studies the bonding strength under different scenarios. Finally, the results elucidate the critical role of shearing velocity and surface roughness in achieving Mg/Fe joint.

36 MATERIALS SCIENCE↗

Discovery of dual-activity small-molecule ligands of Pseudomonas aeruginosa LpxA and LpxD using SPR and X-ray crystallography

The lipid A biosynthesis pathway is essential in Pseudomonas aeruginosa. LpxA and LpxD are the first and third enzymes in this pathway respectively, and are regarded as promising antibiotic targets. The unique structural similarities between these two enzymes make them suitable targets for dual-binding inhibitors, a characteristic that would decrease the likelihood of mutational resistance and increase cell-based activity. We report the discovery of multiple small molecule ligands that bind to P. aeruginosa LpxA and LpxD, including dual-binding ligands. Binding poses were determined for select compounds by X-ray crystallography. The new structures reveal a previously uncharacterized magnesium ion residing at the core of the LpxD trimer. In addition, ligand binding in the LpxD active site resulted in conformational changes in the distal C-terminal helix-bundle, which forms extensive contacts with acyl carrier protein (ACP) during catalysis. These ligand-dependent conformational changes suggest a potential allosteric influence of reaction intermediates on ACP binding, and vice versa. Taken together, the novel small molecule ligands and their crystal structures provide new chemical scaffolds for ligand discovery targeting lipid A biosynthesis, while revealing structural features of interest for future investigation of LpxD function.

59 BASIC BIOLOGICAL SCIENCES↗

Magnesium and Carbon Dioxide - A Rocket Propellant for Mars Missions

A rocket engine for Mars missions is proposed that could utilize CO2 accumulated from the Martian atmosphere as an oxidizer. For use as possible fuel, various metals, their hydrides, and mixtures with hydrogen compounds are considered. Thermodynamic calculations show that beryllium fuels ensure the most impulse but poor inflammability of Be and high toxicity of its compounds put obstacles to their applications. Analysis of the engine performance for other metals together with the parameters of ignition and combustion show that magnesium seems to be the most promising fuel. Ballistic estimates imply that a hopper with the chemical rocket engine on Mg + CO2 propellant could be readily developed. This vehicle would be able to carry out 2-3 ballistic flights on Mars before the final ascent to orbit.

Shafirovich, E. IA.↗

Magnetic and Magnetotransport Characteristics of Cr-Substituted Ni{sub 55}Mn{sub 34}Sn{sub 11} Thin Films Grown by Magnetron Sputtering

Highly oriented Cr-substituted Ni{sub 55}Mn{sub 34}Sn{sub 11} Heusler thin films having thickness ~ 400 nm were deposited by Ultrahigh vacuum dc magnetron sputtering on MgO (100) substrates. At room temperature, the films exhibit a mixture of dominant L2{sub 1} cubic austenite phase, as revealed by the intense (002) and (004) peaks, along with small fraction of the orthorhombic–martensitic phase. Surface morphology of the thin films showed distribution of Cr-rich and Cr-deficit regions together with patterned and aligned magnetic domains, thus bringing out the inherent room temperature ferromagnetism of the film. At temperatures above the Curie temperature, T{sub C} ~ 321 K, the magnetic behaviour of the films is seen to follow the Curie law rather than the Curie–Weiss law. Ferromagnetic to antiferromagnetic transition appears at T{sub N} ~ 247 K, which gives rise to exchange bias at low temperatures due to the coexistence of the two magnetic orders. This phase coexistence also leads to the formation of a spin glass state deep into the martensitic region. The film exhibits metal-like nature at high temperature and semiconductor-like behaviour with the lowering of temperature. A reentrant metallic state is observed at T ≤ 38 K during cooling that persists up to ≤ 62 K in warming cycle. The hysteresis in the ρ–T curve spread over a very wide temperature range confirms the magnetic phase coexistence in the martensitic state in the present thin films. The magnetoresistance (MR) first increases (2.4% at 300 K and H = 50 kOe) with temperature and maximizes to around ~ 3.25% at T = 150 K and then starts decreasing. Its value in the glassy state is very small. This shows that a magnetic liquid like state is more conducive to larger MR.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Catalyst for Carbon Monoxide Oxidation

