Plasma metallurgical production of nanocrystalline borides and carbides

NASA Astrophysics Data System (ADS)

Galevsky, G. V.; Rudneva, V. V.; Cherepanov, A. N.; Galevsky, S. G.; Efimova, K. A.

2016-09-01

he experience in production and study of properties of nanocrystalline borides and chromium carbides, titanium, silicon was summarized. The design and features of the vertical three-jet once-through reactor with power 150 kW, used in the plasma metallurgical production, was described. The technological, thermotechnical and resource characteristics of the reactor were identified. The parameters of borides and carbides synthesis, their main characteristics in the nanodispersed state and equipment-technological scheme of production were provided. Evaluation of engineering-and-economical performance of the laboratory and industrial levels of borides and carbides production and the state corresponding to the segment of the world market was carried out.

Investigation of Hard Boron Rich Solids: Osmium Diboride and β-Rhombohedral Boron

NASA Astrophysics Data System (ADS)

Hebbache, M.; Živković, D.

Recently, we succeeded in synthesizing three osmium borides, i.e., OsB1.1, Os2B3 and OsB2. Up to date, almost nothing is known about the physical properties of these materials. Microhardness measurements show that OsB2 is extremely hard. Ab initio calculations show that it is due to formation of covalent bonds between boron atoms. OsB2 is also a low compressibility material. It can be used for hard coatings. The β-rhombohedral polymorph of boron is the second hardest elemental crystal (H ≈ 33 GPa). It is also very light and a p-type semiconductor. In early 1970s, it has been shown that the doping of boron with 3d transition elements enhances its hardness by about 25%. We predict that, in general, heavily doped samples MBx, with x ≤ 31 or equivalently a dopant concentration larger than 3.2 at.%, should be ultrahard, i.e., H > 43 GPa. The relevant dopants M are Al, Cu, Sc, Mn, Mg and Li. In addition to these properties, boron-rich materials have a very low volatility, a high chemical inertness and high melting point. They are suitable for applications under extreme conditions and thermoelectric equipment.

Characterisation of titanium-titanium boride composites processed by powder metallurgy techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Selva Kumar, M., E-mail: sel_mcet@yahoo.co.in; Chandrasekar, P.; Chandramohan, P.

2012-11-15

In this work, a detailed characterisation of titanium-titanium boride composites processed by three powder metallurgy techniques, namely, hot isostatic pressing, spark plasma sintering and vacuum sintering, was conducted. Two composites with different volume percents of titanium boride reinforcement were used for the investigation. One was titanium with 20% titanium boride, and the other was titanium with 40% titanium boride (by volume). Characterisation was performed using X-ray diffraction, electron probe micro analysis - energy dispersive spectroscopy and wavelength dispersive spectroscopy, image analysis and scanning electron microscopy. The characterisation results confirm the completion of the titanium boride reaction. The results reveal themore » presence of titanium boride reinforcement in different morphologies such as needle-shaped whiskers, short agglomerated whiskers and fine plates. The paper also discusses how mechanical properties such as microhardness, elastic modulus and Poisson's ratio are influenced by the processing techniques as well as the volume fraction of the titanium boride reinforcement. - Highlights: Black-Right-Pointing-Pointer Ti-TiB composites were processed by HIP, SPS and vacuum sintering. Black-Right-Pointing-Pointer The completion of Ti-TiB{sub 2} reaction was confirmed by XRD, SEM and EPMA studies. Black-Right-Pointing-Pointer Hardness and elastic properties of Ti-TiB composites were discussed. Black-Right-Pointing-Pointer Processing techniques were compared with respect to their microstructure.« less

Anthropogenic Osmium in Airborne Particles from Woods Hole, Massachusetts, USA

NASA Astrophysics Data System (ADS)

Peucker-Ehrenbrink, B.; Sen, I. S.; Geboy, N.

2012-12-01

The global geochemical cycle of osmium has been significantly disturbed by the introduction of automobile exhaust catalysts to convert noxious gas emissions into more benign forms. Anthropogenic osmium has been reported in rainwater, snow, and in the urban airborne particles from around the world to reveal global-scale osmium pollution [1, 2]. In this study, we report on the platinum group element (PGE) concentrations and osmium isotope ratios of airborne particles (PM10) collected in Woods Hole, a small coastal town in Massachusetts to better understand inputs of anthropogenic osmium to rural environments. We further investigate the use of osmium isotopes to track sources of airborne particles and support source apportionment studies on a continental scale. The samples used in this study were collected at Woods Hole Oceanographic Institution over one year (2008-2009). From this collection twelve samples for which the backward air mass trajectories have been determined were selected for osmium isotope analyses. Our results show that the osmium and platinum concentrations are an order of magnitude lower when compared to downtown Boston [2]. The average Os, Pt and Ir concentrations are 0.006±0.012, 0.019±0.023, and 0.685±0.634 pg m-3, respectively. The 187Os/188Os of the aerosols range from 0.275 to 0.788. As continental crust is radiogenic (187Os/188Os >1) and PGE ore bodies generally have unradiogenic 187Os/188Os (~0.2), the unradiogenic 187Os/188Os signature of the aerosols indicates anthropogenic contributions. With 95% of the total osmium mobilization on land being attributed to human activities [3], it is clear that human imprint on airborne particles is not restricted to urban centers with high traffic flows, but also affects rural environments. Aerosol particles that have backward air mass trajectories from the Southwest, the densely populated and industrialized Eastern seaboard, are characterized by unradiogenic osmium, while air masses from the North

Osmium coated diffraction grating in the Space Shuttle environment - Performance

NASA Technical Reports Server (NTRS)

Torr, M. R.

1985-01-01

Samples coated with osmium were flown on the early Shuttle test flights, and on the return of these samples, the osmium coating was found to have disappeared, evidently due to the oxidation of the material in the atomic oxygen atmosphere. An instrument flown on the Spacelab 1 mission comprised an array of five spectrometers covering the extreme ultraviolet (EUV) to near-IR wavelengths. The EUV spectrometer contained an osmium-coated reflective grating located fairly deep within the instruments. Here, results of an assessment of the reflectivity and stability of the osmium surface over the course of the ten-day mission are reported. It is concluded that the osmium reflective coating remained stable relative to the spectrometer coated with MgF2 over the course of the mission. In addition, the ratio of sensitivity of these two spectrometers did not change in any major way from the time of the laboratory calibration until the time of flight two years later. Any changes are within the 50-percent calibration uncertainty.

Crystal structure and phase stability of tungsten borides

NASA Astrophysics Data System (ADS)

Li, Quan; Zhou, Dan; Ma, Yanming; Chen, Changfeng

2013-03-01

We address the longstanding and controversial issue of ground-state structures of technically important tungsten borides using a first-principles structural search method via a particle-swarm optimization (PSO) algorithm. We have explored a large set of stable chemical compositions (convex hull) and clarified the ground-state structures for a wide range of boron concentrations, including W2B, W3B2,WB,W2B3, WB2,W2B5, WB3, and WB4. We further assessed relative stability of various tungsten borides and compared the calculated results with previously reported experimental data. The phase diagram predicted by the presented calculations may serve as a useful guide for synthesis of a variety of tungsten borides. This work was supported by DOE Grant No. DE-FC52-06NA26274.

Morphology and structure of borides in as-cast titanium and gamma-titanium aluminide-based alloys

NASA Astrophysics Data System (ADS)

Kitkamthorn, Usanee

In this study, the morphology and structure of the borides in boron-modified Ti- and gamma-TiAl-based alloys have been investigated using SEM, TEM, and HRTEM. A variety of different boride morphologies was observed including plates, needles, and ribbons. For the plate and needle borides, the major boride phase is B27 TiB. The needle borides have their major axis parallel to [010], and are bounded by (100) and {101} type-facets. The plate borides develop the same types of facets as the needles and have habit planes parallel to the (100). There are high densities of intrinsic stacking faults on (100) in these borides and these correspond to thin embedded layers of the Bf structure. The plate borides do not exhibit well-defined ORs with respect to the surrounding phases, suggesting that they develop in the liquid melt and were then trapped by the growing solid. Needle borides are observed mostly at boundaries between lamellar colonies: these needles tend to occur in groups lying nearly parallel to one another and, in some cases, to adopt well-defined ORs with respect to the surrounding phases. Cored borides with metallic phases such as beta, alpha, o and alpha 2+gamma in the center are frequently observed, especially in the Ti-based alloy. These core phases usually adopt well-defined ORs with respect to the surrounding boride which enable low-energy coherent interfaces to form between the phases. The ribbon borides are comprised of thin boride flakes interspersed with thin metallic layers. The major boride phase in these flakes is Bf TiB. The habit plane of the flakes is (010) and there are high densities of faults on this plane corresponding to intergrowths of the Ti3B 4 and TiB2 phases, together with thin layers or occluded pockets of metallic B2 phase. Occasional faults are observed on {110} corresponding to embedded slabs of B27 TiB. There is a well-defined OR between the boride flakes and the B2 phase within the ribbons, but not with the surrounding matrix. The

Amorphous Iron Borides: Preparation, Structure and Magnetic Properties.

DTIC Science & Technology

1982-09-28

temperature. External magnetic field experiments were performed in a superconducting solenoid with both source and absor- ber at 4.2 K. The observed...D-Ai20 919 AMORPHOUS IRON BORIDES: PREPARATION STRUCTURE AND i/i MAGNETIC PROPERTIES(U) JOHNS HOPKINS UNIV LAUREL NO APPLIED PHYSICS LRB K MOORJRNI...NATIONAL BUREAU OF STANOANOS-93-A 10 AMORPHOUS IRON BORIDES: PREPARATION, STRUCTURE ~AND MAGNETIC PROPERTIES FINAL REPORT Kishin Moorjani September 1982 U

Fast turn-on osmium coated cathode

NASA Astrophysics Data System (ADS)

Marrian, C. R. K.; Haas, G. A.; Shih, A.

1984-03-01

This abstract discloses a fast turn-on refractory coated cathode comprising a porous tungsten metal matrix impregnated with barium calcium aluminate and coated with osmium. The osmium coating has a planned series of interruptions with each interruption being on the order of several microns in width to thereby expose the tungsten. These interruptions permit the barium and oxygen from the impregnant to rise to the cathode surface during activation or reactivation to form a desired near monolayer of barium and oxygen to enhance electron emission. Thus, this cathode design provides a fast turn-on characteristic even after shelf storage.

Beta cell device using icosahedral boride compounds

DOEpatents

Aselage, Terrence L.; Emin, David

2002-01-01

A beta cell for converting beta-particle energies into electrical energy having a semiconductor junction that incorporates an icosahedral boride compound selected from B.sub.12 As.sub.2, B.sub.12 P.sub.2, elemental boron having an .alpha.-rhombohedral structure, elemental boron having a .beta.-rhombohedral structure, and boron carbides of the chemical formula B.sub.12-x C.sub.3-x, where 0.15boride compound self-heals, resisting degradation from radiation damage.

Certain physical properties of cobalt and nickel borides

NASA Technical Reports Server (NTRS)

Kostetskiy, I. I.; Lvov, S. N.

1981-01-01

The temperature dependence of the electrical resistivity, the thermal conductivity, and the thermal emf of cobalt and nickel borides were studied. In the case of the nickel borides the magnetic susceptibility and the Hall coefficient were determined at room temperature. The results are discussed with allowance for the current carrier concentration, the effect of various mechanisms of current-carrier scattering and the location of the Fermi level in relation to the 3d band.

Preparation of osmium targets with carbon backing

NASA Astrophysics Data System (ADS)

Fremont, Georges; Ngono-Ravache, Yvette; Schmitt, Christelle; Stodel, Christelle

2018-05-01

For nuclear reaction studies, thin metallic osmium targets, either natural or isotopically enriched (Os-192) of 200-300 µg/cm2 thicknesses deposited on a thin carbon backing are required. A challenging method was successfully performed at GANIL involving firstly the preparation of an aqueous solution of osmium tetrachloride, then its electro-deposition onto a thick copper backing (100 µm); this process was followed by the evaporation of a thin carbon layer (≈40 µg/cm²) and finally the dissolution of the copper material.

CONTRAST BETWEEN OSMIUM-FIXED AND PERMANGANATE-FIXED TOAD SPINAL GANGLIA

PubMed Central

Rosenbluth, Jack

1963-01-01

Chains of vesicles are prominent near the plasma membranes of both the neurons and satellite cells of osmium-fixed toad spinal ganglia. In permanganate-fixed specimens, however, such vesicles are absent, and in their place are continuous invaginations of the plasma membranes of these cells. The discrepancy suggests that the serried vesicles seen in osmium-fixed preparations arise through disintegration of plasma membrane invaginations, and do not represent active pinocytosis, as has been suggested previously. A second difference between ganglia fixed by these two methods is that rows of small, disconnected cytoplasmic globules occur in the sheaths of permanganate-fixed ganglia, but not in osmium-fixed samples. It is suggested that these globules arise from the breakdown of thin sheets of satellite cell cytoplasm which occur as continuous lamellae in osmium-fixed specimens. Possible mechanisms of these membrane reorganizations, and the relevance of these findings to other tissues, are discussed. PMID:13990905

Methods for the separation of rhenium, osmium and molybdenum applicable to isotope geochemistry

USGS Publications Warehouse

Morgan, J.W.; Golightly, D.W.; Dorrzapf, A.F.

1991-01-01

Effective methods are described for the chemical separation of rhenium, osmium and molybdenum. The methods are based on distillation and anion-exchange chromatography, and have been the basis for rhenium-osmium isotope studies of ore deposits and meteorites. Successful anion-exchange separation of osmium requires both recognition and careful control of the osmium species in solution; thus, distillation of osmium tetroxide from a mixture of sulfuric acid and hydrogen peroxide is preferred to anion-exchange. Distribution coefficients measured for perrhenate in sulfuric acid media are sufficiently high (Kd > 500) for rhenium to be directly loaded onto an ion-exchange column from a distillation residue and subsequently eluted with nitric acid. Polymerization of molybdenum species during elution is prevented by use of a solution that is 1M in hydrochloric acid and 1M in sodium chloride. ?? 1991.

Oxidation of pyrimidine nucleosides and nucleotides by osmium tetroxide

PubMed Central

Burton, K.

1967-01-01

1. Pyrimidine nucleosides such as thymidine, uridine or cytidine are oxidized readily at 0° by osmium tetroxide in ammonium chloride buffer. There is virtually no oxidation in bicarbonate buffer of similar pH. Oxidation of 1-methyluracil yields 5,6-dihydro-4,5,6-trihydroxy-1-methyl-2-pyrimidone. 2. Osmium tetroxide and ammonia react reversibly in aqueous solution to form a yellow 1:1 complex, probably OsO3NH. A second molecule of ammonia must be involved in the oxidation of UMP since the rate of this reaction is approximately proportional to the square of the concentration of unprotonated ammonia. 3. 4-Thiouridine reacts with osmium tetroxide much more rapidly than does uridine. The changes of absorption spectra are different in sodium bicarbonate buffer and in ammonium chloride buffer. They occur faster in the latter buffer and, under suitable conditions, cytidine is a major product. 4. Polyuridylic acid is oxidized readily by ammoniacal osmium tetroxide, but its oxidation is inhibited by polyadenylic acid. Pyrimidines of yeast amino acid-transfer RNA are oxidized more slowly than the corresponding mononucleosides, especially the thymine residues. Appreciable oxidation can occur without change of sedimentation coefficient. PMID:6048808

Oxidation of pyrimidine nucleosides and nucleotides by osmium tetroxide.

PubMed

Burton, K

1967-08-01

1. Pyrimidine nucleosides such as thymidine, uridine or cytidine are oxidized readily at 0 degrees by osmium tetroxide in ammonium chloride buffer. There is virtually no oxidation in bicarbonate buffer of similar pH. Oxidation of 1-methyluracil yields 5,6-dihydro-4,5,6-trihydroxy-1-methyl-2-pyrimidone. 2. Osmium tetroxide and ammonia react reversibly in aqueous solution to form a yellow 1:1 complex, probably OsO(3)NH. A second molecule of ammonia must be involved in the oxidation of UMP since the rate of this reaction is approximately proportional to the square of the concentration of unprotonated ammonia. 3. 4-Thiouridine reacts with osmium tetroxide much more rapidly than does uridine. The changes of absorption spectra are different in sodium bicarbonate buffer and in ammonium chloride buffer. They occur faster in the latter buffer and, under suitable conditions, cytidine is a major product. 4. Polyuridylic acid is oxidized readily by ammoniacal osmium tetroxide, but its oxidation is inhibited by polyadenylic acid. Pyrimidines of yeast amino acid-transfer RNA are oxidized more slowly than the corresponding mononucleosides, especially the thymine residues. Appreciable oxidation can occur without change of sedimentation coefficient.

Osmium isotopic tracing of atmospheric emissions from an aluminum smelter

NASA Astrophysics Data System (ADS)

Gogot, Julien; Poirier, André; Boullemant, Amiel

2015-09-01

We present for the first time the use of osmium isotopic composition as a tracer of atmospheric emissions from an aluminum smelter, where alumina (extracted from bauxite) is reduced through electrolysis into metallic aluminum using carbonaceous anodes. These anodes are consumed in the process; they are made of petroleum coke and pitch and have high Re/Os elementary ratio. Due to the relatively large geological age of their source material, their osmium shows a high content of radiogenic 187Os produced from in situ187Re radioactive decay. The radiogenic isotopic composition (187Os/188Os ∼ 2.5) of atmospheric particulate emissions from this smelter is different from that of other typical anthropogenic osmium sources (that come from ultramafic geological contexts with unradiogenic Os isotopes, e.g., 187Os/188Os < 0.2) and also different from average eroding continental crust 187Os/188Os ratios (ca. 1.2). This study demonstrates the capacity of osmium measurements to monitor particulate matter emissions from the Al-producing industry.

In Situ Solid-Gas Reactivity of Nanoscaled Metal Borides from Molten Salt Synthesis.

PubMed

Gouget, Guillaume; Debecker, Damien P; Kim, Ara; Olivieri, Giorgia; Gallet, Jean-Jacques; Bournel, Fabrice; Thomas, Cyril; Ersen, Ovidiu; Moldovan, Simona; Sanchez, Clément; Carenco, Sophie; Portehault, David

2017-08-07

Metal borides have mostly been studied as bulk materials. The nanoscale provides new opportunities to investigate the properties of these materials, e.g., nanoscale hardening and surface reactivity. Metal borides are often considered stable solids because of their covalent character, but little is known on their behavior under a reactive atmosphere, especially reductive gases. We use molten salt synthesis at 750 °C to provide cobalt monoboride (CoB) nanocrystals embedded in an amorphous layer of cobalt(II) and partially oxidized boron as a model platform to study morphological, chemical, and structural evolutions of the boride and the superficial layer exposed to argon, dihydrogen (H 2 ), and a mixture of H 2 and carbon dioxide (CO 2 ) through a multiscale in situ approach: environmental transmission electron microscopy, synchrotron-based near-ambient-pressure X-ray photoelectron spectroscopy, and near-edge X-ray absorption spectroscopy. Although the material is stable under argon, H 2 triggers at 400 °C decomposition of CoB, leading to cobalt(0) nanoparticles. We then show that H 2 activates CoB for the catalysis of CO 2 methanation. A similar decomposition process is also observed on NiB nanocrystals under oxidizing conditions at 300 °C. Our work highlights the instability under reactive atmospheres of nanocrystalline cobalt and nickel borides obtained from molten salt synthesis. Therefore, we question the general stability of metal borides with distinct compositions under such conditions. These results shed light on the actual species in metal boride catalysis and provide the framework for future applications of metal borides in their stability domains.