In many applications, it is highly desirable to operate a CO2 laser in a sealed condition, for in an open system the laser requires a continuous flow of laser gas to remove the dissociation products that occur in the discharge zone of the laser, in order to maintain a stable power output. This adds to the operating cost of the laser, and in airborne or space applications, it also adds to the weight penalty of the laser. In a sealed CO2 laser, a small amount of CO2 gas is decomposed in the electrical discharge zone into corresponding quantities of CO and O2. As the laser continues to operate, the concentration of CO2 decreases, while the concentrations of CO and O2 correspondingly increase. The increasing concentration of O2 reduces laser power, because O2 scavenges electrons in the electrical discharge, thereby causing arcing in the electric discharge and a loss of the energetic electrons required to boost CO2 molecules to lasing energy levels. As a result, laser power decreases rapidly. The primary object of this invention is to provide a catalyst that, by composition of matter alone, contains chemisorbed water within and upon its structure. Such bound moisture renders the catalyst highly active and very long-lived, such that only a small quantity of it needs to be used with a CO2 laser under ambient operating conditions. This object is achieved by a catalyst that consists essentially of about 1 to 40 percent by weight of one or more platinum group metals (Pt, Pd, Rh, Ir, Ru, Os, Pt being preferred); about 1 to 90 percent by weight of one or more oxides of reducible metals having multiple valence states (such as Sn, Ti, Mn, Cu, and Ce, with SnO2 being preferred); and about 1 to 90 percent by weight of a compound that can bind water to its structure (such as silica gel, calcium chloride, magnesium sulfate, hydrated alumina, and magnesium perchlorate, with silica gel being preferred). Especially beneficial results are obtained when platinum is present in the catalyst composition in an amount of about 5 to 25 (especially 7) percent by weight, SnO2 is present in an amount of about 30 to 40 (especially 40) percent by weight, and silica gel is present in an amount of 45 to 55 (especially 50) percent by weight. The composition of this catalyst was suggested by preliminary experiments in which a Pt/SnO2 catalyst was needed for bound water to enhance its activity. These experimental results suggested that if the water were bound to the surface, this water would enhance and prolong catalyst activity for long time periods. Because the catalyst is to be exposed to a laser gas mixture, and because a CO2 laser can tolerate only a very small amount of moisture, a hygroscopic support for the catalyst would provide the needed H2O into the gas. Silica gel is considered to be superior because of its property to chemisorb water on its surface over a wide range of moisture content.

Davis, Patricia↗

Degradation of TATP, TNT, and RDX using mechanically alloyed metals

Bimetallic alloys prepared in a ball milling process, such as iron nickel (FeNi), iron palladium (FePd), and magnesium palladium (MgPd) provide in situ catalyst system for remediating and degrading nitro explosive compounds. Specifically, munitions, such as, 2,4,6-trinitrotoluene (TNT), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), nitrocellulose and nitroglycerine that have become contaminants in groundwater, soil, and other structures are treated on site to remediate explosive contamination.

Clausen, Christian↗

Experimental X-ray Charge-Density Studies–A Suitable Probe for Superconductivity? A Case Study on MgB 2

Case studies of 1T-TiSe 2 and YBa 2 Cu 3 O 7-δ have demonstrated that X-ray diffraction (XRD) studies can be used to trace even subtle structural phase transitions which are inherently connected with the onset of superconductivity in these benchmark systems. However, the utility of XRD in the investigation of superconductors like MgB 2 lacking an additional symmetry-breaking structural phase transition is not immediately evident. Nevertheless, high-resolution powder XRD experiments on MgB 2 in combination with maximum entropy method analyses hinted at differences between the electron density distributions at room temperature and 15 K, that is, below the T c of approx. 39 K. The high-resolution single-crystal XRD experiments in combination with multipolar refinements presented here can reproduce these results but show that the observed temperature-dependent density changes are almost entirely due to a decrease of atomic displacement parameters as a natural consequence of a reduced thermal vibration amplitude with decreasing temperature. Our investigations also shed new light on the presence or absence of magnesium vacancies in MgB 2 samples–a defect type claimed to control the superconducting properties of the compound. Here, we propose that previous reports on the tendency of MgB 2 to form non-stoichiometric Mg 1–x B 2 phases (1 – x ~ 0.95) during high-temperature (HT) synthesis might result from the interpretation of XRD data of insufficient resolution and/or usage of inflexible refinement models. Indeed, advanced refinements based on an Extended Hansen–Coppens multipolar model and high-resolution X-ray data, which consider explicitly the contraction of core and valence shells of the magnesium cations, do not provide any significant evidence for the formation of non-stoichiometric Mg 1–x B 2 phases during HT synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Interfacial Structure on Heterogeneous Nucleation of Amorphous Carbonates