Osmium Isotopic Composition of the Sumbar Cretaceous- Tertiary Boundary, Turkmenia

NASA Astrophysics Data System (ADS)

Meisel, T.; Krahenbuhl, U.; Nazarov, M. A.

1992-07-01

Turekian (1982) propagated the use of the osmium isotopic composition as a cosmic indicator for the origin of the high osmium (and iridium) layers at the K/T boundaries. He did not consider the osmium isotopic signature of the terrestrial mantle, which also has a chondritic evolution of the Re-Os system. Osmium cannot serve alone as an infallible indicator of the impact theory, but interesting results can be obtained from their investigation. Different K/T boundary section have been analyzed so far for ^187Os/^186Os. An overview of the values is presented in the table. Boundary Clay layer Os ratio Reference Stevns Klint fish clay 1.66 Luck and Turekian, 1983 Woodside Creek 1.12 Lichte et al., 1986 Raton Basin 1.23 Kraehenbuehl et al., 1988 Raton Basin (several) 1.15-1.23 Esser and Turekian, 1989 Sumbar (0-1 cm) 1.16 This work We obtained a complete marine section of the K/T boundary in southern Turkmenia (decribed by Alekseyev, 1988). It shows a very high Ir concentration (66 ppb) at the boundary layer and a remarkable Ir enrichment over crustal rocks continuing up to 30 cm above the boundary. Our aim of this investigation is to analyze several samples from above and below the boundary for the ^187Os/^186Os ratio to obtain a complete picture of the isotopic evolution of the section. We want to evaluate mixing of Os with chondritic ratios with Os from upper crustal rocks. Another goal is to investigate a mobilization of Os. So far only one sample has been analyzed with NTI-MS after fire assay digestion of the sample. The sample 0 to 1 cm has an ^187Os/^186Os ratio of 1.162 +- 13, which is quite low. We expect an even lower value for the boundary clay (0 cm) itself not taking into account a contribution of radiogenic osmium from the decay of terrestrial rhenium. This might put this K/T boundary section closest of all to the present day chondritic value (approx. 1.05). Further analysis will be presented at the meeting. References Alekseyev A. S., Nazarov M. A

Seasonal shift of diet in bank voles explains trophic fate of anthropogenic osmium?

PubMed

Ecke, Frauke; Berglund, Åsa M M; Rodushkin, Ilia; Engström, Emma; Pallavicini, Nicola; Sörlin, Dieke; Nyholm, Erik; Hörnfeldt, Birger

2018-05-15

Diet shifts are common in mammals and birds, but little is known about how such shifts along the food web affect contaminant exposure. Voles are staple food for many mammalian and avian predators. There is therefore a risk of transfer of contaminants accumulated in voles within the food chain. Osmium is one of the rarest earth elements with osmium tetroxide (OsO 4 ) as the most toxic vapor-phase airborne contaminant. Anthropogenic OsO 4 accumulates in fruticose lichens that are important winter food of bank voles (Myodes glareolus). Here, we test if a) anthropogenic osmium accumulates in bank voles in winter, and b) accumulation rates and concentrations are lower in autumn when the species is mainly herbivorous. Our study, performed in a boreal forest impacted by anthropogenic osmium, supported the hypotheses for all studied tissues (kidney, liver, lung, muscle and spleen) in 50 studied bank voles. In autumn, osmium concentrations in bank voles were even partly similar to those in the graminivorous field vole (Microtus agrestis; n=14). In autumn but not in late winter/early spring, osmium concentrations were generally negatively correlated with body weight and root length of the first mandible molar, i.e. proxies of bank vole age. Identified negative correlations between organ-to-body weight ratios and osmium concentrations in late winter/early spring indicate intoxication. Our results suggest unequal accumulation risk for predators feeding on different cohorts of bank voles. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

The Nature of the Microstructure and Interface Boundary Formation in Directionally Solidified Ceramic Boride Composites

DTIC Science & Technology

2015-02-19

boride composites *Volodymyr Borysovych Filipov SCIENCE AND TECHNOLOGY CENTER IN UKRAINE METALISTIV 7A, KYIV, UKRAINE *FRANTSEVICH...microstructure and interface boundary formation in directionally solidified ceramic boride composites 5a. CONTRACT NUMBER STCU P-512 5b. GRANT NUMBER...BOUNDARY FORMATION IN DIRECTIONALLY SOLIDIFIED CERAMIC BORIDE COMPOSITES Project manager: Filipov Volodymyr Borysovych Phone: (+380.44) 424-13-67

Metal-boride phase formation on tungsten carbide (WC-Co) during microwave plasma chemical vapor deposition

NASA Astrophysics Data System (ADS)

Johnston, Jamin M.; Catledge, Shane A.

2016-02-01

Strengthening of cemented tungsten carbide by boriding is used to improve the wear resistance and lifetime of carbide tools; however, many conventional boriding techniques render the bulk carbide too brittle for extreme conditions, such as hard rock drilling. This research explored the variation in metal-boride phase formation during the microwave plasma enhanced chemical vapor deposition process at surface temperatures from 700 to 1100 °C. We showed several well-adhered metal-boride surface layers consisting of WCoB, CoB and/or W2CoB2 with average hardness from 23 to 27 GPa and average elastic modulus of 600-730 GPa. The metal-boride interlayer was shown to be an effective diffusion barrier against elemental cobalt; migration of elemental cobalt to the surface of the interlayer was significantly reduced. A combination of glancing angle X-ray diffraction, electron dispersive spectroscopy, nanoindentation and scratch testing was used to evaluate the surface composition and material properties. An evaluation of the material properties shows that plasma enhanced chemical vapor deposited borides formed at substrate temperatures of 800 °C, 850 °C, 900 °C and 1000 °C strengthen the material by increasing the hardness and elastic modulus of cemented tungsten carbide. Additionally, these boride surface layers may offer potential for adhesion of ultra-hard carbon coatings.

Osmium (VI) complexes of the 3', 5'-dinucleoside monophosphates, ApU and UpA.

PubMed

Daniel, F B; Behrman, E J

1976-02-10

The dinucleoside monophosphates, ApU and UpA, react with potassium osmate (VI) and 2,2'-bipyridyl to form the corresponding oxo-osmium (VI) bipyridyl sugar ester in which the osmate group is bonded to the terminal 2',3'-glycol. Osmium (VIII) tetroxide and 2,2'-bipyridyl react with the dinucleosides to form the corresponding oxo-osmium (VI) bipyridyl heterocyclic esters which result from addition of the tetroxide to the 5,6-double bond of the uracil residue. Although capable of transesterification reactions, these heterocyclic esters are exceptionally stable toward exchange reactions in solution. No apparent exchange was observed after 1 month. This reaction thus seems promising for single-site osmium labeling in polynucleotides.

Kinetics and Tribological Characterization of Pack-Borided AISI 1025 Steel

NASA Astrophysics Data System (ADS)

Gómez-Vargas, O. A.; Keddam, M.; Ortiz-Domínguez, M.

2017-03-01

In this present study, the AISI 1025 steel was pack-borided in the temperature range of 1,123-1,273 K for different treatment times ranging from 2 to 8 h. A diffusion model was suggested to estimate the boron diffusion coefficients in the Fe2B layers. As a result, the boron activation energy for the AISI 1025 steel was estimated as 174.36 kJ/mol. This value of energy was compared with the literature data. To extend the validity of the present model, other additional boriding conditions were considered. The boride layers formed on the AISI 1025 steel were characterized by the following experimental techniques: scanning electron microscopy, X-ray diffraction analysis and the Daimler-Benz Rockwell-C indentation technique. Finally, the scratch and pin-on-disc tests for wear resistance were achieved using an LG Motion Ltd and a CSM tribometer, respectively, under dry sliding conditions.

Plasma boriding of a cobalt-chromium alloy as an interlayer for nanostructured diamond growth

NASA Astrophysics Data System (ADS)

Johnston, Jamin M.; Jubinsky, Matthew; Catledge, Shane A.

2015-02-01

Chemical vapor deposited (CVD) diamond coatings can potentially improve the wear resistance of cobalt-chromium medical implant surfaces, but the high cobalt content in these alloys acts as a catalyst to form graphitic carbon. Boriding by high temperature liquid baths and powder packing has been shown to improve CVD diamond compatibility with cobalt alloys. We use the microwave plasma-enhanced (PE) CVD process to deposit interlayers composed primarily of the borides of cobalt and chromium. The use of diborane (B2H6) in the plasma feedgas allows for the formation of a robust boride interlayer for suppressing graphitic carbon during subsequent CVD of nano-structured diamond (NSD). This metal-boride interlayer is shown to be an effective diffusion barrier against elemental cobalt for improving nucleation and adhesion of NSD coatings on a CoCrMo alloy. Migration of elemental cobalt to the surface of the interlayer is significantly reduced and undetectable on the surface of the subsequently-grown NSD coating. The effects of PECVD boriding are compared for a range of substrate temperatures and deposition times and are evaluated using glancing-angle X-ray diffraction (XRD), cross-sectional scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and micro-Raman spectroscopy. Boriding of CoCrMo results in adhered nanostructured diamond coatings with low surface roughness.

Bioimaging of isosteric osmium and ruthenium anticancer agents by LA-ICP-MS.

PubMed

Klose, Matthias H M; Theiner, Sarah; Kornauth, Christoph; Meier-Menches, Samuel M; Heffeter, Petra; Berger, Walter; Koellensperger, Gunda; Keppler, Bernhard K

2018-03-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to study the spatial distribution of two metallodrugs with anticancer activities in vivo, namely the organoruthenium plecstatin-1 (1) and its isosteric osmium analogue (2), in liver, kidneys, muscles and tumours of treated mice bearing a CT-26 tumour after single-dose i.p. administration. To the best of our knowledge, this is the first time that the spatial distribution of an osmium drug candidate has been investigated using LA-ICP-MS in tissues. Independent measurements of the average ruthenium and osmium concentration via microwave digestion and ICP-MS in organs and tumours were in good agreement with the LA-ICP-MS results. Matrix-matched standards (MMS) ranging from 1 to 30 μg g -1 were prepared to quantify the spatial distributions of the metals and the average metal content of the MMS samples was additionally quantified by ICP-MS after microwave digestion. The recoveries for osmium and ruthenium in the MMS were 105% and 101% on average, respectively, validating the sample preparation procedure of the MMS. Preparation of MMS was carried out under an argon atmosphere to prevent oxidation of osmium-species to the volatile OsO 4 . The highest metal concentrations were found in the liver, followed by kidney, lung and tumour tissues, while muscles displayed only very low quantities of the respective metal. Both metallodrugs accumulated in the cortex of the kidneys more strongly compared to the medulla. Interestingly, osmium from 2 was largely located at the periphery and tissue edges, whereas ruthenium from 1 was observed to penetrate deeper into the organs and tumours.

Magnetization Analysis of Magnesium Boride Wires

NASA Astrophysics Data System (ADS)

Cave, J. R.; Zhu, W.

2006-03-01

Cycled applied field magnetization curves contain a wealth of information on critical current density and flux pinning that is not commonly exploited. Detailed magnetization data for magnesium boride wire cores have been analyzed for critical state model consistency. The iron-sheathed silicon nitride doped magnesium boride wires were prepared from pure magnesium and boron powders with nano-scale silicon nitride additions (MgB2-x(Si3N4)x/7 with x = 0 - 0.4). A subsequent short annealing heat treatment, 800 degrees C and of 1 hour duration in Argon, was applied to create the desired phase. Magnetization critical current densities were up to ˜340 kA/cm2 at 5K and 1T. Major and minor loop analysis will be described, for field sweeps up to 3 tesla at fixed temperatures and for temperature sweeps from 5K to 45K in fixed fields, with respect to parameters describing the critical state model.

Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination

PubMed Central

Chen, Cynthia; Sedwick, Peter N.; Sharma, Mukul

2009-01-01

Osmium is one of the rarer elements in seawater, with typical concentration of ≈10 × 10−15 g g−1 (5.3 × 10−14 mol kg−1). The osmium isotope composition (187Os/188Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (≈1.3) and mantle/cosmic dust (≈0.13). Here, we show that the 187Os/188Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (≈0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower 187Os/188Os ratio (≈0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts. PMID:19416862

Anthropogenic osmium in rain and snow reveals global-scale atmospheric contamination.

PubMed

Chen, Cynthia; Sedwick, Peter N; Sharma, Mukul

2009-05-12

Osmium is one of the rarer elements in seawater, with typical concentration of approximately 10 x 10(-15) g g(-1) (5.3 x 10(-14) mol kg(-1)). The osmium isotope composition ((187)Os/(188)Os ratio) of deep oceans is 1.05, reflecting a balance between inputs from continental crust (approximately 1.3) and mantle/cosmic dust (approximately 0.13). Here, we show that the (187)Os/(188)Os ratios measured in rain and snow collected around the world range from 0.16 to 0.48, much lower than expected (>1), but similar to the isotope composition of ores (approximately 0.2) that are processed to extract platinum and other metals to be used primarily in automobile catalytic converters. Present-day surface seawater has a lower (187)Os/(188)Os ratio (approximately 0.95) than deep waters, suggesting that human activities have altered the isotope composition of the world's oceans and impacted the global geochemical cycle of osmium. The contamination of the surface ocean is particularly remarkable given that osmium has few industrial uses. The pollution may increase with growing demand for platinum-based catalysts.

Rhenium-osmium-isotope constraints on the age of iron meteorites

NASA Technical Reports Server (NTRS)

Horan, M. F.; Morgan, J. W.; Walker, R. J.; Grossman, J. N.

1992-01-01

Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately +/-31 million years for meteorites about 4500 million years old. Although an absolute rhenium-osmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of Re-187, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

Rhenium-osmium isotope constraints on the age of iron meteorites

USGS Publications Warehouse

Horan, M.F.; Morgan, J.W.; Walker, R.J.; Grossman, J.N.

1992-01-01

Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately ??31 million years for meteorites ???4500 million years old. Although an absolute rhenium-osmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of 187Re, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

Isotopic determinations of rhenium and osmium in meteorites by using fusion, distillation and ion-exchange separations

USGS Publications Warehouse

Morgan, J.W.; Walker, R.J.

1989-01-01

A stable isotope-dilution method using resonance ionization mass spectrometry is suitable for the determination of rhenium and osmium abundances and osmium isotopic composition in carbonaceous chondrites and iron meteorites. The chemical procedure involves sodium peroxide fusion, followed by distillation of osmium from sulfuric acid/hydrogen peroxide and subsequent anion-exchange separation of rhenium from the same solution. ?? 1989.

Clustering of transmutation elements tantalum, rhenium and osmium in tungsten in a fusion environment

NASA Astrophysics Data System (ADS)

You, Yu-Wei; Kong, Xiang-Shan; Wu, Xuebang; Liu, C. S.; Fang, Q. F.; Chen, J. L.; Luo, G.-N.

2017-08-01

The formation of transmutation solute-rich precipitates has been reported to seriously degrade the mechanical properties of tungsten in a fusion environment. However, the underlying mechanisms controlling the formation of the precipitates are still unknown. In this study, first-principles calculations are therefore performed to systemically determine the stable structures and binding energies of solute clusters in tungsten consisting of tantalum, rhenium and osmium atoms as well as irradiation-induced vacancies. These clusters are known to act as precursors for the formation of precipitates. We find that osmium can easily segregate to form clusters even in defect-free tungsten alloys, whereas extremely high tantalum and rhenium concentrations are required for the formation of clusters. Vacancies greatly facilitate the clustering of rhenium and osmium, while tantalum is an exception. The binding energies of vacancy-osmium clusters are found to be much higher than those of vacancy-tantalum and vacancy-rhenium clusters. Osmium is observed to strongly promote the formation of vacancy-rhenium clusters, while tantalum can suppress the formation of vacancy-rhenium and vacancy-osmium clusters. The local strain and electronic structure are analyzed to reveal the underlying mechanisms governing the cluster formation. Employing the law of mass action, we predict the evolution of the relative concentration of vacancy-rhenium clusters. This work presents a microscopic picture describing the nucleation and growth of solute clusters in tungsten alloys in a fusion reactor environment, and thereby explains recent experimental phenomena.

Himalayan uplift and osmium isotopes in oceans and rivers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, M.; Wasserburg, G.J.; Hofmann, A.W.

1999-12-01

Previous studies have shown that {sup 187}Os/{sup 188}Os in seawater has become increasingly radiogenic over the last 409 Ma in a manner analogous to strontium. This rapid rise in the marine {sup 187}Os/{sup 188}Os over the last 17 Ma has been attributed to an increase in the bulk silicate weathering rates resulting from the rise of the Himalayas and/or selective weathering and erosion of highly radiogenic organic rich ancient sediments. The key test of this hypothesis is the {sup 187}Os/{sup 188}Os and the total osmium concentration of the Himalayan rivers. The authors report the concentration and isotopic composition of osmiummore » in the Ganges, the Brahmaputra, and the Indus rivers. The {sup 187}Os/{sup 188}Os of the Ganges close to its source (at Kaudiyal) is 2.65 and [Os] = 45 fM/kg. A second sample of the lower reaches of the Ganges at Patna gives {sup 187}Os/{sup 188}Os = 1.59 and [Os] = 171 fM/kg. The {sup 187}Os/{sup 188}Os of the Brahmaputra at Guwahati is 1.07 and [Os] = 52 fM/kg. A sample of the Indus (Besham) has a {sup 187}Os/{sup 188}Os of 1.2 and [Os] = 59 fM/kg. The authors infer that the Himalayas do not provide either a high flow of osmium of a highly radiogenic osmium component to the oceans. The overall trend for osmium and strontium could be explained by a regularly increasing input of global continental weathering sources but the Himalayas themselves appear not to be the dominant source.« less

The Growth Behavior of Titanium Boride Layers in α and β Phase Fields of Titanium

NASA Astrophysics Data System (ADS)

Lv, Xiaojun; Hu, Lingyun; Shuang, Yajing; Liu, Jianhua; Lai, Yanqing; Jiang, Liangxing; Li, Jie

2016-07-01

In this study, the commercially pure titanium was successfully electrochemical borided in a borax-based electrolyte. The process was carried out at a constant cathodic current density of 300 mA cm-2 and at temperatures of 1123 K and 1223 K (850 °C and 950 °C) for 0.5, 1, 2, 3, and 5 hours. The growth behavior of titanium boride layers in the α phase field of titanium was compared with that in the β phase field. After boriding, the presence of both the TiB2 top layer and TiB whisker sub-layer was confirmed by the X-ray diffraction (XRD) and scanning electron microscope. The relationship between the thickness of boride layers and boriding time was found to have a parabolic character in both α and β phase fields of titanium. The TiB whiskers showed ultra-fast growth rate in the β phase field. Its growth rate constant was found to be as high as 3.2002 × 10-13 m2 s-1. Besides, the chemical resistance of the TiB2 layer on the surface of titanium substrate was characterized by immersion tests in molten aluminum.