For this work, classical molecular dynamics simulations were performed to provide physical insight into the impact of interfacial structure on the heterogeneous nucleation of amorphous calcium carbonate (ACC, CaCO 3 ·H 2 O) and amorphous magnesium carbonate (AMC, MgCO 3 ·H 2 O) by using α-quartz as a model substrate. Interfacial structure and energies were computed for ACC and AMC in contact with the (100), (001), and (101) α-quartz surfaces. The simulations showed α-quartz surfaces drew water molecules out of the carbonate nuclei to form a partial hydration layer. The formation of a partial hydration layer and its disruption to the ACC/AMC structure meant the α-quartz–ACC/AMC interfaces were not energetically favored relative to separate α-quartz–water and ACC/AMC–water interfaces and, thus, homogeneous ACC/AMC nucleation was favored over heterogeneous nucleation. The CMD simulations hence provided an atomic-level explanation for a reported nonclassical growth mechanism whereby carbonate minerals grow via homogeneous nucleation and subsequent surface attachment of amorphous intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

2D Mg-Cu Intermetallic Compounds with Nontrivial Band Topology and Dirac Nodal Lines

Synthesis of vertical heterostructures that include atomically thin layers of materials with topologically nontrivial energy bands is desirable for exploring exotic quantum states. In this study, the authors report on atomic-layer-by-layer deposition of magnesium on copper(111) surface by molecular beam epitaxy, monitored in situ by low-energy electron microscopy and diffraction, and modeled by ab initio theory. It is found that a 2D MgCu 2 intermetallic compound forms during initial Mg deposition and persists till a full monolayer of Mg is formed. Deposition of additional Mg triggers a phase transition from the commensurate MgCu 2 to an incommensurate Mg 2 Cu layer and enables growth of the second layer of Mg. Ab initio calculations indicate non-trivial topology of the electron bands in the interfacial Mg 2 Cu layer and the existence of Dirac nodal lines near the Fermi level. The new 2D Mg 2 Cu material emerges as a promising platform to study new topological states of matter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Aluminum Alloy and Article Cast Therefrom

A cast article from an aluminum alloy, which has improved mechanical properties at elevated temperatures, has the following composition in weight percent: Silicon 14 - 25.0, Copper 5.5 - 8.0, Iron 0.05 - 1.2, Magnesium 0.5 - 1.5, Nickel 0.05 - 0.9, Manganese 0.05 - 1.0, Titanium 0.05 - 1.2, Zirconium 0.05 - 1.2, Vanadium 0.05 - 1.2, Zinc 0.05 - 0.9, Phosphorus 0.001 - 0.1, and the balance is Aluminum, wherein the silicon-to-magnesium ratio is 10 - 25, and the copper-to-magnesium ratio is 4 - 15. The aluminum alloy contains a simultaneous dispersion of three types of Al3X compound particles (X=Ti, V, Zr) having a LI2, crystal structure, and their lattice parameters are coherent to the aluminum matrix lattice. A process for producing this cast article is also disclosed, as well as a metal matrix composite, which includes the aluminum alloy serving as a matrix and containing up to about 60% by volume of a secondary filler material.

Lee, Jonathan A.↗

High Strength Aluminum Alloy For High Temperature Applications

A cast article from an aluminum alloy has improved mechanical properties at elevated temperatures. The cast article has the following composition in weight percent: Silicon 6.0-25.0, Copper 5.0-8.0, Iron 0.05-1.2, Magnesium 0.5-1.5, Nickel 0.05-0.9, Manganese 0.05-1.2, Titanium 0.05-1.2, Zirconium 0.05-1.2, Vanadium 0.05-1.2, Zinc 0.05-0.9, Strontium 0.001-0.1, Phosphorus 0.001-0.1, and the balance is Aluminum, wherein the silicon-to-magnesium ratio is 10-25, and the copper-to-magnesium ratio is 4-15. The aluminum alloy contains a simultaneous dispersion of three types of Al3X compound particles (X=Ti, V, Zr) having a LI2 crystal structure, and their lattice parameters are coherent to the aluminum matrix lattice. A process for producing this cast article is also disclosed, as well as a metal matrix composite, which includes the aluminum alloy serving as a matrix containing up to about 60% by volume of a secondary filler material.