Osmium isotope constraints on Earth's late accretionary history

USGS Publications Warehouse

Morgan, J.W.

1985-01-01

Osmium isotope measurements reported by Alle??gre and Luck 1,2 indicate that terrestrial osmiridiums evolved in a mantle source region in which the osmium/rhenium ratio falls strictly within the range found in chondrites. This suggests that the highly siderophile elements in the Earth's mantle were introduced by a late influx of chondritic material and are not a result of endogenous processes. I have now examined the available data in more detail and conclude that the inferred Os/Re ratio of the Earth's mantle matches the E group and C3 chondrites, but that C1 and probably C2 chondrites were not major components of the material accreted in the late stages of mantle formation. ?? 1985 Nature Publishing Group.

Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides.

PubMed

Wang, Zixing; Kochat, Vidya; Pandey, Prafull; Kashyap, Sanjay; Chattopadhyay, Soham; Samanta, Atanu; Sarkar, Suman; Manimunda, Praveena; Zhang, Xiang; Asif, Syed; Singh, Abhisek K; Chattopadhyay, Kamanio; Tiwary, Chandra Sekhar; Ajayan, Pulickel M

2017-08-01

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal-carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum-copper bilayer with corresponding precursor (C 2 H 2 , B powder, and NH 3 ). The ultrathin crystals are found on the copper surface (opposite of the metal-metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal-metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Osmium-191/iridium-191m radionuclide

DOEpatents

Knapp, Jr., Furn F.; Butler, Thomas A.; Brihaye, Claude

1987-01-01

A generator system to provide iridium-191m for clinical imaging applications comprises an activated carbon adsorbent loaded with a compound containing the parent nuclide, osmium-191. The generator, which has a shelf-life in excess of two weeks and does not require a scavenger column, can be eluted with physiologically compatible saline.

Osmium Tag for Posttranscriptionally Modified RNA.

PubMed

Debnath, Turja Kanti; Okamoto, Akimitsu

2018-05-25

Nucleotide modifications of cellular RNA are highly abundant and diverse, but their origin and functions have not yet been investigated. 5-Methylcytidine (m5C) and 5-methyluridine (m5U) are highly abundant posttranscriptionally modified nucleotides observed in various natural RNAs. Such nucleotides have been labeled through a chemical approach as both undergo oxidation at the C5-C6 double bond, leading to the formation of osmium-bipyridine complexes, which are identified by mass spectrometry. This osmium tag made it possible to distinguished m5C and m5U from their isomers 2'-O-methylcytidine and 2'-O-methyluridine, respectively. Queuosine and 2-methylthio-N6-isopentenyladenosine in tRNA were also tagged through this complex formation--this is the first time that this has ever been achieved. Osmylation has emerged as a structure-selective reaction and largely governed by the environment of the target site (the steric and higher order structure), therefore it could be helpful for studying the structure and dynamics of RNA-protein interactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Osmium-191/iridium-191m radionuclide

DOEpatents

Knapp, F.F. Jr.; Butler, T.A.; Brihaye, C.

1985-08-26

A generator system to provide iridium-191m for clinical imaging applications comprises an activated carbon adsorbent loaded with a compound containing the parent nuclide, osmium-191. The generator, which has a shelf-life in excess of two weeks and does not require a scavenger column, can be eluted with physiologically compatible saline. 4 figs. 3 tabs.

Nano-Disperse Borides and Carbides: Plasma Technology Production, Specific Properties, Economic Evaluation

NASA Astrophysics Data System (ADS)

Galevskii, G. V.; Rudneva, V. V.; Galevskii, S. G.; Tomas, K. I.; Zubkov, M. S.

2016-04-01

The experience of production and study on properties of nano-disperse chromium and titanium borides and carbides, and silicon carbide has been generalized. The structure and special service aspects of utilized plasma-metallurgical complex equipped with a three-jet direct-flow reactor with a capacity of 150 kW have been outlined. Processing, heat engineering and service life characteristics of the reactor are specified. The synthesis parameters of borides and carbides, as well as their basic characteristics in nano-disperse condition and their production flow diagram are outlined. Engineering and economic performance of synthesizing borides in laboratory and industrial conditions is assessed, and the respective segment of the international market as well. The work is performed at State Siberian Industrial University as a project part of the State Order of Ministry of Science and Education of the Russian Federation No. 11.1531/2014/K.

The effect of boriding on wear resistance of cold work tool steel

NASA Astrophysics Data System (ADS)

Anzawa, Y.; Koyama, S.; Shohji, I.

2017-05-01

Recently, boriding has attracted extensive attention as surface stiffening processing of plain steel. In this research, the influence of processing time on the formation layer of cold work tool steel (KD11MAX) by Al added fused salt bath was examined. In addition, in order to improve the abrasion resistance of KD11MAX, the effect of the treatment of boronization on the formation layer has been investigated. Boriding were performed in molten borax which contained about 10 mass% Al at processing time of 1.8 ~ 7.2 ks (processing temperature of 1303 K). As a result of the examination, the hardness of the boriding layer becomes about 1900 HV when the processing time of 3.6 ks. Also the abrasion resistance has improved remarkably. Furthermore, it was revealed that the formation layer was boronized iron from the Vickers hardness and analysis of the X-ray diffraction measurement.

New method for the measurement of osmium isotopes applied to a New Zealand Cretaceous/Tertiary boundary shale

USGS Publications Warehouse

Lichte, F.E.; Wilson, S.M.; Brooks, R.R.; Reeves, R.D.; Holzbecher, J.; Ryan, D.E.

1986-01-01

The determination of osmium content and isotopic abundances in geological materials has received increasing attention in recent years following the proposal of Alvarez et al.1 that mass extinctions at the end of the Cretaceous period were caused by the impact of a large (???10km) meteorite which left anomalously high iridium levels as a geochemical signature in the boundary shales. Here we report a new and simple method for measuring osmium in geological materials, involving fusion of the sample with sodium peroxide, distillation of the osmium as the tetroxide using perchloric acid, extraction into chloroform, and absorption of the chloroform extract onto graphite powder before instrumental neutron activation analysis. In a variant of this technique, the chloroform extract is back-extracted into an aqueous phase and the osmium isotopes are determined by plasma-source mass spectrometry (ICPMS). We have used this method on the Woodside Creek (New Zealand) Cretaceous/Tertiary boundary clay and have obtained the first osmium content (6g ng g-1) for this material. The 187Os/186Os ratio is 1.12??0.16, showing a typical non-crustal signature. This combined distillation-extraction- ICPMS method will prove to be useful for measuring osmium isotopes in other geological materials. ?? 1986 Nature Publishing Group.

Method of making an icosahedral boride structure

DOEpatents

Hersee, Stephen D.; Wang, Ronghua; Zubia, David; Aselage, Terrance L.; Emin, David

2005-01-11

A method for fabricating thin films of an icosahedral boride on a silicon carbide (SiC) substrate is provided. Preferably the icosahedral boride layer is comprised of either boron phosphide (B.sub.12 P.sub.2) or boron arsenide (B.sub.12 As.sub.2). The provided method achieves improved film crystallinity and lowered impurity concentrations. In one aspect, an epitaxially grown layer of B.sub.12 P.sub.2 with a base layer or substrate of SiC is provided. In another aspect, an epitaxially grown layer of B.sub.12 As.sub.2 with a base layer or substrate of SiC is provided. In yet another aspect, thin films of B.sub.12 P.sub.2 or B.sub.12 As.sub.2 are formed on SiC using CVD or other vapor deposition means. If CVD techniques are employed, preferably the deposition temperature is above 1050.degree. C., more preferably in the range of 1100.degree. C. to 1400.degree. C., and still more preferably approximately 1150.degree. C.

Niobium boride layers deposition on the surface AISI D2 steel by a duplex treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kon, O., E-mail: okon42@htotmail.com; Pazarlioglu, S.; Sen, S.

2015-03-30

In this paper, we investigated the possibility of deposition of niobium boride layers on the surface of AISI D2 steel by a duplex treatment. At the first step of duplex treatment, boronizing was performed on AISI D2 steel samples at 1000{sup o}C for 2h and then pre-boronized samples niobized at 850°C, 900°C and 950°C using thermo-reactive deposition method for 1–4 h. The presence of the niobium boride layers such as NbB, NbB{sub 2} and Nb{sub 3}B{sub 4} and also iron boride phases such as FeB, Fe{sub 2}B were examined by X-ray diffraction analysis. Scanning electron microscope (SEM) and micro-hardness measurementsmore » were realized. Experimental studies showed that the depth of the coating layers increased with increasing temperature and times and also ranged from 0.42 µm to 2.43 µm, depending on treatment time and temperature. The hardness of the niobium boride layer was 2620±180 HV{sub 0.005}.« less

η2-SO2 Linkage Photoisomer of an Osmium Coordination Complex.

PubMed

Cole, Jacqueline M; Velazquez-Garcia, Jose de J; Gosztola, David J; Wang, SuYin Grass; Chen, Yu-Sheng

2018-03-05

We report the discovery of an η 2 -SO 2 linkage photoisomer in the osmium pentaammine coordination complex, [Os(NH 3 ) 5 (SO 2 )][Os(NH 3 ) 5 (HSO 3 )]Cl 4 (1). Its dark- and light-induced crystal structures are determined via synchrotron X-ray crystallography, at 100 K, where the photoinduced state is metastable in a single crystal that has been stimulated by 505 nm light for 2.5 h. The SO 2 photoisomer in the [Os(NH 3 ) 5 (SO 2 )] 2+ cation contrasts starkly with the photoinactivity of the HSO 3 ligand in its companion [Os(NH 3 ) 5 (HSO 3 )] + cation within the crystallographic asymmetric unit of this single crystal. Panchromatic optical absorption characteristics of this single crystal are revealed in both dark- and light-induced states, using concerted absorption spectroscopy and optical microscopy. Its absorption halves across most of its visible spectrum, upon exposure to 505 nm light. The SO 2 ligand seems to be responsible for this photoinduced bleaching effect, judging from a comparison of the dark- and light-induced crystal structures of 1. The SO 2 photoisomerism is found to be thermally reversible, and so 1 presents a rare example of an osmium-based solid-state optical switch. Such switching in an osmium complex is significant because bottom-row transition metals stand to offer linkage photoisomerism with the greatest photoconversion levels and thermal stability. The demonstration of η 2 -SO 2 bonding in this complex also represents a fundamental contribution to osmium coordination chemistry.

Computational-Experimental Processing of Boride/Carbide Composites by Reactive Infusion of Hf Alloy Melts into B4C

DTIC Science & Technology

2015-09-16

AFRL-AFOSR-VA-TR-2015-0314 Computational -Experimental Processing of Boride /Carbide Composites by Reactive Infusion of Hf Alloy Melts into B4C...Computational -Experimental Processing of Boride /Carbide Composites by Reactive Infusion of Hf Alloy Melts into B4C 5a.  CONTRACT NUMBER 5b.  GRANT...with a packed bed of B4C to form boride - carbide precipitates. Although the ultimate goal of the research endeavor is to enhance significantly the

Growth kinetics of borided layers: Artificial neural network and least square approaches

NASA Astrophysics Data System (ADS)

Campos, I.; Islas, M.; Ramírez, G.; VillaVelázquez, C.; Mota, C.

2007-05-01

The present study evaluates the growth kinetics of the boride layer Fe 2B in AISI 1045 steel, by means of neural networks and the least square techniques. The Fe 2B phase was formed at the material surface using the paste boriding process. The surface boron potential was modified considering different boron paste thicknesses, with exposure times of 2, 4 and 6 h, and treatment temperatures of 1193, 1223 and 1273 K. The neural network and the least square models were set by the layer thickness of Fe 2B phase, and assuming that the growth of the boride layer follows a parabolic law. The reliability of the techniques used is compared with a set of experiments at a temperature of 1223 K with 5 h of treatment time and boron potentials of 2, 3, 4 and 5 mm. The results of the Fe 2B layer thicknesses show a mean error of 5.31% for the neural network and 3.42% for the least square method.

Selection of peptides binding to metallic borides by screening M13 phage display libraries.

PubMed

Ploss, Martin; Facey, Sandra J; Bruhn, Carina; Zemel, Limor; Hofmann, Kathrin; Stark, Robert W; Albert, Barbara; Hauer, Bernhard

2014-02-10

Metal borides are a class of inorganic solids that is much less known and investigated than for example metal oxides or intermetallics. At the same time it is a highly versatile and interesting class of compounds in terms of physical and chemical properties, like semiconductivity, ferromagnetism, or catalytic activity. This makes these substances attractive for the generation of new materials. Very little is known about the interaction between organic materials and borides. To generate nanostructured and composite materials which consist of metal borides and organic modifiers it is necessary to develop new synthetic strategies. Phage peptide display libraries are commonly used to select peptides that bind specifically to metals, metal oxides, and semiconductors. Further, these binding peptides can serve as templates to control the nucleation and growth of inorganic nanoparticles. Additionally, the combination of two different binding motifs into a single bifunctional phage could be useful for the generation of new composite materials. In this study, we have identified a unique set of sequences that bind to amorphous and crystalline nickel boride (Ni3B) nanoparticles, from a random peptide library using the phage display technique. Using this technique, strong binders were identified that are selective for nickel boride. Sequence analysis of the peptides revealed that the sequences exhibit similar, yet subtle different patterns of amino acid usage. Although a predominant binding motif was not observed, certain charged amino acids emerged as essential in specific binding to both substrates. The 7-mer peptide sequence LGFREKE, isolated on amorphous Ni3B emerged as the best binder for both substrates. Fluorescence microscopy and atomic force microscopy confirmed the specific binding affinity of LGFREKE expressing phage to amorphous and crystalline Ni3B nanoparticles. This study is, to our knowledge, the first to identify peptides that bind specifically to amorphous and

Friction and wear of radiofrequency-sputtered borides, silicides, and carbides

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Wheeler, D. R.

1978-01-01

The friction and wear properties of several refractory compound coatings were examined. These compounds were applied to 440 C bearing steel surfaces by radiofrequency (RF) sputtering. The refractory compounds were the titanium and molybdenum borides, the titanium and molybdenum silicides, and the titanium, molybdenum, and boron carbides. Friction testing was done with a pin-on-disk wear apparatus at loads from 0.1 to 5.0 newtons. Generally, the best wear properties were obtained when the coatings were bias sputtered onto 440 C disks that had been preoxidized. Adherence was improved because of the better bonding of the coatings to the iron oxide formed during preoxidation. As a class the carbides provided wear protection to the highest loads. Titanium boride coatings provided low friction and good wear properties to moderate loads.

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

NASA Astrophysics Data System (ADS)

Yamaura, Kazunari

2016-04-01

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO3, LiOsO3, and Na2OsO4, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal-insulator transition in NaOsO3, a ferroelectric-like transition in LiOsO3, and high-temperature ferrimagnetism driven by a local structural distortion in Ca2FeOsO6 may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices.

Low temperature InP /Si wafer bonding using boride treated surface

NASA Astrophysics Data System (ADS)

Huang, Hui; Ren, Xiaomin; Wang, Wenjuan; Song, Hailan; Wang, Qi; Cai, Shiwei; Huang, Yongqing

2007-04-01

An approach for InP /Si wafer bonding based on boride-solution treatment was presented. The bonding energy is higher than the InP fracture energy by annealing at 280°C. An In0.53Ga0.47As/InP multiple-quantum-well (MQW) structure grown on InP was transferred onto Si substrate via the bonding process. X-ray diffraction and photoluminescence reveal that crystal quality of the bonded MQW was preserved. A thin B2O3-POx-SiO2 oxide layer of about 28nm thick at the bonding interface was detected. X-ray photoelectron spectroscopy and Raman analyses indicate that the formation of oxygen bridging bonds by boride treatment is responsible for the strong fusion obtained at such low temperature.

Subminiature eddy current transducers for studying boride coatings

NASA Astrophysics Data System (ADS)

Dmitriev, S. F.; Ishkov, A. V.; Malikov, V. N.; Sagalakov, A. M.

2016-07-01

Strengthening of parts and units of machines, increased reliability and longer service life is an important task of modern mechanical engineering. The main objects of study in the work were selected steel 65G and 50HGA, wear-resistant boride coatings ternary system Fe-B-Fe n B which were investigated by scanning electron microscopy and eddy-current nondestructive methods.

Micro-Abrasion Wear Resistance of Borided 316L Stainless Steel and AISI 1018 Steel

NASA Astrophysics Data System (ADS)

Reséndiz-Calderon, C. D.; Rodríguez-Castro, G. A.; Meneses-Amador, A.; Campos-Silva, I. E.; Andraca-Adame, J.; Palomar-Pardavé, M. E.; Gallardo-Hernández, E. A.

2017-11-01

The 316L stainless steel has high corrosion resistance but low tribological performance. In different industrial sectors (biomedical, chemical, petrochemical, and nuclear engineering), improvement upon wear resistance of 316L stainless steel components using accessible and inexpensive methods is critical. The AISI 1018 steel is widely used in industry, but its tribological performance is not the best among steels. Therefore, in this study the behavior of the borided 316L stainless steel and 1018 steel is evaluated under micro-abrasion wear. The boriding was carried out at 1223 K over 6 h of exposure time, resulting in a biphase layer composed of FeB/Fe2B phases. In order to evaluate Fe2B phase with no influence from FeB phase, AISI 1018 steel samples were borided at 1273 K for over 20 min and then diffusion annealed at 1273 K over 2 h to obtain a Fe2B mono-phase layer. Micro-abrasion wear resistance was evaluated by a commercial micro-abrasion testing rig using a mix of F-1200 SiC particles with deionized water as abrasive slurry. The obtained wear rates for FeB and Fe2B phases and for the 316L stainless steel were compared. Wear resistance of 316L stainless steel increases after boriding. The wear mechanisms for both phases and for the stainless steel were identified. Also, transient conditions for rolling and grooving abrasion were determined for the FeB and Fe2B phases.

Synthesis and Characterization of Low-Cost Superhard Transition-Metal Borides

NASA Astrophysics Data System (ADS)

Kaner, Richard

2013-06-01

The increasing demand for high-performance cutting and forming tools, along with the shortcomings of traditional tool materials such as diamond (unable to cut ferrous materials), cubic boron nitride (expensive) and tungsten carbide (relatively-low hardness), has motivated the search for new superhard materials for these applications. This has led us to a new class of superhard materials, dense refractory transition-metal borides, which promise to address some of the existing problems of conventional superhard materials. For example, we have synthesized rhenium diboride (ReB2) using arc melting at ambient pressure. This superhard material has demonstrated an excellent electrical conductivity and superior mechanical properties, including a Vickers hardness of 48.0 GPa (under an applied load of 0.49 N). To further increase the hardness and lower the materials costs, we have begun exploring high boron content metal borides including tungsten tetraboride (WB4) . We have synthesized WB4 by arc melting and studied its hardness and high-pressure behavior. With a similar Vickers hardness (43.3 GPa under a load of 0.49 N) and bulk modulus (326-339 GPa) to ReB2, WB4 offers a lower cost alternative and has the potential to be used in cutting tools. To further enhance the hardness of this superhard metal, we have created the binary and ternary solid solutions of WB4 with Cr, Mn and Ta, the results of which show a hardness increase of up to 20 percent. As with other metals, these metallic borides can be readily cut and shaped using electric discharge machining (EDM).