Jonathan A Lee↗

Process for making manganese dioxide and its polymorphs reversible

A method of forming a layered manganese dioxide for use in a cathode of a battery comprises disposing a cathode into a housing of an electrochemical cell, disposing an anode into the housing, disposing a polymeric separator between the anode and the cathode such that the anode and the cathode are electrically separated, adding an alkaline electrolyte to the housing, cycling the electrochemical cell into the 2nd electron capacity of the manganese dioxide, and forming a layered manganese dioxide having a layered manganese dioxide structure with the one or more additives incorporated into the layered manganese dioxide structure. The cathode comprising a cathode material comprising: a manganese dioxide compound, one or more additives selected from the group consisting of bismuth, copper, tin, lead, silver, cobalt, nickel, magnesium, aluminum, potassium, lithium, calcium, gold, antimony, iron, zinc, and combinations thereof, and a conductive carbon.

Yadav, Gautam G.↗

Synthesis of Samarium Nitride Thin Films on Magnesium Oxide (001) Substrates Using Molecular Beam Epitaxy

Rare-earth nitrides are an exciting family of materials with a wide variety of properties desirable for new physics and applications in spintronics and superconducting devices. Among them, samarium nitride is an interesting compound reported to have ferromagnetic behavior coupled with the potential existence of p-wave superconductivity. Synthesis of high-quality thin films is essential in order to manifest these behaviors and understand the impact that vacancies, structural distortions, and doping can have on these properties. In this study, we report the synthesis of samarium nitride monocrystalline thin films on magnesium oxide (001) substrates with a chromium nitride capping layer using molecular beam epitaxy (MBE). We observed a high-quality monocrystalline SmN film with matching orientation to the substrate, then optimized the growth temperature. Despite the initial 2 nm of growth showing formation of a potential samarium oxide layer, the subsequent layers showed high-quality SmN, with semiconducting behavior revealed by an increase in resistivity with decreasing temperature. These promising results highlight the importance of studying diverse heteroepitaxial schemes and open the door for integration of rare-earth nitrides and transition metal nitrides for future spintronic devices.

36 MATERIALS SCIENCE↗

Carboxylic and dicarboxylic acids extracted from crushed magnesium oxide single crystals

Carboxylic and dicarboxylic acids (glycolic, oxalic, malonic and succinic) have been extracted with tetrahydrofuran (THF) and H2O from large synthetic MgO crystals, crushed to a medium fine powder. The extracts were characterized by infrared spectroscopy and 1H-NMR. The THF extracts were derivatized with tert-butyldimethylsilyl (t-BDMS) for GC-MS analysis. A single crystal separated from the extract was used for an x-ray structure analysis, giving the monoclinic unit cell, space group P21/c with ao = 5.543 A, bo = 8.845 A, co = 5.086 A, and beta = 91.9 degrees, consistent with beta-succinic acid, HOOC(CH2)COOH. The amount of extracted acids is estimated to be of the order of 0.1 to 0.5 mg g-1 MgO. The MgO crystals from which these organic acids were extracted grew from the 2860 degrees C hot melt, saturated with CO/CO2 and H2O, thereby incorporating small amounts of the gaseous components to form a solid solution (ss) with MgO. Upon cooling, the ss becomes supersaturated, causing solute carbon and other solute species to segregate not only to the surface but also internally, to dislocations and subgrain boundaries. The organic acids extracted from the MgO crystals after crushing appear to derive from these segregated solutes that formed C-C, C-H and C-O bonds along dislocations and other defects in the MgO structure, leading to entities that can generically be described as (HxCyOz)n-. The processes underlying the formation of these precursors are fundamental in nature and expected to be operational in any minerals, preferentially those with dense structures, that crystallized in H2O-CO2-laden environments. This opens the possibility that common magmatic and metamorphic rocks when weathering at the surface of a tectonically active planet like Earth may be an important source of abiogenically formed complex organic compounds.