The Effects of Borides on the Mechanical Properties of TLPB Repaired Inconel 738 Superalloy

NASA Astrophysics Data System (ADS)

Wei, J.; Ye, Y.; Sun, Z.; Zou, G.; Bai, H.; Wu, A.; Liu, L.

2017-10-01

The transient liquid phase diffusion bonding (TLPB) method was used to repair an artificial crack in Inconel 738, which was notched by a femtosecond laser. Mixed ratios of BNi-1a:DF-4B were investigated at the bonding temperature of 1373 K (1100 °C) for 2 to 36 hours. The effect of borides on the mechanical properties of TLPB repaired joints was studied through analysis of the microstructure, fracture path, and morphology observations. The borides formation, morphology, distribution, and joints strength were studied in detail. The results showed that the diffusion of B can either increase or decrease the joint strength, depending on its distribution and morphology. The amount of large blocky Ni-B compounds in the precipitate zone were reduced with increasing holding time, which resulted in an increase in joint strength. Nevertheless, further increasing the holding time led to a decrease in joint strength because of the formation of continuous acicular borides in the diffusion-affected zone. The fracture modes of TLPB joints were also discussed on the basis of the microstructure and fractography.

Interlayer utilization (including metal borides) for subsequent deposition of NSD films via microwave plasma CVD on 316 and 440C stainless steels

NASA Astrophysics Data System (ADS)

Ballinger, Jared

Diamond thin films have promising applications in numerous fields due to the extreme properties of diamonds in conjunction with the surface enhancement of thin films. Biomedical applications are numerous including temporary implants and various dental and surgical instruments. The unique combination of properties offered by nanostructured diamond films that make it such an attractive surface coating include extreme hardness, low obtainable surface roughness, excellent thermal conductivity, and chemical inertness. Regrettably, numerous problems exist when attempting to coat stainless steel with diamond generating a readily delaminated film: outward diffusion of iron to the surface, inward diffusion of carbon limiting necessary surface carbon precursor, and the mismatch between the coefficients of thermal expansion yielding substantial residual stress. While some exotic methods have been attempted to overcome these hindrances, the most common approach is the use of an intermediate layer between the stainless steel substrate and the diamond thin film. In this research, both 316 stainless steel disks and 440C stainless steel ball bearings were tested with interlayers including discrete coatings and graded, diffusion-based surface enhancements. Titanium nitride and thermochemical diffusion boride interlayers were both examined for their effectiveness at allowing for the growth of continuous and adherent diamond films. Titanium nitride interlayers were deposited by cathodic arc vacuum deposition on 440C bearings. Lower temperature diamond processing resulted in improved surface coverage after cooling, but ultimately, both continuity and adhesion of the nanostructured diamond films were unacceptable. The ability to grow quality diamond films on TiN interlayers is in agreement with previous work on iron and low alloy steel substrates, and the similarly seen inadequate adhesion strength is partially a consequence of the lacking establishment of an interfacial carbide phase

Effect of borides on hot deformation behavior and microstructure evolution of powder metallurgy high borated stainless steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Xuan

To investigate borides effect on the hot deformation behavior and microstructure evolution of powder metallurgy high borated stainless steel, hot compression tests at the temperatures of 950– 1150 °C and the strain rates of 0.01– 10 s{sup −1} were performed. Flow stress curves indicated that borides increased the material's stress level at low temperature but the strength was sacrificed at temperatures above 1100 °C. A hyperbolic-sine equation was used to characterize the dependence of the flow stress on the deformation temperature and strain rate. The hot deformation activation energy and stress exponent were determined to be 355 kJ/mol and 3.2,more » respectively. The main factors leading to activation energy and stress exponent of studied steel lower than those of commercial 304 stainless steel were discussed. Processing maps at the strains of 0.1, 0.3, 0.5, and 0.7 showed that flow instability mainly concentrated at 950– 1150 °C and strain rate higher than 0.6 s{sup −1}. Results of microstructure illustrated that dynamic recrystallization was fully completed at both high temperature-low strain rate and low temperature-high strain rate. In the instability region cracks were generated in addition to cavities. Interestingly, borides maintained a preferential orientation resulting from particle rotation during compression. - Highlights: •The decrement of activation energy was affected by boride and boron solution. •The decrease of stress exponent was influenced by composition and Cottrell atmosphere. •Boride represented a preferential orientation caused by particle rotation.« less

First-principles study of low compressibility osmium borides

NASA Astrophysics Data System (ADS)

Gou, Huiyang; Hou, Li; Zhang, Jingwu; Li, Hui; Sun, Guifang; Gao, Faming

2006-05-01

Using first-principles total energy calculations we investigate the structural, elastic, and electronic properties of OsB2 and OsB, respectively. The calculated equilibrium structural parameters of OsB2 are in agreement with the available experimental results. The calculations indicate that OsB in tungsten carbide is more energetically stable under the ambient condition than the metastable cesium chloride phase of OsB. Results of bulk modulus show that they are potential low compressible materials. The hardness of OsB2 is estimated by employing a semiempirical theory. The results indicate that OsB2 is an ultraincompressible material, but not a superhard material. The method designing superhard materials is different from one creating ultraincompressible materials.

Rhenium-osmium concentration and isotope systematics in group IIAB iron meteorites

USGS Publications Warehouse

Morgan, J.W.; Horan, M.F.; Walker, R.J.; Grossman, J.N.

1995-01-01

Rhenium and osmium abundances, and osmium isotopic compositions were measured by negative thermal ionization mass spectrometry in thirty samples, including replicates, of five IIA and eight IIB iron meteorites. Log plots of Os vs. Re abundances for IIA and IIB irons describe straight lines that approximately converge on Lombard, which has the lowest Re and Os abundances and highest 187Re/188Os measured in a IIA iron to date. The linear IIA trend may be exactly reproduced by fractional crystallization, but is not well fitted using variable partition coefficients. The IIB iron trend, however, cannot be entirely explained by simple fractional crystallization. One explanation is that small amounts of Re and Os were added to the asteroid core during the final stages of crystallization. Another possibility is that diffusional enrichment of Os may have occurred in samples most depleted in Re and Os. -from Authors

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

2013-09-03

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

2014-10-28

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Deposition and characterization of aluminum magnesium boride thin film coatings

NASA Astrophysics Data System (ADS)

Tian, Yun

Boron-rich borides are a special group of materials possessing complex structures typically comprised of B12 icosahedra. All of the boron-rich borides sharing this common structural unit exhibit a variety of exceptional physical and electrical properties. In this work, a new ternary boride compound AlMgB14, which has been extensively studied in bulk form due to its novel mechanical properties, was fabricated into thin film coatings by pulsed laser deposition (PLD) technology. The effect of processing conditions (laser operating modes, vacuum level, substrate temperature, and postannealing, etc.) on the composition, microstructure evolution, chemical bonding, and surface morphology of AlMgB14 thin film coatings has been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectrometry; the mechanical, electrical, and optical properties of AlMgB14 thin films have been characterized by nanoindentation, four-point probe, van der Pauw Hall measurement, activation energy measurement, and UV-VIS-NIR spectrophotometer. Experimental results show that AlMgB14 films deposited in the temperature range of 300 K - 873 K are amorphous. Depositions under a low vacuum level (5 x 10-5 Torr) can introduce a significant amount of C and O impurities into AlMgB14 films and lead to a complex oxide glass structure. Orthorhombic AlMgB14 phase cannot be obtained by subsequent high temperature annealing. By contrast, the orthorhombic AlMgB 14 crystal structure can be attained via high temperature-annealing of AlMgB14 films deposited under a high vacuum level (< 3 x 10-6 Torr), accompanied by strong texture formation. Low vacuum level-as deposited AlMgB14 films have low hardness (10 GPa), but high vacuum level-as deposited AlMgB14 films exhibit an extremely high hardness (45 GPa - 51 GPa), and the higher deposition temperature results in still higher hardness

Rhenium-osmium evidence for regional mineralization in southwestern north america.

PubMed

McCandless, T E; Ruiz, J

1993-09-03

More than 40 base metal porphyry ore deposits in southwestern North America are associated with the Laramide orogeny (about 90 million to 50 million years ago). Rhenium-osmium dates on molybdenite, a rhenium-enriched sulfide common in many of the deposits, reveal that in individual deposits mineralization occurs near the final stages of magmatic activity irrespective of the time of inception, magnitude, or duration of magmatism. Deposits that differ widely in location and in the extent and timing of magmatism have nearly identical ages for mineralization. Rhenium-osmium-ages suggest that mineralization occurred during two distinct intervals from about 74 million to 70 million years ago and from 60 million to 55 million years ago. Most deposits that formed in the oldest interval are within the older Precambrian basement of northwestern Arizona, whereas the younger deposits are restricted to the younger Precambrian basement in southern Arizona and northern Mexico. Synchronous, widespread mineralization indicates that similar crust-mantle interaction occurred on a regional scale for ore deposits once thought to be the product of localized processes.

New phases of osmium carbide from evolutionary algorithm and ab initio computations

NASA Astrophysics Data System (ADS)

Fadda, Alessandro; Fadda, Giuseppe

2017-09-01

New crystal phases of osmium carbide are presented in this work. These results were found with the CA code, an evolutionary algorithm (EA) presented in a previous paper which takes full advantage of crystal symmetry by using an ad hoc search space and genetic operators. The new OsC2 and Os2C structures have a lower enthalpy than any known so far. Moreover, the layered pattern of OsC2 serves as a blueprint for building new crystals by adding or removing layers of carbon and/or osmium and generating many other Os  +  C structures like Os2C, OsC, OsC2 and OsC4. These again have a lower enthalpy than all the investigated structures, including those of the present work. The mechanical, vibrational and electronic properties are discussed as well.

Ancient mantle in a modern arc: osmium isotopes in izu-bonin-mariana forearc peridotites

PubMed

Parkinson; Hawkesworth; Cohen

1998-09-25

Mantle peridotites drilled from the Izu-Bonin-Mariana forearc have unradiogenic 187Os/188Os ratios (0.1193 to 0.1273), which give Proterozoic model ages of 820 to 1230 million years ago. If these peridotites are residues from magmatism during the initiation of subduction 40 to 48 million years ago, then the mantle that melted was much more depleted in incompatible elements than the source of mid-ocean ridge basalts (MORB). This result indicates that osmium isotopes record information about ancient melting events in the convecting upper mantle not recorded by incompatible lithophile isotope tracers. Subduction zones may be a graveyard for ancient depleted mantle material, and portions of the convecting upper mantle may be less radiogenic in osmium isotopes than previously recognized.

Suppression of Boride Formation in Transient Liquid Phase Bonding of Pairings of Parent Superalloy Materials with Different Compositions and Grain Structures and Resulting Mechanical Properties

NASA Astrophysics Data System (ADS)

Steuer, Susanne; Singer, Robert F.

2014-07-01

Two Ni-based superalloys, columnar grained Alloy 247 and single-crystal PWA1483, are joined by transient liquid phase bonding using an amorphous brazing foil containing boron as a melting point depressant. At lower brazing temperatures, two different morphologies of borides develop in both base materials: plate-like and globular ones. Their ratio to each other is temperature dependent. With very high brazing temperatures, the deleterious boride formation in Alloy 247 can be totally avoided, probably because the three-phase-field moves to higher alloying element contents. For the superalloy PWA1483, the formation of borides cannot be completely avoided at high brazing temperatures as incipient melting occurs. During subsequent solidification of these areas, Chinese-script-like borides precipitate. The mechanical properties (tensile tests at room and elevated temperatures and short-term creep rupture tests at elevated temperatures) for brazed samples without boride precipitation are very promising. Tensile strengths and creep times to 1 pct strain are comparable, respectively, higher than the ones of the weaker parent material for all tested temperatures and creep conditions (from 90 to 100 pct rsp. 175 to 250 pct).

Wiring microbial biofilms to the electrode by osmium redox polymer for the performance enhancement of microbial fuel cells.

PubMed

Yuan, Yong; Shin, Hyosul; Kang, Chan; Kim, Sunghyun

2016-04-01

An osmium redox polymer, PAA-PVI-[Os(4,4'-dimethyl-2,2'-bipyridine)2Cl]+/2+ that has been used in enzymatic fuel cells and microbial sensors, was applied for the first time to the anode of single-chamber microbial fuel cells with the mixed culture inoculum aiming at enhancing performance. Functioning as a molecular wire connecting the biofilm to the anode, power density increased from 1479 mW m(-2) without modification to 2355 mW m(-2) after modification of the anode. Evidence from cyclic voltammetry showed that the catalytic activity of an anodic biofilm was greatly enhanced in the presence of an osmium redox polymer, indicating that electrons were more efficiently transferred to the anode via co-immobilized osmium complex tethered to wiring polymer chains at the potential range of -0.3 V-+0.1 V (vs. SCE). The optimum amount of the redox polymer was determined to be 0.163 mg cm(-2). Copyright © 2015 Elsevier B.V. All rights reserved.

New ternary tantalum borides containing boron dumbbells: Experimental and theoretical studies of Ta2OsB2 and TaRuB

NASA Astrophysics Data System (ADS)

Mbarki, Mohammed; Touzani, Rachid St.; Rehorn, Christian W. G.; Gladisch, Fabian C.; Fokwa, Boniface P. T.

2016-10-01

The new ternary transition metal-rich borides Ta2OsB2 and TaRuB have been successfully synthesized by arc-melting the elements in a water-cooled crucible under an argon atmosphere. The crystal structures of both compounds were solved by single-crystal X-ray diffraction and their metal compositions were confirmed by EDX analysis. It was found that Ta2OsB2 and TaRuB crystallize in the tetragonal Nb2OsB2 (space group P4/mnc, no. 128) and the orthorhombic NbRuB (space group Pmma, no. 51) structure types with lattice parameters a=5.878(2) Å, c=6.857(2) Å and a=10.806(2) Å, b=3.196(1) Å, c=6.312(2) Å, respectively. Furthermore, crystallographic, electronic and bonding characteristics have been studied by density functional theory (DFT). Electronic structure relaxation has confirmed the crystallographic parameters while COHP bonding analysis indicates that B2-dummbells are the strongest bonds in both compounds. Moreover, the formation of osmium dumbbells in Ta2OsB2 through a Peierls distortion along the c-axis, is found to be the origin of superstructure formation. Magnetic susceptibility measurements reveal that the two phases are Pauli paramagnets, thus confirming the theoretical DOS prediction of metallic character. Also hints of superconductivity are found in the two phases, however lack of single phase samples has prevented confirmation. Furthermore, the thermodynamic stability of the two modifications of AMB (A=Nb, Ta; M =Ru, Os) are studied using DFT, as new possible phases containing either B4- or B2-units are predicted, the former being the most thermodynamically stable modification.

A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

PubMed

Jothi, Palani R; Yubuta, Kunio; Fokwa, Boniface P T

2018-04-01

Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boron-Based Hydrogen Storage: Ternary Borides and Beyond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vajo, John J.

DOE continues to seek reversible solid-state hydrogen materials with hydrogen densities of ≥11 wt% and ≥80 g/L that can deliver hydrogen and be recharged at moderate temperatures (≤100 °C) and pressures (≤100 bar) enabling incorporation into hydrogen storage systems suitable for transportation applications. Boron-based hydrogen storage materials have the potential to meet the density requirements given boron’s low atomic weight, high chemical valance, and versatile chemistry. However, the rates of hydrogen exchange in boron-based compounds are thus far much too slow for practical applications. Although contributing to the high hydrogen densities, the high valance of boron also leads to slowmore » rates of hydrogen exchange due to extensive boron-boron atom rearrangements during hydrogen cycling. This rearrangement often leads to multiple solid phases occurring over hydrogen release and recharge cycles. These phases must nucleate and react with each other across solid-solid phase boundaries leading to energy barriers that slow the rates of hydrogen exchange. This project sought to overcome the slow rates of hydrogen exchange in boron-based hydrogen storage materials by minimizing the number of solid phases and the boron atom rearrangement over a hydrogen release and recharge cycle. Two novel approaches were explored: 1) developing matched pairs of ternary borides and mixed-metal borohydrides that could exchange hydrogen with only one hydrogenated phase (the mixed-metal borohydride) and only one dehydrogenated phase (the ternary boride); and 2) developing boranes that could release hydrogen by being lithiated using lithium hydride with no boron-boron atom rearrangement.« less

Structure of superhard tungsten tetraboride: A missing link between MB2 and MB12 higher borides

PubMed Central

Lech, Andrew T.; Turner, Christopher L.; Mohammadi, Reza; Tolbert, Sarah H.; Kaner, Richard B.

2015-01-01

Superhard metals are of interest as possible replacements with enhanced properties over the metal carbides commonly used in cutting, drilling, and wear-resistant tooling. Of the superhard metals, the highest boride of tungsten—often referred to as WB4 and sometimes as W1–xB3—is one of the most promising candidates. The structure of this boride, however, has never been fully resolved, despite the fact that it was discovered in 1961—a fact that severely limits our understanding of its structure–property relationships and has generated increasing controversy in the literature. Here, we present a new crystallographic model of this compound based on refinement against time-of-flight neutron diffraction data. Contrary to previous X-ray–only structural refinements, there is strong evidence for the presence of interstitial arrangements of boron atoms and polyhedral bonding. The formation of these polyhedra—slightly distorted boron cuboctahedra—appears to be dependent upon the defective nature of the tungsten-deficient metal sublattice. This previously unidentified structure type has an intermediary relationship between MB2 and MB12 type boride polymorphs. Manipulation of the fractionally occupied metal and boron sites may provide insight for the rational design of new superhard metals. PMID:25733870

Microstructure and mechanical properties of Ni and Fe-base boride-dispersion-strengthened microcrystalline alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wade, C.S.; Park, H.G.; Hoagland, R.G.

This paper considers the relation between microstructure and mechanical properties of two Ni-base and two Fe-base Boride-Dispersion-Strengthened Microcrystalline (BDSM) alloys. In these very fine grained materials the borides were primarily Cr, Mo, and MoFe in a fcc matrix in three of the alloys, and a bcc in one of the Fe-base alloys. Strength data and resistance to stress corrosion cracking are reported and, in the latter case, extraordinary resistance to SCC in NaCl, Na{sub 2}S{sub 2}O{sub 3} and boiling MgCl{sub 2} environments was observed in every case. The fcc BDSM alloys also demonstrated excellent thermal stability in terms of strengthmore » and fracture roughness up to 1000 C. The bcc alloy suffered severe loss of toughness. The fracture mode involved ductile rupture in all alloys and they display a reasonably linear correlation between K{sub Ic} and the square root of particle spacing.« less

Superabrasive boride and a method of preparing the same by mechanical alloying and hot pressing

DOEpatents

Cook, Bruce A.; Harringa, Joel L.; Russell, Alan M.

2002-08-13

A ceramic material which is an orthorhombic boride of the general formula: AlMgB.sub.14 :X, with X being a doping agent. The ceramic is a superabrasive, and in most instances provides a hardness of 40 GPa or greater.

Slater-Pauling behavior within quaternary intermetallic borides of the Ti{sub 3}Co{sub 5}B{sub 2} structure-type

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burghaus, Jens; Dronskowski, Richard, E-mail: drons@HAL9000.ac.rwth-aachen.d; Miller, Gordon J.

2009-10-15

First-principles, density-functional studies of several intermetallic borides of the general type M{sub 2}M'Ru{sub 5-n}Rh{sub n}B{sub 2} (n=0-5; M=Sc, Ti, Nb; M'=Fe, Co) show that the variation in saturation magnetic moment with valence-electron count follows a Slater-Pauling curve, with a maximum moment occurring typically at 66 valence electrons. The magnetic moments in these compounds occur primarily from the 3d electrons of the magnetically active M' sites, with some contribution from the Ru/Rh sites via magnetic polarization. Electronic DOS curves reveal that a rigid-band approach is a reasonable approximation for the estimation of saturation moments and the analysis of orbital interactions inmore » this family of complex borides. COHP analyses of the M'-M' orbital interactions indicate optimized interactions in the minority spin states for Co-containing phases, but strong bonding interactions remaining in Fe-containing phases. - Graphical abstract: Theoretically determined (spin-polarized LMTO-GGA) local magnetic moments as a function of the chemical valence Z for various intermetallic borides.« less

Amorphous nickel boride membrane on a platinum-nickel alloy surface for enhanced oxygen reduction reaction.

PubMed

He, Daping; Zhang, Libo; He, Dongsheng; Zhou, Gang; Lin, Yue; Deng, Zhaoxiang; Hong, Xun; Wu, Yuen; Chen, Chen; Li, Yadong

2016-08-09

The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9 V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.

Synthesis, Structure, and Properties of Refractory Hard-Metal Borides

NASA Astrophysics Data System (ADS)

Lech, Andrew Thomas

As the limits of what can be achieved with conventional hard compounds, such as tungsten carbide, are nearing reach, super-hard materials are an area of increasing industrial interest. The refractory hard metal borides, such as ReB2 and WB4, offer an increasingly attractive alternative to diamond and cubic boron nitride as a next-generation tool material. In this Thesis, a thorough discussion is made of the progress achieved by our laboratory towards understanding the synthesis, structure, and properties of these extremely hard compounds. Particular emphasis is placed on structural manipulation, solid solution formation, and the unique crystallographic manifestations of what might also be called "super-hard metals".

Surface decoration through electrostatic interaction leading to enhanced reactivity: Low temperature synthesis of nanostructured chromium borides (CrB and CrB{sub 2})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Menaka,; Kumar, Bharat; Kumar, Sandeep

The present study describes a novel low temperature route at ambient pressure for the synthesis of nanocrystalline chromium borides (CrB and CrB{sub 2}) without using any flux or additives. The favorable and intimate mixing of nanoparticles of chromium acetate (Cr source) and boron forms an active chromium–boron precursor which decomposes at much lower temperature (400 °C) to form CrB (which is ∼1000 °C less than the known ambient pressure synthesis). The chromium acetate nanoparticles (∼5 nm) decorate the larger boron particles (150–200 nm) due to electrostatic interactions resulting from opposing surface charges of boron (zeta potential:+48.101 mV) and chromium acetatemore » (zeta potential:−4.021 mV) in ethanolic medium and is evident in the TEM micrographs. The above method leads to the formation of pure CrB film like structure at 400 °C and nanospheres (40–60 nm) at 600 °C. Also, chromium diboride (CrB{sub 2}) nanoparticles (25 nm) could be obtained at 1000 °C. - Graphical abstract: Variation of surface charge of reactants, precursor and the products, chromium borides (CrB and CrB{sub 2}). Highlights: ► Novel borothermal reduction process for synthesis of chromium boride. ► Significant lowering of reaction temperature to obtain nanocrystalline chromium boride. ► Enhanced reactivity due to appropriate surface interactions.« less

Electroplating of the superconductive boride MgB2 from molten salts

NASA Astrophysics Data System (ADS)

Abe, Hideki; Yoshii, Kenji; Nishida, Kenji; Imai, Motoharu; Kitazawa, Hideaki

2005-02-01

An electroplating technique of the superconductive boride MgB2 onto graphite substrates is reported. Films of MgB2 with a thickness of tens micrometer were fabricated on the planar and curved surfaces of graphite substrates by means of electrolysis on a mixture of magnesium chloride, potassium chloride, sodium chloride, and magnesium borate fused at 600 °C under an Ar atmosphere. The electrical resistivity and magnetization measurements revealed that the electroplated MgB2 films undergo a superconducting transition with the critical temperature (Tc) of 36 K.

Easy To Synthesize, Robust Organo‐osmium Asymmetric Transfer Hydrogenation Catalysts

PubMed Central

Coverdale, James P. C.; Sanchez‐Cano, Carlos; Clarkson, Guy J.; Soni, Rina

2015-01-01

Abstract Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori‐type RuII catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X‐ray crystal structures of the 16‐electron OsII catalysts are almost identical to those of RuII. Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The OsII catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones. PMID:25853228

Osmium isotope constraints on ore metal recycling in subduction zones

PubMed

McInnes; McBride; Evans; Lambert; Andrew

1999-10-15

Veined peridotite xenoliths from the mantle beneath the giant Ladolam gold deposit on Lihir Island, Papua New Guinea, are 2 to 800 times more enriched in copper, gold, platinum, and palladium than surrounding depleted arc mantle. Gold ores have osmium isotope compositions similar to those of the underlying subduction-modified mantle peridotite source region, indicating that the primary origin of the metals was the mantle. Because the mantle is relatively depleted in gold, copper, and palladium, tectonic processes that enhance the advective transport and concentration of these fluid soluble metals may be a prerequisite for generating porphyry-epithermal copper-gold deposits.

Design of cemented tungsten carbide and boride-containing shields for a fusion power plant

NASA Astrophysics Data System (ADS)

Windsor, C. G.; Marshall, J. M.; Morgan, J. G.; Fair, J.; Smith, G. D. W.; Rajczyk-Wryk, A.; Tarragó, J. M.

2018-07-01

Results are reported on cemented tungsten carbide (cWC) and boride-containing composite materials for the task of shielding the centre column of a superconducting tokamak power plant. The shield is based on five concentric annular shells consisting of cWC and water layers of which the innermost cWC shield can be replaced with boride composites. Sample materials have been fabricated changing the parameters of porosity P, binder alloy fraction f binder and boron weight fraction f boron. For the fabricated materials, and other hypothetical samples with chosen parameters, Monte Carlo studies are made of: (i) the power deposition into the superconducting core, (ii) the fast neutron and gamma fluxes and (iii) the attenuation coefficients through the shield for the deposited power and neutron and gamma fluxes. It is shown that conventional Co-based cWC binder alloy can be replaced with a Fe–Cr alloy (92 wt.% Fe, 8 wt.% Cr), which has lower activation than cobalt with minor changes in shield performance. Boride-based composite materials have been prepared and shown to give a significant reduction in power deposition and flux, when placed close to the superconducting core. A typical shield of cemented tungsten carbide with 10 wt.% of Fe–8Cr binder and 0.1% porosity has a power reduction half-length of 0.06 m. It is shown that the power deposition increases by 4.3% for every 1% additional porosity, and 1.7% for every 1 wt.% additional binder. Power deposition decreased by 26% for an initial 1 wt.% boron addition, but further increases in f boron showed only a marginal decrease. The dependences of power deposited in the core, the maximum neutron and gamma fluxes on the core surface, and the half attenuation distances through the shield have been fitted to within a fractional percentage error by analytic functions of the porosity, metallic binder alloy and boron weight fractions.

Synthesis of Binary Transition Metal Nitrides, Carbides and Borides from the Elements in the Laser-Heated Diamond Anvil Cell and Their Structure-Property Relations

PubMed Central

Friedrich, Alexandra; Winkler, Björn; Juarez-Arellano, Erick A.; Bayarjargal, Lkhamsuren

2011-01-01

Transition metal nitrides, carbides and borides have a high potential for industrial applications as they not only have a high melting point but are generally harder and less compressible than the pure metals. Here we summarize recent advances in the synthesis of binary transition metal nitrides, carbides and borides focusing on the reaction of the elements at extreme conditions generated within the laser-heated diamond anvil cell. The current knowledge of their structures and high-pressure properties like high-(p,T) stability, compressibility and hardness is described as obtained from experiments. PMID:28824101

Electronic Structure Properties and a Bonding Model of Thermoelectric Half-Heusler and Boride Phases

NASA Astrophysics Data System (ADS)

Simonson, Jack William

Half-Heusler alloys MNiSn and MCoSb (M = Ti, Zr, Hf) and layered boride intermetallics with structure types YCrB4 and Er 3CrB7 were designed, synthesized, and characterized. The thermoelectric properties of these two classes of alloys were measured from room temperature to 1100 K with the intent of indirectly studying their electronic structure properties and gauging not only their suitability but that of related alloys for high temperature thermoelectric power generation. In the case of the half-Heusler alloys, transition metals were substituted to both the M and Ni/Co sites to study the resultant modifications of the d-orbital-rich portion of the electronic structure near the Fermi energy. This modification and subsequent pinning of the Fermi energy within the gap is discussed herein in terms of first principles electronic structure calculations from the literature. In the half-Heusler alloys, it was found that substitution of transition metals invariably led to a decrease in the thermopower, while the resistivity typically maintained its semiconducting trend. On the other hand, Sn doping in MCoSb type alloys -- a dopant that has been known for some time to be efficient -- was shown to result in high ZT at temperatures in excess of 1000 K. Moreover, the band gaps of the transition metal-doped alloys measured in this work offer insight into the discrepancy between the predicted and measured band gaps in the undoped parent compositions. In the case of the layered boride alloys, on the other hand, few electronic calculations have been published, thus prompting the generalization of a well-known electron counting rule -- which is typically used to study molecular organometallics, boranes, and metallocenes -- to predict the trends in the densities of states of crystalline solids that possess the requisite deltahedral bonding geometry. In accordance with these generalized electronic counting rules, alloys of the form RMB4 (R = Y, Gd, Ho; M = Cr, Mo, W) were measured to

Investigation of diffusional interaction between P91 grade ferritic steel and Fe-15 wt.%B alloy and study of kinetics of boride formation at high temperature

NASA Astrophysics Data System (ADS)

Rai, Arun Kumar; Vijayashanthi, N.; Tripathy, H.; Hajra, R. N.; Raju, S.; Murugesan, S.; Saroja, S.

2017-11-01

In the present study, the feasibility of employing the indigenously developed ferroboron alloy (Fe-15 wt.%B) as an alternate neutron shield material in combination with 9Cr-based ferritic steel (P91) clad in future Indian fast breeder reactors (FBR), has been investigated from a metallurgical perspective. Towards this goal, a series of diffusion couple experiments have been conducted at three different temperatures namely, 600, 700 and 800 °C for time durations up to 5000 h. The thickness of interaction layer has been monitored using standard metallographic procedures. The experiments revealed that ferroboron/P91 combination exhibited a tendency to form complex intermetallic borides at the interface. The structural and microstructural characterization of the interface confirmed that the reaction layer consists predominantly of borides of Fe and Cr of type FeB, Fe2B, (Fe,Cr)2B and (Fe,Cr)B. The measured variation of interaction layer thickness as a function of time and temperature have been modelled in terms of diffusion mediated interaction. The growth kinetics of borided layer has followed the parabolic law at each temperature, and the apparent activation energy for boride layer formation is found to be of the order of 115 kJ mol-1. This indicates that the kinetics of boriding could be governed by diffusion of B into the P91 matrix. Based on the findings of present study, an extrapolative estimate of the clad attack thickness at 550 °C for 60 years of operating time has been made and it turns out to be 210 ± 15 μm, which is less than the clad thickness of FBR shielding subassembly (4 mm) [1]. Thus, this study confirms that at testing temperatures from 550 to 600 °C, the ferroboron/P91 steel combination can be safely employed for shielding subassembly applications in fast reactors.

Effect of Heat Treatment on Borides Precipitation and Mechanical Properties of CoCrFeNiAl1.8Cu0.7B0.3Si0.1 High-Entropy Alloy Prepared by Arc-Melting and Laser-Cladding

NASA Astrophysics Data System (ADS)

Zhang, H.; Tang, H.; He, Y. Z.; Zhang, J. L.; Li, W. H.; Guo, S.

2017-11-01

Effects of heat treatment on borides precipitation and mechanical properties of arc-melted and laser-cladded CoCrNiFeAl1.8Cu0.7B0.3Si0.1 high-entropy alloys were comparatively studied. The arc-melted alloy contains lots of long strip borides distributed in the body-centered cubic phase, with a hardness about 643 HV0.5. Laser-cladding can effectively inhibit the boride precipitation and the laser-cladded alloy is mainly composed of a simple bcc solid solution, with a high hardness about 769 HV0.5, indicating the strengthening effect by interstitial boron atoms is greater than the strengthening by borides precipitation. Heat treatments between 800°C and 1200°C can simultaneously improve the hardness and fracture toughness of arc-melted alloys, owing to the boride spheroidization, dissolution, re-precipitation, and hence the increased boron solubility and nano-precipitation in the bcc solid solution. By contrast, the hardness of laser-cladded alloys reduce after heat treatments in the same temperature range, due to the decreased boron solubility in the matrix.

Thermal properties of zirconium diboride -- transition metal boride solid solutions

NASA Astrophysics Data System (ADS)

McClane, Devon Lee

This research focuses on the thermal properties of zirconium diboride (ZrB2) based ceramics. The overall goal was to improve the understanding of how different transition metal (TM) additives influence thermal transport in ZrB2. To achieve this, ZrB2 with 0.5 wt% carbon, and 3 mol% of individual transition metal borides, was densified by hot-press sintering. The transition metals that were investigated were: Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The room temperature thermal diffusivities of the compositions ranged from 0.331 cm2/s for nominally pure ZrB2 to 0.105 cm2/s for (Zr,Cr)B2 and converged around 0.155cm2/s at higher temperatures for all compositions. Thermal conductivities were calculated from the diffusivities, using temperature-dependent values for density and heat capacity. The electron contribution to thermal conductivity was calculated from measured electrical resistivity according to the Wiedemann-Franz law. The phonon contribution to thermal conductivity was calculated by subtracting the electron contribution from the total thermal conductivity. Rietveld refinement of x-ray diffraction data was used to determine the lattice parameters of the compositions. The decrease in thermal conductivity for individual additives correlated directly to the metallic radius of the additive. Additional strain appeared to exist for additives when the stable TM boride for that metal had different crystal symmetries than ZrB2. This research provided insight into how additives and impurities affect thermal transport in ZrB2. The research potentially offers a basis for future modeling of thermal conductivity in ultra-high temperature ceramics based on the correlation between metallic radius and the decrease in thermal conductivity.

Rhenium-osmium isotope systematics of carbonaceous chondrites

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.

1989-01-01

Rhenium and osmium concentrations and Os isotopic compositions of eight carbonaceous chondrites, one LL3 ordinary chondrite, and two iron meteorites were determined by resonance ionization mass spectrometry. Iron meteorite 187Re/186Os and 187OS/186Os ratios plot on the previously determined iron meteorite isochron, but most chondrite data plot 1 to 2 percent above this meteorite isochron. This suggests either that irons have significantly younger Re-Os closure ages than chondrites or that chondrites were formed from precursor materials with different chemical histories from the precursors of irons. Some samples of Semarkona (LL3) and Murray (C2M) meteorites plot 4 to 6 percent above the iron meteorite isochron, well above the field delineated by other chondrites. Murray may have lost Re by aqueous leaching during its preterrestrial history. Semarkona could have experienced a similar loss of Re, but only slight aqueous alteration is evident in the meteorite. Therefore, the isotopic composition of Semarkona could reflect assembly of isotopically heterogeneous components subsequent to 4.55 billion years ago or Os isotopic heterogeneities in the primordial solar nebula.

Infiltration processing of boron carbide-, boron-, and boride-reactive metal cermets

DOEpatents

Halverson, Danny C.; Landingham, Richard L.

1988-01-01

A chemical pretreatment method is used to produce boron carbide-, boron-, and boride-reactive metal composites by an infiltration process. The boron carbide or other starting constituents, in powder form, are immersed in various alcohols, or other chemical agents, to change the surface chemistry of the starting constituents. The chemically treated starting constituents are consolidated into a porous ceramic precursor which is then infiltrated by molten aluminum or other metal by heating to wetting conditions. Chemical treatment of the starting constituents allows infiltration to full density. The infiltrated precursor is further heat treated to produce a tailorable microstructure. The process at low cost produces composites with improved characteristics, including increased toughness, strength.

Nucleosynthetic osmium isotope anomalies in acid leachates of the Murchison meteorite

NASA Astrophysics Data System (ADS)

Reisberg, L.; Dauphas, N.; Luguet, A.; Pearson, D. G.; Gallino, R.; Zimmermann, C.

2009-01-01

We present osmium isotopic results obtained by sequential leaching of the Murchison meteorite, which reveal the existence of very large internal anomalies of nucleosynthetic origin (ɛ 184Os from - 108 to 460; ɛ 186Os from - 14.1 to 12.6; ɛ 188Os from - 2.6 to 1.6; ɛ 190Os from - 1.7 to 1.1). Despite these large variations, the isotopic composition of the total leachable osmium (weighted average of the leachates) is close to that of bulk chondrites. This is consistent with efficient large-scale mixing of Os isotopic anomalies in the protosolar nebula. The Os isotopic anomalies are correlated, and can be explained by the variable contributions of components derived from the s, r and p-processes of nucleosynthesis. Surprisingly, much of the s-process rich osmium is released by relatively mild leaching, suggesting the existence of an easily leachable s-process rich presolar phase, or alternatively, of a chemically resistant r-process rich phase. Taken together with previous evidence for a highly insoluble s-process rich carrier, such as SiC, these results argue for the presence of several presolar phases with anomalous nucleosynthetic compositions in the Murchison meteorite. The s-process composition of Os released by mild leaching diverges slightly from that released by aggressive digestion techniques, perhaps suggesting that the presolar phases attacked by these differing procedures condensed in different stellar environments. The correlation between ɛ 190Os and ɛ 188Os can be used to constrain the s-process 190Os/ 188Os ratio to be 1.275 ± 0.043. Such a ratio can be reproduced in a nuclear reaction network for a MACS value for 190Os of ~ 200 ± 22 mbarn at 30 keV. More generally, these results can help refine predictions of the s-process in the Os mass region, which can be used in turn to constrain the amount of cosmoradiogenic 187Os in the solar system and hence the age of the Galaxy. We also present evidence for extensive internal variation of 184Os

Kinetics of electrolysis current reversal boriding of tool steels in a boron-containing oxychloride melt based on CaCl2

NASA Astrophysics Data System (ADS)

Chernov, Ya. B.; Filatov, E. S.