NASA Discipline Exobiology↗

Synthesis and characterization of 5,15-bis(hydroxymethyl)porphyrins – simple compounds distantly inspired by the chlorosomal bacteriochlorophylls

A self-assembly paradigm is provided in green photosynthetic bacteria by the chlorin macrocycle bacteriochlorophyll (BChl) c, which contains a 3-(1-hydroxyethyl) substituent, central magnesium ion, and 13-keto group. The assembled BChl c structure is a powerful light-harvesting apparatus that can support life even under extreme low-light conditions. Here, inspired by the work of Balaban, two far simpler porphyrins have been synthesized, 5,15-bis(hydroxymethyl)-10,20-diphenylporphinatozinc(II) (Ph/CH 2 OH) and 5,15-bis(hydroxymethyl)porphinatozinc(II) (H/CH 2 OH), and analogues wherein ethyl replaces hydroxymethyl (Ph/Et and H/Et). Examination of Ph/CH 2 OH and H/CH 2 OH by time-resolved spectroscopy showed an ∼2-fold enhancement in the singlet excited-state lifetime compared to meso-tetraphenylporphinatozinc(II) (ZnTPP). The single-crystal X-ray diffraction revealed distinct packing patterns. Porphyrin Ph/CH 2 OH exhibited double staircases wherein (1) each zinc is pentacoordinate (by apical coordination of one hydroxymethyl group of a porphyrin in the same staircase), (2) the second hydroxymethyl group is hydrogen-bonded to an apically coordinated hydroxymethyl oxygen atom in the adjacent staircase, (3) the porphyrins in a given staircase are coplanar but cofacially offset with each other, and (4) the adjacent staircases are oriented approximately 72° relative to each other. Porphyrin H/CH 2 OH assembled wherein (1) each zinc is hexacoordinate by ligation of hydroxymethyl moieties, (2) each hydroxymethyl –OH is hydrogen-bonded with an acetonitrile solvent molecule in the lattice, and (3) the planes of the four nearest neighbor porphyrins are essentially perpendicular to a given porphyrin. Study of the solid-state packing patterns of sparsely substituted porphyrins enables insights into how the structural design of tetrapyrroles can guide their aggregate self-assembly.

Tran, Vy-Phuong [North Carolina State University, ↗

Lunar and Planetary Science XXXVI, Part 1

Contents include the following: Observations with Near Infrared Spectrometer for Hayabusa Mission in the Cruising Phase. First Results of Quadrantid Meteor Spectrum. Compositional Investigation of Binary Near-Earth Asteroid 66063 (1998 RO1): A Potentially Undifferentiated Assemblage. Impact-induced Hydrothermal Activity on Early Mars. HRTEM and EFTEM Studies of Phyllosilicate-Organic Matter Associations in Matrix and Dark Inclusions in the EET92042 CR2 Carbonaceous Chondrite. Volumetric Analysis of Martian Rampart Craters. High Pressure Melting of H-Chondrite: A Match for the Martian Basalt Source Mantle. MERView: A New Computer Program for Easy Display of MER-acquired M ssbauer Data. Distribution, Exchange, and Topographic Control of Subsurface Ice on Mars. Shock-induced Damage Beneath Normal and Oblique Impact Craters. Amphitrites Patera Studied from the Mars Express HRSC Data. Oxygen Isotope Microanalysis of Enveloping Compound Chondrules in CV3 and LL3 Chondrites. Gamma-Ray Irradiation in the Early Solar System and the Conundrum of the Lu-176 Decay Constant. Magnesium Isotope Mapping of Silica-rich Grains Having. Extreme Oxygen Isotope Anomalies Extreme Oxygen Isotopic Anomalies from Irradiation in the Early Solar System, Re-Examining the Role of Chondrules in Producing the Elemental Fractionations in Chondrites. Meteorite Data on the Solar Modulation of Galactic Cosmic Rays and an Inference on the Solar Activity Influence on Climate of the Earth. Volatiles Enrichments and Composition of Jupiter. Thinking Like a Wildcatter Prospecting for Methane in Arabia Terra, Mars. Size Distribution of Genesis Solar Wind Array Collector Fragments. Initial Subdivision of Genesis Early Science Polished Aluminum Collector. Presolar Graphite and Its Noble Gases. Young Pb-Isotopic Ages of Chondrules in CB Carbonaceous Chondrites. Fe Isotopic Composition of Martian Meteorites. Petrology and Geochemistry of Nakhlite MIL 03346: A New Martian Meteorite from Antarctica.

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