2017-08-01

The kinetics of thermal diffusion boriding in a melt based on calcium chloride with a boron oxide additive is studied using reversed current. The main temperature, concentration, and current parameters of the process are determined. The phase composition of the coating is determined by a metallographic method.

Thermodynamic modelling of phase equilibrium in system Ti-B-Si-C, synthesis and phases composition of borides and carbides layers on titanic alloyVT-1 at electron beam treatment in vacuum

NASA Astrophysics Data System (ADS)

Smirnyagina, N. N.; Khaltanova, V. M.; Lapina, A. E.; Dasheev, D. E.

2017-01-01

Composite layers on the basis of carbides and borides the titan and silicon on titanic alloy VT-1 are generated at diffused saturation in vacuum. Formation in a composite of MAX phase Ti3SiC2 is shown. Thermodynamic research of phase equilibrium in systems Ti-Si-C and Ti-B-C in the conditions of high vacuum is executed. The thermodynamics, formation mechanisms of superfirm layers borides and carbides of the titan and silicon are investigated.

Pt-B System Revisited: Pt2B, a New Structure Type of Binary Borides. Ternary WAl12-Type Derivative Borides.

PubMed

Sologub, Oksana; Salamakha, Leonid; Rogl, Peter; Stöger, Berthold; Bauer, Ernst; Bernardi, Johannes; Giester, Gerald; Waas, Monika; Svagera, Robert

2015-11-16

On the basis of a detailed study applying X-ray single-crystal and powder diffraction, differential scanning calorimetry, and scanning electron microscopy analysis, it was possible to resolve existing uncertainties in the Pt-rich section (≥65 atom % Pt) of the binary Pt-B phase diagram above 600 °C. The formation of a unique structure has been observed for Pt2B [X-ray single-crystal data: space group C2/m, a = 1.62717(11) nm, b = 0.32788(2) nm, c = 0.44200(3) nm, β = 104.401(4)°, RF2 = 0.030]. Within the homogeneity range of "Pt3B", X-ray powder diffraction phase analysis prompted two structural modifications as a function of temperature. The crystal structure of "hT-Pt3B" complies with the hitherto reported structure of anti-MoS2 [space group P63/mmc, a = 0.279377(2) nm, c = 1.04895(1) nm, RF = 0.075, RI = 0.090]. The structure of the new "[Formula: see text]T-Pt3B" is still unknown. The formation of previously reported Pt∼4B has not been confirmed from binary samples. Exploration of the Pt-rich section of the Pt-Cu-B system at 600 °C revealed a new ternary compound, Pt12CuB6-y [X-ray single-crystal data: space group Im3̅, a = 0.75790(2) nm, y = 3, RF2 = 0.0129], which exhibits the filled WAl12-type structure accommodating boron in the interstitial trigonal-prismatic site 12e. The isotypic platinum-aluminum-boride was synthesized and studied. The solubility of copper in binary platinum borides has been found to attain ∼7 atom % Cu for Pt2B but to be insignificant for "[Formula: see text]T-Pt3B". The architecture of the new Pt2B structure combines puckered layers of boron-filled and empty [Pt6] octahedra (anti-CaCl2-type fragment) alternating along the x axis with a double layer of boron-semifilled [Pt6] trigonal prisms interbedded with a layer of empty tetrahedra and tetragonal pyramids (B-deficient α-T[Formula: see text]I fragment). Assuming boron vacancies ordering (space group R3), the Pt12CuB6-y structure exhibits serpentine-like columns of edge

Structural, electronic and thermal properties of super hard ternary boride, WAlB

NASA Astrophysics Data System (ADS)

Rajpoot, Priyanka; Rastogi, Anugya; Verma, U. P.

2018-04-01

A first principle study of the structural, electronic and thermal properties of Tungsten Aluminum Boride (WAlB) using full-potential linearized augmented plane wave (FP-LAPW) in the frame work of density function theory (DFT) have been calculated. The calculated equilibrium structural parameters are in excellent agreement with available experimental results. The calculated electronic band structure reveals that WAlB is metallic in nature. The quasi-harmonic Debye model is applied to study of the temperature and pressure effect on volume, Debye temperature, thermal expansion coefficient and specific heat at constant volume and constant pressure. To the best of our knowledge theoretical investigation of these properties of WAlB is reported for the first time.

A Simple Kinetic Model for the Growth of Fe2B Layers on AISI 1026 Steel During the Powder-pack Boriding

NASA Astrophysics Data System (ADS)

Flores-Rentería, M. A.; Ortiz-Domínguez, M.; Keddam, M.; Damián-Mejía, O.; Elias-Espinosa, M.; Flores-González, M. A.; Medina-Moreno, S. A.; Cruz-Avilés, A.; Villanueva-Ibañez, M.

2015-02-01

This work focused on the determination of boron diffusion coefficient through the Fe2B layers on AISI 1026 steel using a mathematical model. The suggested model solves the mass balance equation at the (Fe2B/substrate) interface. This thermochemical treatment was carried out in the temperature range of 1123-1273 K for a treatment time ranging from 2 to 8 h. The generated boride layers were characterized by different experimental techniques such as light optical microscopy, scanning electron microscopy, XRD analysis and the Daimler-Benz Rockwell-C indentation technique. As a result, the boron activation energy for AISI 1026 steel was estimated as 178.4 kJ/mol. Furthermore, this kinetic model was validated by comparing the experimental Fe2B layer thickness with the predicted one at a temperature of 1253 K for 5 h of treatment. A contour diagram relating the layer thickness to the boriding parameters was proposed to be used in practical applications.

PREFACE: The 16th International Symposium on Boron, Borides and Related Materials (ISBB 2008)

NASA Astrophysics Data System (ADS)

Tanaka, Takaho

2009-07-01

This volume of Journal of Physics: Conference Series contains invited and contributed peer-reviewed papers that were presented at the 16th International Symposium on Boron, Borides and Related Materials (ISBB 2008), which was held on 7-12 September 2008, at Kunibiki Messe, Matsue, Japan. This triennial symposium has a half-century long history starting from the 1st meeting in 1959 at Asbury Park, New Jersey. We were very pleased to organize ISBB 2008, which gathered chemists, physicists, materials scientists as well as diamond and high-pressure researchers. This meeting had a strong background in the boron-related Japanese research history, which includes the discovery of superconductivity in MgB2 and development of Nd-Fe-B hard magnets and of YB66 soft X-ray monochromator. The scope of ISBB 2008 spans both basic and applied interdisciplinary research that is centered on boron, borides and related materials, and the collection of articles defines the state of the art in research on these materials. The topics are centered on: 1. Preparation of new materials (single crystals, thin films, nanostructures, ceramics, etc) under normal or extreme conditions. 2. Crystal structure and chemical bonding (new crystal structures, nonstoichiometry, defects, clusters, quantum-chemical calculations). 3. Physical and chemical properties (band structure, phonon spectra, superconductivity; optical, electrical, magnetic, emissive, mechanical properties; phase diagrams, thermodynamics, catalytic activity, etc) in a wide range of temperatures and pressures. 4. Applications and prospects (thermoelectric converters, composites, ceramics, coatings, etc) There were a few discoveries of new materials, such as nanomaterials, and developments in applications. Many contributions were related to 4f heavy Fermion systems of rare-earth borides. Exotic mechanisms of magnetism and Kondo effects have been discussed, which may indicate another direction of development of boride. Two special sessions

Theoretical survey of the reaction between osmium and acetaldehyde

NASA Astrophysics Data System (ADS)

Dai, Guo-Liang; Wang, Chuan-Feng

2012-05-01

The mechanism of the reaction of osmium atom with acetaldehyde has been investigated with a DFT approach. All the stationary points are determined at the UB3LYP/ sdd/6-311++G** level of the theory. Both ground and excited state potential energy surfaces are investigated in detail. The present results show that the title reaction start with the formation of a CH3CHO-metal complex followed by C-C, aldehyde C-H, C-O, and methyl C-H activation. These reactions can lead to four different products (HOsCH3 + CO, OsCO + CH4, OsCOCH3 + H, and OsO + C2H4). The minimum energy reaction path is found to involve the spin inversion in the initial reaction step. This potential energy curve-crossing dramatically affects reaction exothermic. The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction.

Magnetic and magnetothermal studies of iron boride (FeB) nanoparticles

NASA Astrophysics Data System (ADS)

Hamayun, M. Asif; Abramchuk, Mykola; Alnasir, Hisham; Khan, Mohsin; Pak, Chongin; Lenhert, Steven; Ghazanfari, Lida; Shatruk, Michael; Manzoor, Sadia

2018-04-01

We report magnetic and magnetothermal properties of iron boride (FeB) nanoparticles prepared by surfactant-assisted ball milling of arc-melted bulk ingots of this binary alloy. Size-dependent magnetic properties were used to identify the transition to the single domain limit and calculate the anisotropy and exchange stiffness constants for this system. Extended milling is seen to produce coercivity enhancement and exchange bias of up to 270 Ôe at room temperature. The magnetothermal properties were investigated by measuring the response of single domain FeB nanoparticles to externally applied ac magnetic fields. All investigated particle sizes show a significant heating response, demonstrating their potential as candidates for magnetically induced hyperthermia. FeB nanoparticles were encapsulated into lipophilic domains of liposomes as evidenced by TEM. Exposure of HeLa cells to these liposomes did not affect cell viability, suggesting the biocompatibility of these new magnetic nanomaterials.

Tracing Anthropogenic Osmium around Japan using the Osmium Isotopic Composition of Macroalgae

NASA Astrophysics Data System (ADS)

Sproson, A. D.; Selby, D. S.; Suzuki, K.

2016-12-01

The present-day open ocean seawater 187Os/188Os value of 1.06 is seen to reflect the balance between unradiogenic mantle derived osmium (Os) and radiogenic continental Os. However, Os released by anthropogenic activities has been detected in coastal sediments, lakes, estuaries, rain and snow from sources such as sewage sludge, catalytic convertors, smelting, fossil fuel burning and use as a staining reagent, thereby impacting the global Os budget. Despite over two decades of research, contemporary Os inputs into the ocean are believed to be underestimated by a factor of 3, leading to discrepancies in oceanic Os residence times estimated from mass balance calculations. This, in part, is due to the problems associated with directly measuring ultra-low concentrations of Os in seawater. Recently, it has been proposed that the 187Os/188Os of macroalgae (seaweed) reflects that of the seawater in which it lives. This suggests macroalgae can act as a proxy for the Os isotopic composition of seawater. We present Os isotope data for macroalgae collected from Tokyo Bay, Osaka Bay, the Noto Peninsula, Izu Peninsula and Hokkaido. Macroalgae close to the major cities of Tokyo and Osaka exhibit unradiogenic 187Os/188Os values as low as 0.45, in agreement with published sediment data. As you move away from central Tokyo and Osaka, 187Os/188Os values become more radiogenic, reaching values as high as 0.95 due to the entrainment of more radiogenic seawater. Macroalgae from the less urbanised Noto and Izu Peninsulas show a radiogenic 187Os/188Os range of 0.70-0.91, close to global river estimates suggesting little contamination from anthropogenic processes. Deep-water species off the coast of Hokkaido exhibit 187Os/188Os values in agreement with published Pacific Ocean seawater data. We propose macroalgae is recording the influence of anthropogenic processes - in particular sewage sludge production and catalytic convertor exhaust - on the Os budget of Japanese waters. Therefore

Crystal structures and compressibility of novel iron borides Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} synthesized at high pressure and high temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bykova, E., E-mail: elena.bykova@uni-bayreuth.de; Laboratory of Crystallography, University of Bayreuth, D-95440 Bayreuth; Gou, H.

2015-10-15

We present here a detailed description of the crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} with various iron content (x=1.01(1), 1.04(1), 1.32(1)), synthesized at high pressures and high temperatures. As revealed by high-pressure single-crystal X-ray diffraction, the structure of Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds, which make it as stiff as diamond in one crystallographic direction. The volume compressibility of Fe{sub 2}B{sub 7} (the bulk modulus K{sub 0}= 259(1.8) GPa, K{sub 0}′= 4 (fixed)) is even lower than that of FeB{sub 4} and comparable with that of MnB{sub 4}, known for highmore » bulk moduli among 3d metal borides. Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B, in which Fe atoms occupy an interstitial position. Fe{sub x}B{sub 50} does not show considerable anisotropy in the elastic behavior. - Graphical abstract: Crystal structures of novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50} (x=1.01(1), 1.04(1), 1.32(1)). - Highlights: • Novel iron borides, Fe{sub 2}B{sub 7} and Fe{sub x}B{sub 50}, were synthesized under HPHT conditions. • Fe{sub 2}B{sub 7} has a unique orthorhombic structure (space group Pbam). • Fe{sub 2}B{sub 7} possesses short incompressible B–B bonds that results in high bulk modulus. • Fe{sub x}B{sub 50} adopts the structure of the tetragonal δ-B composed of B{sub 12} icosahedra. • In Fe{sub x}B{sub 50} intraicosahedral bonds are stiffer than intericosahedral ones.« less

Rhenium and osmium isotopes in black shales and Ni-Mo-PGE-rich sulfide layers, Yukon Territory, Canada, and Hunan and Guizhou provinces, China

USGS Publications Warehouse

Horan, M.F.; Morgan, J.W.; Grauch, R.I.; Coveney, R.M.; Murowchick, J.B.; Hulbert, L.J.

1994-01-01

Rhenium and osmium abundances and osmium isotopic compositions were determined by negative thermal ionization mass spectrometry for samples of Devonian black shale and an associated Ni-enriched sulfide layer from the Yukon Territory, Canada. The same composition information was also obtained for samples of early Cambrian Ni-Mo-rich sulfide layers hosted in black shale in Guizhou and Hunan provinces, China. This study was undertaken to constrain the origin of the PGE enrichment in the sulfide layers. Samples of the Ni sulfide layer from the Yukon Territory are highly enriched in Re, Os, and other PGE, with distinctly higher Re/192Os but similar Pt/Re, compared to the black shale host. Re-Os isotopic data of the black shale and the sulfide layer are approximately isochronous, and the data plot close to reference isochrons which bracket the depositional age of the enclosing shales. Samples of the Chinese sulfide layers are also highly enriched in Re, Os, and the other PGE. Re/192Os are lower than in the Yukon sulfide layer. Re-Os isotopic data for the sulfide layers lie near a reference isochron with an age of 560 Ma, similar to the depositional age of the black shale host. The osmium isotopic data suggest that Re and PGE enrichment of the brecciated sulfide layers in both the Yukon Territory and in southern China may have occurred near the time of sediment deposition or during early diagenesis, during the middle to late Devonian and early Cambrian, respectively. ?? 1994.

Osmium isotope stratigraphy of a marine ferromanganese crust

USGS Publications Warehouse

Klemm, V.; Levasseur, S.; Frank, M.; Hein, J.R.; Halliday, A.N.

2005-01-01

Ferromanganese crusts provide records of long term change in ocean circulation and continental weathering. However, calibrating their age prior to 10 Ma has been entirely based on empirical growth rate models using Co concentrations, which have inherently large uncertainties and fail to detect hiatuses and erosional events. We present a new method for dating these crusts by measuring their osmium (Os) isotope record and matching it to the well-known marine Os isotope evolution of the past 80 Ma. The well-characterised crust CD29-2 from the central Pacific, was believed to define a record of paleooceanographic change from 50 Ma. Previous growth rate estimates based on the Co method are consistent with the new Os isotope stratigraphy but the dating was grossly inaccurate due to long hiatuses that are now detectable. The new chronology shows that it in fact started growing prior to 70 Ma in the late Cretaceous and stopped growing or was eroded between 13.5 and 47 Ma. With this new technique it is now possible to exploit the full potential of the oceanographic and climatic records stored in Fe-Mn crusts. ?? 2005 Elsevier B.V. All rights reserved.

Ionization cross section, pressure shift and isotope shift measurements of osmium

NASA Astrophysics Data System (ADS)

Hirayama, Yoshikazu; Mukai, Momo; Watanabe, Yutaka; Oyaizu, Michihiro; Ahmed, Murad; Kakiguchi, Yutaka; Kimura, Sota; Miyatake, Hiroari; Schury, Peter; Wada, Michiharu; Jeong, Sun-Chan

2017-11-01

In-gas-cell laser resonance ionization spectroscopy of neutral osmium atoms was performed with the use of a two-color two-step laser resonance ionization technique. Saturation curves for the ionization scheme were measured, and the ionization cross section was experimentally determined by solving the rate equations for the ground, intermediate and ionization continuum populations. The pressure shift and pressure broadening in the resonance spectra of the excitation transition were measured. The electronic factor {F}247 for the transition {λ }1=247.7583 nm to the intermediate state was deduced from the measured isotope shifts of stable {}{188,189,{190,192}}Os isotopes. The efficient ionization scheme, pressure shift, nuclear isotope shift and {F}247 are expected to be useful for applications of laser ion sources to unstable nuclei and for nuclear spectroscopy based on laser ionization techniques.

Osmium isotope evidence for a large Late Triassic impact event

PubMed Central

Sato, Honami; Onoue, Tetsuji; Nozaki, Tatsuo; Suzuki, Katsuhiko

2013-01-01

Anomalously high platinum group element concentrations have previously been reported for Upper Triassic deep-sea sediments, which are interpreted to be derived from an extraterrestrial impact event. Here we report the osmium (Os) isotope fingerprint of an extraterrestrial impact from Upper Triassic chert successions in Japan. Os isotope data exhibit a marked negative excursion from an initial Os isotope ratio (187Os/188Osi) of ∼0.477 to unradiogenic values of ∼0.126 in a platinum group element-enriched claystone layer, indicating the input of meteorite-derived Os into the sediments. The timing of the Os isotope excursion coincides with both elevated Os concentrations and low Re/Os ratios. The magnitude of this negative Os isotope excursion is comparable to those found at Cretaceous–Paleogene boundary sites. These geochemical lines of evidence demonstrate that a large impactor (3.3–7.8 km in diameter) produced a global decrease in seawater 187Os/188Os ratios in the Late Triassic. PMID:24036603

A superconducting battery material: Lithium gold boride (LiAu3B)

NASA Astrophysics Data System (ADS)

Aydin, Sezgin; Şimşek, Mehmet

2018-04-01

The superconducting and potential cathode material properties of ternary boride of LiAu3B have been investigated by density functional first principles. The Li-concentration effects on the actual electronic and structural properties, namely the properties of LixAu9B3 (x = 0, 1, 2) sub-systems are studied. It is remarkably shown that the existence of Li-atoms has no considerable effect on the structural properties of Au-B skeleton in LiAu3B. Then, it can be offered as a potential cathode material for Li-ion batteries with the very small volume deviation of 0.42%, and the suitable average open circuit voltage of ∼1.30 V. Furthermore, the vibrational and superconducting properties such as electron-phonon coupling constant (λ) and critical temperature (Tc) of LiAu3B are studied. The calculated results suggest that LiAu3B should be a superconductor with Tc ∼5.8 K, also.

Fine structure of the K X-ray absorption spectra of titanium in some hydrides, borides, and silicides (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vainshtein, �. E.; Zhurakovskii, E. A.

1959-08-01

X-ray spectral analyses confirmed the hypothesis on the metal-like state of hydrogen in tithnium hydrides. Experiments with titunium borides and silicides indicate the special character and degree of the 3d--level participation in the metallic'' bond between the atoms of various complexes. The structure of metalloid elements becomes more complicated with an increase in the specific number of boron and silicon atoms and the bond between the atoms tends to become covalent. (R.V.J.)

Spectroscopic Identification of the Carbyne Hydride Structure of the Dehydrogenation Product of Methane Activation by Osmium Cations

NASA Astrophysics Data System (ADS)

Armentrout, P. B.; Kuijpers, Stach E. J.; Lushchikova, Olga V.; Hightower, Randy L.; Boles, Georgia C.; Bakker, Joost M.

2018-04-01

The present work explores the structures of species formed by dehydrogenation of methane (CH4) and perdeuterated methane (CD4) by the 5d transition metal cation osmium (Os+). Using infrared multiple photon dissociation (IRMPD) action spectroscopy and density functional theory (DFT), the structures of the [Os,C,2H]+ and [Os,C,2D]+ products are explored. This study complements previous work on the related species formed by dehydrogenation of methane by four other 5d transition metal cations (M+ = Ta+, W+, Ir+, and Pt+). Osmium cations are formed in a laser ablation source, react with methane pulsed into a reaction channel downstream, and the resulting products spectroscopically characterized through photofragmentation using the Free-Electron Laser for IntraCavity Experiments (FELICE) in the 300-1800 cm-1 range. Photofragmentation was monitored by the loss of H2/D2. Comparison of the experimental spectra and DFT calculated spectra leads to identification of the ground state carbyne hydride, HOsCH+ (2A') as the species formed, as previously postulated theoretically. Further, a full description of the systematic spectroscopic shifts observed for deuterium labeling of these complexes, some of the smallest systems to be studied using IRMPD action spectroscopy, is achieved. A full rotational contour analysis explains the observed linewidths as well as the observation of doublet structures in several bands, consistent with previous observations for HIrCH+ (2A'). [Figure not available: see fulltext.

Confirmation of a meteoritic component in impact-melt rocks of the Chesapeake Bay impact structure, Virginia, USA - Evidence from osmium isotopic and PGE systematics

USGS Publications Warehouse

Lee, S.R.; Horton, J. Wright; Walker, R.J.

2006-01-01

The osmium isotope ratios and platinum-group element (PGE) concentrations of impact-melt rocks in the Chesapeake Bay impact structure were determined. The impact-melt rocks come from the cored part of a lower-crater section of suevitic crystalline-clast breccia in an 823 m scientific test hole over the central uplift at Cape Charles, Virginia. The 187Os/188Os ratios of impact-melt rocks range from 0.151 to 0.518. The rhenium and platinum-group element (PGE) concentrations of these rocks are 30-270?? higher than concentrations in basement gneiss, and together with the osmium isotopes indicate a substantial meteoritic component in some impact-melt rocks. Because the PGE abundances in the impact-melt rocks are dominated by the target materials, interelemental ratios of the impact-melt rocks are highly variable and nonchondritic. The chemical nature of the projectile for the Chesapeake Bay impact structure cannot be constrained at this time. Model mixing calculations between chondritic and crustal components suggest that most impact-melt rocks include a bulk meteoritic component of 0.01-0.1% by mass. Several impact-melt rocks with lowest initial 187Os/188Os ratios and the highest osmium concentrations could have been produced by additions of 0.1%-0.2% of a meteoritic component. In these samples, as much as 70% of the total Os may be of meteoritic origin. At the calculated proportions of a meteoritic component (0.01-0.1% by mass), no mixtures of the investigated target rocks and sediments can reproduce the observed PGE abundances of the impact-melt rocks, suggesting that other PGE enrichment processes operated along with the meteoritic contamination. Possible explanations are 1) participation of unsampled target materials with high PGE abundances in the impact-melt rocks, and 2) variable fractionations of PGE during syn- to post-impact events. ?? The Meteoritical Society, 2006.

Identification of delamination failure of boride layer on common Cr-based steels

NASA Astrophysics Data System (ADS)

Taktak, Sukru; Tasgetiren, Suleyman

2006-10-01

Adhesion is an important aspect in the reliability of coated components. With low-adhesion of interfaces, different crack paths may develop depending on the local stress field at the interface and the fracture toughness of the coating, substrate, and interface. In the current study, an attempt has been made to identify the delamination failure of coated Cr-based steels by boronizing. For this reason, two commonly used steels (AISI H13, AISI 304) are considered. The steels contain 5.3 and 18.3 wt.% Cr, respectively. Boriding treatment is carried out in a slurry salt bath consisting of borax, boric acid, and ferrosilicon at a temperature range of 800 950 °C for 3, 5, and 7 h. The general properties of the boron coating are obtained by mechanical and metallographic characterization tests. For identification of coating layer failure, some fracture toughness tests and the Daimler-Benz Rockwell-C adhesion test are used.

Osmium isotopes in Ivory Coast tektites: Confirmation of a meteoritic component and rhenium depletion

NASA Technical Reports Server (NTRS)

Koeberl, Christian; Shirey, Steven B.

1993-01-01

The sensitive negative thermal ionization mass spectrometry method was used for the measurement of concentrations and isotopic ratios of osmium and rhenium in four Ivory Coast tektites. These tektites have crustal major and trace element composition, as well as large negative epsilon(sub Nd)(-20) and positive epsilon(sub Sr)(+260 to +300) which are characteristic for old continental crust. Os concentrations ranging from 0.09 to 0.30 ppb were found, clearly much higher than average crustal values, Os-187/Os-186 ratios of about 1.2-1.7, and low Re-187/Os-186 ratios. These results show unambiguously the existence of a meteoritic component (on the order of 0.06%) in the Ivory Coast tektites. Low Re abundances are the result of fractionation of Re during the impact.

Abundances and isotopic compositions of rhenium and osmium in pyrite samples from the Huaibei coalfield, Anhui, China

USGS Publications Warehouse

Liu, Gaisheng; Chou, C.-L.; Peng, Z.; Yang, G.

2008-01-01

Two pyrite samples from the Shihezi Formation (Lower Permian), Huaibei coalfield, Anhui, China, have been analyzed for abundances and isotopic compositions of rhenium and osmium using negative thermal ion mass spectrometry. The Re-Os ages of the pyrites are 64.4 and 226 Ma, which are younger than the formation age of the coal seam. The pyrite samples may consist of pyrite formed at various stages during the history of coal formation. The ??Osvalues of the two pyrite samples are +17 and +18, respectively. Such high ??Osvalues are reported for the first time for recycles crustal materials from a sedimentary basin. ?? Springer-Verlag 2007.

Osmium-Isotope and Platinum-Group-Element Systematics of Impact-Melt Rocks, Chesapeake Bay Impact Structure, Virginia, USA

NASA Technical Reports Server (NTRS)

Lee, Seung Ryeol; Wright Horton, J., Jr.; Walker, Richard J.

2005-01-01

Osmium (Os) isotopes and platinum-group elements (PGEs) are useful for geochemically identifying a meteoritic component within impact structures, because meteorites are typically characterized by low (187)Os/(188)Os ratios and high PGE concentrations. In contrast, most types of crustal target rocks have high radiogenic Os and very low PGE concentrations. We have examined Os isotope and PGE systematics of impact-melt rocks and pre-impact target rocks from a 2004 test hole in the late Eocene Chesapeake Bay impact structure and from nearby coreholes. Our goal is to determine the proportion of the projectile component in the melt rock Additional information is included in the original extended abstract.

Deep levels in osmium doped p-type GaAs grown by metal organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Iqbal, M. Zafar; Majid, A.; Dadgar, A.; Bimberg, D.

2005-06-01

Results of a preliminary study on deep level transient spectroscopy (DLTS) investigations of osmium (Os) impurity in p-type GaAs, introduced in situ during MOCVD crystal growth, are reported for the first time. Os is clearly shown to introduce two prominent deep levels in the lower half-bandgap of GaAs at energy positions Ev + 0.42 eV (OsA) and Ev + 0.72 eV (OsB). A minority-carrier emitting defect feature observed in the upper half-bandgap is shown to consist of a band of Os-related deep levels with a concentration significantly higher than that of the majority carrier emitting deep levels. Detailed data on the emission rate signatures and related parameters of the Os-related deep levels are reported.

Reactivity of nitrido complexes of ruthenium(VI), osmium(VI), and manganese(V) bearing Schiff base and simple anionic ligands.

PubMed

Man, Wai-Lun; Lam, William W Y; Lau, Tai-Chu

2014-02-18

Nitrido complexes (M≡N) may be key intermediates in chemical and biological nitrogen fixation and serve as useful reagents for nitrogenation of organic compounds. Osmium(VI) nitrido complexes bearing 2,2':6',2″-terpyridine (terpy), 2,2'-bipyridine (bpy), or hydrotris(1-pyrazolyl)borate anion (Tp) ligands are highly electrophilic: they can react with a variety of nucleophiles to generate novel osmium(IV)/(V) complexes. This Account describes our recent results studying the reactivity of nitridocomplexes of ruthenium(VI), osmium(VI), and manganese(V) that bear Schiff bases and other simple anionic ligands. We demonstrate that these nitrido complexes exhibit rich chemical reactivity. They react with various nucleophiles, activate C-H bonds, undergo N···N coupling, catalyze the oxidation of organic compounds, and show anticancer activities. Ruthenium(VI) nitrido complexes bearing Schiff base ligands, such as [Ru(VI)(N)(salchda)(CH3OH)](+) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion), are highly electrophilic. This complex reacts readily at ambient conditions with a variety of nucleophiles at rates that are much faster than similar reactions using Os(VI)≡N. This complex also carries out unique reactions, including the direct aziridination of alkenes, C-H bond activation of alkanes and C-N bond cleavage of anilines. The addition of ligands such as pyridine can enhance the reactivity of [Ru(VI)(N)(salchda)(CH3OH)](+). Therefore researchers can tune the reactivity of Ru≡N by adding a ligand L trans to nitride: L-Ru≡N. Moreover, the addition of various nucleophiles (Nu) to Ru(VI)≡N initially generate the ruthenium(IV) imido species Ru(IV)-N(Nu), a new class of hydrogen-atom transfer (HAT) reagents. Nucleophiles also readily add to coordinated Schiff base ligands in Os(VI)≡N and Ru(VI)≡N complexes. These additions are often stereospecific, suggesting that the nitrido ligand has a directing effect on the incoming nucleophile. M≡N is also

Metallic Borides, La 2 Re 3 B 7 and La 3 Re 2 B 5 , Featuring Extensive Boron–Boron Bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bugaris, Daniel E.; Malliakas, Christos D.; Chung, Duck Young

We synthesized La 2Re 3B 7 and La 3Re 2B 5 in single-crystalline form from a molten La/Ni eutectic at 1000°C, in the first example of the flux crystal growth of ternary rare-earth rhenium borides. Both compounds crystallize in their own orthorhombic structure types, with La 2Re 3B 7 (space group Pcca) having lattice parameters a = 7.657(2) Å, b = 6.755(1) Å, and c = 11.617(2) Å, and La 3Re 2B 5 (space group Pmma) having lattice parameters a = 10.809(2) Å, b = 5.287(1) Å, and c = 5.747(1) Å. Furthermore, the compounds possess three-dimensional framework structures thatmore » are built up from rhenium boride polyhedra and boron-boron bonding. La 3Re 2B 5 features fairly common B 2 dumbbells, whereas La 2Re 3B 7 has unique one-dimensional subunits composed of alternating triangular B3 and trans-B4 zigzag chain fragments. Also observed in La 3Re 2B 5 is an unusual coordination of B by an octahedron of La atoms. Electronic band structure calculations predict that La 2Re 3B 7 is a semimetal, which is observed in the electrical resistivity data as measured on single crystals, with behavior obeying the Bloch-Grüneisen model and a room-temperature resistivity ρ300K of ~ 375 μΩ cm. The electronic band structure calculations also suggest that La 3Re 2B 5 is a regular metal.« less

Correlation between structural stability of LiBH4 and cation electronegativity in metal borides: an experimental insight for catalyst design.

PubMed

Cai, Weitong; Yang, Yuanzheng; Tao, Pingjun; Ouyang, Liuzhang; Wang, Hui

2018-04-03

Nanosized metal borides MBx (M = Mg, Ti, Fe, Si) are found to play an important role in enhancing the hydrogen storage performance of LiBH4 in this work. The hydrogen storage behavior and mechanism of these modified systems are investigated through TPD-MS, XRD, FTIR and SEM characterization methods. By introducing these metal borides into LiBH4 through ball milling, the systems display three dehydrogenation stages disclosing their similarity and distinction. The 1st stage starts at 190 °C, the 2nd stage ranges from 280 °C to 400 °C and the 3rd stage ends at 550 °C with a peak at round 440 °C similar to that of pristine LiBH4. Distinguishing features exist at the 2nd stage revealing the effectiveness of MBx in an order of MgB2 < TiB2 < FeB < SiB4. Significantly, reversibility up to 9.7 wt% is achieved from LiBH4 with assistance of SiB4. The catalytic effect of MBx is influenced by the Pauling electronegativity of M in MBx and the interfacial contact characteristic between LiBH4 and MBx. The larger electronegativity leads to an enhanced catalytic effect and consequently lower temperature at the major stage. In contrast to the components in the solid state, the molten LiBH4 promotes a catalytic effect due to a superior interfacial contact. These results provide an insight into designing high-performance catalysts applied to LiBH4 as a hydrogen storage material.

Metallic Borides, La 2 Re 3 B 7 and La 3 Re 2 B 5 , Featuring Extensive Boron–Boron Bonding

DOE PAGES

Bugaris, Daniel E.; Malliakas, Christos D.; Chung, Duck Young; ...

2016-01-26

We synthesized La 2Re 3B 7 and La 3Re 2B 5 in single-crystalline form from a molten La/Ni eutectic at 1000°C, in the first example of the flux crystal growth of ternary rare-earth rhenium borides. Both compounds crystallize in their own orthorhombic structure types, with La 2Re 3B 7 (space group Pcca) having lattice parameters a = 7.657(2) Å, b = 6.755(1) Å, and c = 11.617(2) Å, and La 3Re 2B 5 (space group Pmma) having lattice parameters a = 10.809(2) Å, b = 5.287(1) Å, and c = 5.747(1) Å. Furthermore, the compounds possess three-dimensional framework structures thatmore » are built up from rhenium boride polyhedra and boron-boron bonding. La 3Re 2B 5 features fairly common B 2 dumbbells, whereas La 2Re 3B 7 has unique one-dimensional subunits composed of alternating triangular B3 and trans-B4 zigzag chain fragments. Also observed in La 3Re 2B 5 is an unusual coordination of B by an octahedron of La atoms. Electronic band structure calculations predict that La 2Re 3B 7 is a semimetal, which is observed in the electrical resistivity data as measured on single crystals, with behavior obeying the Bloch-Grüneisen model and a room-temperature resistivity ρ300K of ~ 375 μΩ cm. The electronic band structure calculations also suggest that La 3Re 2B 5 is a regular metal.« less

Boride Formation Induced by pcBN Tool Wear in Friction-Stir-Welded Stainless Steels

NASA Astrophysics Data System (ADS)

Park, Seung Hwan C.; Sato, Yutaka S.; Kokawa, Hiroyuki; Okamoto, Kazutaka; Hirano, Satoshi; Inagaki, Masahisa

2009-03-01

The wear of polycrystalline cubic boron nitride (pcBN) tool and its effect on second phase formation were investigated in stainless steel friction-stir (FS) welds. The nitrogen content and the flow stress were analyzed in these welds to examine pcBN tool wear. The nitrogen content in stir zone (SZ) was found to be higher in the austenitic stainless steel FS welds than in the ferritic and duplex stainless steel welds. The flow stress of austenitic stainless steels was almost 1.5 times larger than that of ferritic and duplex stainless steels. These results suggest that the higher flow stress causes the severe tool wear in austenitic stainless steels, which results in greater nitrogen pickup in austenitic stainless steel FS welds. From the microstructural observation, a possibility was suggested that Cr-rich borides with a crystallographic structure of Cr2B and Cr5B3 formed through the reaction between the increased boron and nitrogen and the matrix during FS welding (FSW).

The low-lying quartet electronic states of group 14 diatomic borides XB (X = C, Si, Ge, Sn, Pb)

NASA Astrophysics Data System (ADS)

Pontes, Marcelo A. P.; de Oliveira, Marcos H.; Fernandes, Gabriel F. S.; Da Motta Neto, Joaquim D.; Ferrão, Luiz F. A.; Machado, Francisco B. C.

2018-04-01

The present work focuses in the characterization of the low-lying quartet electronic and spin-orbit states of diatomic borides XB, in which X is an element of group 14 (C, Si, Ge, Sn, PB). The wavefunction was obtained at the CASSCF/MRCI level with a quintuple-ζ quality basis set. Scalar relativistic effects were also taken into account. A systematic and comparative analysis of the spectroscopic properties for the title molecular series was carried out, showing that the (1)4Π→X4Σ- transition band is expected to be measurable by emission spectroscopy to the GeB, SnB and PbB molecules, as already observed for the lighter CB and SiB species.

History of ``NANO''-Scale VERY EARLY Solid-State (and Liquid-State) Physics/Chemistry/Metallurgy/ Ceramics; Interstitial-Alloys Carbides/Nitrides/Borides/...Powders and Cermets, Rock Shocks, ...

NASA Astrophysics Data System (ADS)

Maiden, Colin; Siegel, Edward

History of ``NANO'': Siegel-Matsubara-Vest-Gregson[Mtls. Sci. and Eng. 8, 6, 323(`71); Physica Status Solidi (a)11,45(`72)] VERY EARLY carbides/nitrides/borides powders/cermets solid-state physics/chemistry/metallurgy/ ceramics FIRST-EVER EXPERIMENTAL NANO-physics/chemistry[1968 ->Physica Status Solidi (a)11,45(`72); and EARLY NANO-``physics''/NANO-``chemistry'' THEORY(after: Kubo(`62)-Matsubara(`60s-`70s)-Fulde (`65) [ref.: Sugano[Microcluster-Physics, Springer('82 `98)

Rhenium-osmium and samarium-neodymium isotopic systematics of the stillwater complex

USGS Publications Warehouse

Lambert, D.D.; Morgan, J.W.; Walker, R.J.; Shirey, S.B.; Carlson, R.W.; Zientek, M.L.; Koski, M.S.

1989-01-01

Isotopic data for the Stillwater Complex, Montana , which formed about 2700 Ma (million years ago), were obtained to evaluate the role of magma mixing in the formation of strategic platinum-group element (PGE) ore deposits. Neodymium and osmium isotopic data indicate that the intrusion formed from at least two geochemically distinct magmas. Ultramafic affinity (U-type) magmas had initial ??Nd of -0.8 to -3.2 and a chondritic initial 187Os/186Os ratio of ???0.88, whereas anorthositic affinity (A-type) magmas had ??Nd of -0.7 to +1.7 and an initial 187Os/186Os ratio of ???1.13. These data suggest that U-type magmas were derived from a lithospheric mantle source containing recycled crustal materials whereas A-type magmas originated either by crustal contamination of basaltic magmas or by partial melting of basalt in the lower crust. The Nd and Os isotopic data also suggest that Os, and probably the other PGEs in ore horizons such as the J-M Reef, was derived from A-type magmas. The Nd and Os isotopic heterogeneity observed in rocks below the J-M Reef also suggests that A-type magmas were injected into the Stillwater U-type magma chamber at several stages during the development of the Ultramafic series.

Processing development of 4 tantalum carbide-hafnium carbide and related carbides and borides for extreme environments

NASA Astrophysics Data System (ADS)

Gaballa, Osama Gaballa Bahig

Carbides, nitrides, and borides ceramics are of interest for many applications because of their high melting temperatures and good mechanical properties. Wear-resistant coatings are among the most important applications for these materials. Materials with high wear resistance and high melting temperatures have the potential to produce coatings that resist degradation when subjected to high temperatures and high contact stresses. Among the carbides, Al4SiC4 is a low density (3.03 g/cm3), high melting temperature (>2000°C) compound, characterized by superior oxidation resistance, and high compressive strength. These desirable properties motivated this investigation to (1) obtain high-density Al4SiC4 at lower sintering temperatures by hot pressing, and (2) to enhance its mechanical properties by adding WC and TiC to the Al4SiC4. Also among the carbides, tantalum carbide and hafnium carbide have outstanding hardness; high melting points (3880°C and 3890°C respectively); good resistance to chemical attack, thermal shock, and oxidation; and excellent electronic conductivity. Tantalum hafnium carbide (Ta4HfC 5) is a 4-to-1 ratio of TaC to HfC with an extremely high melting point of 4215 K (3942°C), which is the highest melting point of all currently known compounds. Due to the properties of these carbides, they are considered candidates for extremely high-temperature applications such as rocket nozzles and scramjet components, where the operating temperatures can exceed 3000°C. Sintering bulk components comprised of these carbides is difficult, since sintering typically occurs above 50% of the melting point. Thus, Ta4 HfC5 is difficult to sinter in conventional furnaces or hot presses; furnaces designed for very high temperatures are expensive to purchase and operate. Our research attempted to sinter Ta4HfC5 in a hot press at relatively low temperature by reducing powder particle size and optimizing the powder-handling atmosphere, milling conditions, sintering

Osmium uptake, distribution, and 187Os/188Os and 187Re/188Os compositions in Phaeophyceae macroalgae, Fucus vesiculosus: Implications for determining the 187Os/188Os composition of seawater

NASA Astrophysics Data System (ADS)

Racionero-Gómez, B.; Sproson, A. D.; Selby, D.; Gannoun, A.; Gröcke, D. R.; Greenwell, H. C.; Burton, K. W.

2017-02-01

The osmium isotopic composition (187Os/188Os) of seawater reflects the balance of input from mantle-, continental- and anthropogenic-derived sources. This study utilizes the Phaeophyceae, Fucus vesiculosus, to analyse its Os abundance and uptake, as well as to assess if macroalgae records the Os isotope composition of the seawater in which it lives. The data demonstrates that Os is not located in one specific biological structure within macroalgae, but is found throughout the organism. Osmium uptake was measured by culturing F. vesiculosus non-fertile tips with different concentrations of Os with a known 187Os/188Os composition (∼0.16), which is significantly different from the background isotopic composition of local seawater (∼0.94). The Os abundance of cultured non-fertile tips show a positive correlation to the concentration of the Os doped seawater. Moreover, the 187Os/188Os composition of the seaweed equalled that of the culture medium, strongly confirming the possible use of macroalgae as a biological proxy for the Os isotopic composition of the seawater.

POP-pincer osmium-polyhydrides: head-to-head (Z)-dimerization of terminal alkynes.

PubMed

Alós, Joaquín; Bolaño, Tamara; Esteruelas, Miguel A; Oliván, Montserrat; Oñate, Enrique; Valencia, Marta

2013-05-20

A wide range of osmium-polyhydride complexes stabilized by the POP-pincer ligand xant(P(i)Pr2)2 (9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) have been synthesized through cis-OsCl2{κ-S-(DMSO)4} (1, DMSO = dimethyl sulfoxide). Treatment of toluene solutions of this adduct with the diphosphine, under reflux, leads to OsCl2{xant(P(i)Pr2)2}(κ-S-DMSO) (2). The reaction of 2 with H2 in the presence of Et3N affords OsH3Cl{xant(P(i)Pr2)2} (3), which can be also prepared by addition of xant(P(i)Pr2)2 to toluene solutions of the unsaturated d(4)-trihydride OsH3Cl(P(i)Pr3)2 (5). Complex 3 reductively eliminates H2 in toluene at 90 °C. In the presence of dimethyl sulfoxide, the resulting monohydride is trapped by the S-donor molecule to give OsHCl{xant(P(i)Pr2)2}(κ-S-DMSO) (6). The reaction of 2 with H2 is sensible to the Brønsted base. Thus, in contrast to Et3N, NaH removes both chloride ligands and the hexahydride OsH6{xant(P(i)Pr2)2} (7), containing a κ(2)-P-binding diphosphine, is formed under 3 atm of hydrogen at 50 °C. Complex 7 releases a H2 molecule to yield the tetrahydride OsH4{xant(P(i)Pr2)2} (8), which can be also prepared by reaction of OsH6(P(i)Pr3)2 (9) with xant(P(i)Pr2)2. Complex 8 reduces H(+) to give, in addition to H2, the oxidized OsH4-species [OsH4(OTf){xant(P(i)Pr2)2}](+) (10, OTf = trifluoromethanesulfonate). The redox process occurs in two stages via the OsH5-cation [OsH5{xant(P(i)Pr2)2}](+) (11). The metal oxidation state four can be recovered. The addition of acetonitrile to 10 leads to [OsH2(η(2)-H2)(CH3CN){xant(P(i)Pr2)2}](2+) (12). The deprotonation of 12 yields the osmium(IV) trihydride [OsH3(CH3CN){xant(P(i)Pr2)2}](+) (13), which is also formed by addition of HOTf to the acetonitrile solutions of 8. The latter is further an efficient catalyst precursor for the head-to-head (Z)-dimerization of phenylacetylene and tert-butylacetylene. During the activation process of the tetrahydride, the bis(alkynyl)vinylidene derivatives Os

Analysis of the spectrum of the (5d6+5d56s) -(5d56p+5d46s6p) transitions of two times ionized osmium (Os III)

NASA Astrophysics Data System (ADS)

Azarov, Vladimir I.; Tchang-Brillet, W.-Ü. Lydia; Gayasov, Robert R.

2018-05-01

The spectrum of osmium was observed in the (225-2100) Å wavelength region. The (5d6 + 5d56s) - (5d56p + 5d46s6p) transition array of two times ionized osmium, Os III, has been investigated and 1039 spectral lines have been classified in the region. The analysis has led to the determination of the 5d6, 5d56s, 5d56p and 5d46s6p configurations. Fifty-eight levels of the 5d6 and 5d56s configurations in the even system and 142 levels of the 5d56p and 5d46s6p configurations in the odd system have been established. The orthogonal operators technique was used to calculate the level structure and transition probabilities. The energy parameters have been determined by the least squares fit to the observed levels. Calculated transition probability and energy values, as well as LS-compositions obtained from the fitted parameters are presented.

Magnetism and structural chemistry of ternary borides RE2MB 6 ( RE = rare earth, M = Ru, Os)

NASA Astrophysics Data System (ADS)

Hiebl, K.; Rogl, P.; Nowotny, H.

1984-10-01

The magnetic behavior of the ternary borides RE2RuB 6 and RE2OsB 6 ( RE = Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) was studied in the temperature range 1.5 K < T < 1100 K. All compounds crystallize with the Y 2ReB 6-type structure and are characterized by direct RE- RE contacts and the formation of planar infinite two-dimensional rigid boron nets. The magnetic properties reveal a typical Van Vleck paramagnetism of free RE3+-ions at temperatures higher than 200 K with ferromagnetic interaction in the low-temperature range T < 55 K. The ferromagnetic ordering temperatures vary with the De Gennes factor. There is no indication for a magnetic contribution from the Ru(Os)-sublattice. Above 1.8 K none of the samples were found to be superconducting.

Osmium(III) analogues of KP1019: electrochemical and chemical synthesis, spectroscopic characterization, X-ray crystallography, hydrolytic stability, and antiproliferative activity.

PubMed

Kuhn, Paul-Steffen; Büchel, Gabriel E; Jovanović, Katarina K; Filipović, Lana; Radulović, Siniša; Rapta, Peter; Arion, Vladimir B

2014-10-20

A one-electron reduction of osmium(IV) complexes trans-[Os(IV)Cl4(Hazole)2], where Hazole = 1H-pyrazole ([1](0)), 2H-indazole ([2](0)), 1H-imidazole ([3](0)), and 1H-benzimidazole ([4](0)), afforded a series of eight new complexes as osmium analogues of KP1019, a lead anticancer drug in clinical trials, with the general formula (cation)[trans-Os(III)Cl4(Hazole)2], where cation = H2pz(+) (H2pz[1]), H2ind(+) (H2ind[2]), H2im(+) (H2im[3]), Ph4P(+) (Ph4P[3]), nBu4N(+) (nBu4N[3]), H2bzim(+) (H2bzim[4]), Ph4P(+) (Ph4P[4]), and nBu4N(+) (nBu4N[4]). All complexes were characterized by elemental analysis, (1)H NMR spectroscopy, electrospray ionization mass spectrometry, UV-vis spectroscopy, cyclic voltammetry, while H2pz[1], H2ind[2], and nBu4[3], in addition, by X-ray diffraction. The reduced species [1](-) and [4](-) are stable in aqueous media in the absence of air oxygen and do not react with small biomolecules such as amino acids and the nucleotide 5'-dGMP. Cell culture experiments in five different human cancer cell lines (HeLa, A549, FemX, MDA-MB-453, and LS-174) and one noncancerous cell line (MRC-5) were performed, and the results were discussed and compared to those for KP1019 and cisplatin. Benzannulation in complexes with similar structure enhances antitumor activity by several orders of magnitude, implicating different mechanisms of action of the tested compounds. In particular, complexes H2ind[2] and H2bzim[4] exhibited significant antiproliferative activity in vitro when compared to H2pz[1] and H2im[3].

Preliminary investigation of zirconium boride ceramals for gas-turbine blade applications

NASA Technical Reports Server (NTRS)

Hoffman, Charles A

1953-01-01

Zirconium boride ZrB2 ceramals were investigated for possible gas-turbine-blade application. Included in the study were thermal shock evaluations of disks, preliminary turbine-blade operation, and observations of oxidation resistance. Thermal shock disks of the following three compositions were studied: (a) 97.5 percent ZrB2 plus 2.5 percent B by weight; (b) 92.5 percent ZrB2 plus 7.5 percent B by weight; and (c) 100 percent ZrB2. Thermal shock disks were quenched from temperatures of 1800 degrees, 2000 degrees, 2200 degrees, and 2400 degrees F. The life of turbine blades containing 93 percent ZrB2 plus 7 percent B by weight was determined in gas-turbine tests. The blades were run at approximately 1600 degrees F and 15,000 to 26,000 rpm. The thermal shock resistance of the 97.5 percent ZrB2 plus 2.5 percent boron ceramals compares favorably with that of TiC plus Co and TiC plus Ni ceramals. Oxidation of the disks during the thermal shock evaluation was slight for the comparatively short time (8.3 hr) up through 2000 degrees F. Oxidation of a specimen was severe, however, after 100 hours at 2000 degrees F. The turbine blade performance evaluation of the 93 percent ZrB2 plus 7 percent B composition was preliminary in scope ; no conclusions can be drawn.

Electronic, structural and magnetic studies of niobium borides of group 8 transition metals, Nb2MB2 (M=Fe, Ru, Os) from first principles calculations

NASA Astrophysics Data System (ADS)

Touzani, Rachid St.; Fokwa, Boniface P. T.

2014-03-01

The Nb2FeB2 phase (U3Si2-type, space group P4/mbm, no. 127) is known for almost 50 years, but until now its magnetic properties have not been investigated. While the synthesis of Nb2OsB2 (space group P4/mnc, no. 128, a twofold superstructure of U3Si2-type) with distorted Nb-layers and Os2-dumbbells was recently achieved, "Nb2RuB2" is still not synthesized and its crystal structure is yet to be revealed. Our first principles density functional theory (DFT) calculations have confirmed not only the experimental structures of Nb2FeB2 and Nb2OsB2, but also predict "Nb2RuB2" to crystalize with the Nb2OsB2 structure type. According to chemical bonding analysis, the homoatomic B-B interactions are optimized and very strong, but relatively strong heteroatomic M-B, B-Nb and M-Nb bonds (M=Fe, Ru, Os) are also found. These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of these ternary borides. The density-of-states at the Fermi level predicts metallic behavior, as expected, from metal-rich borides. Analysis of possible magnetic structures concluded preferred antiferromagnetic ordering for Nb2FeB2, originating from ferromagnetic interactions within iron chains and antiferromagnetic exchange interactions between them.

High Pressure Elastic Constants of High-Pressure Iron Analog Osmium

NASA Astrophysics Data System (ADS)

Godwal, B. K.; Geballe, Z.; Jeanloz, R.

2011-12-01

Understanding the elasticity of hcp iron is important both for ascertaining the stable phase and for explaining the observed seismic anomalies of Earth's inner core. A systematic experimental study of analog materials is warranted because experiments at inner-core conditions remain exceptionally challenging and theory has yielded conflicting results for iron. The deformation of hexagonal close-packed (hcp) Os, an analog for the high-pressure hcp form of Fe, has been characterized under non-hydrostatic stresses using synchrotron-based angular-dispersive radial x-ray diffraction to pressures of 60 GPa at room temperature. Starting with published ultrasonic values of elastic constants and previous measurements of linear and volume compressibilities, we estimate the single-crystal elasticity tensor of osmium to 60 GPa and find that the crystal orientation with the largest shear modulus, (002), accommodates the largest shear stress (10 GPa) and a differential strain surpassing the Voigt iso-strain limit. We find the conventional elastic model, bounded by Reuss (iso-stress) and Voigt limits, inadequate for explaining our measurements. Instead, we infer that plastic deformation limits the amount of shear stress supported by the crystal planes near the a-axis, causing the more elastically strong c-axis to support the majority of the differential strain. This conclusion is consistent with the elasto-plastic self-consistent approach used to model the effect of plasticity on the high-pressure deformation of hcp-Co (Merkel et al, PRB 79, 064110 (2009)). Importantly, we document a strength anisotropy so large that the Voigt (elastic) limit is clearly surpassed.

Transition metal carbides, nitrides and borides, and their oxygen containing analogs useful as water gas shift catalysts

DOEpatents

Thompson, Levi T.; Patt, Jeremy; Moon, Dong Ju; Phillips, Cory

2003-09-23

Mono- and bimetallic transition metal carbides, nitrides and borides, and their oxygen containing analogs (e.g. oxycarbides) for use as water gas shift catalysts are described. In a preferred embodiment, the catalysts have the general formula of M1.sub.A M2.sub.B Z.sub.C O.sub.D, wherein M1 is selected from the group consisting of Mo, W, and combinations thereof; M2 is selected from the group consisting of Fe, Ni, Cu, Co, and combinations thereof; Z is selected from the group consisting of carbon, nitrogen, boron, and combinations thereof; A is an integer; B is 0 or an integer greater than 0; C is an integer; O is oxygen; and D is 0 or an integer greater than 0. The catalysts exhibit good reactivity, stability, and sulfur tolerance, as compared to conventional water shift gas catalysts. These catalysts hold promise for use in conjunction with proton exchange membrane fuel cell powered systems.

Low-cost industrially available molybdenum boride and carbide as "platinum-like" catalysts for the hydrogen evolution reaction in biphasic liquid systems.

PubMed

Scanlon, Micheál D; Bian, Xiaojun; Vrubel, Heron; Amstutz, Véronique; Schenk, Kurt; Hu, Xile; Liu, BaoHong; Girault, Hubert H

2013-02-28

Rarely reported low-cost molybdenum boride and carbide microparticles, both of which are available in abundant quantities due to their widespread use in industry, adsorb at aqueous acid-1,2-dichloroethane interfaces and efficiently catalyse the hydrogen evolution reaction in the presence of the organic electron donor - decamethylferrocene. Kinetic studies monitoring biphasic reactions by UV/vis spectroscopy, and further evidence provided by gas chromatography, highlight (a) their superior rates of catalysis relative to other industrially significant transition metal carbides and silicides, as well as a main group refractory compound, and (b) their highly comparable rates of catalysis to Pt microparticles of similar dimensions. Insight into the catalytic processes occurring for each adsorbed microparticle was obtained by voltammetry at the liquid-liquid interface.

X-Ray photoelectron spectroscopy study of radiofrequency-sputtered titanium, carbide, molybdenum carbide, and titanium boride coatings and their friction properties

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Wheeler, D. R.

1977-01-01

Radiofrequency sputtered coatings of titanium carbide, molybdenum carbide and titanium boride were tested as wear resistant coatings on stainless steel in a pin on disk apparatus. X-ray photoelectron spectroscopy (XPS) was used to analyze the sputtered films with regard to both bulk and interface composition in order to obtain maximum film performance. Significant improvements in friction behavior were obtained when properly biased films were deposited on deliberately preoxidized substrates. XPS depth profile data showed thick graded interfaces for bias deposited films even when adherence was poor. The addition of 10 percent hydrogen to the sputtering gas produced coatings with thin poorly adherent interfaces. Results suggest that some of the common practices in the field of sputtering may be detrimental to achieving maximum adherence and optimum composition for these refractory compounds.

The Influence of Nano-Scale Silicon Nitride Additions on the Physical and Magnetic Properties of Iron Sheathed Magnesium Boride Wires

NASA Astrophysics Data System (ADS)

Zhu, W.; Cave, J.

2006-03-01

The enhancement of flux line pinning in magnesium boride wires is a critical issue for their future applications in devices and machines. It is well known that small size dopants can significantly influence the current densities of these materials. Here, the influence of nanometric (<30nm) silicon nitride on physical properties and current density is presented. The iron-sheathed powder in tube wires were prepared using pure magnesium and boron powders with silicon nitride additions. The wires were rolled flat and treated at up to 900 degrees C in flowing argon. SEM and XRD were used to identify phases and microstructures. Magnetization critical currents, up to several 100 of thousands A/cm2, at various temperatures and fields (5K - 20K and up to 3 tesla) show that there are competing mechanisms from chemical and flux pinning effects.

High-pressure structural parameters and equation of state of osmium to 207 GPa

DOE PAGES

Perreault, Christopher S.; Velisavljevic, Nenad; Vohra, Yogesh K.; ...

2017-09-08

We studied the most incompressible transition metal osmium (Os) under high pressure. There is significant interest in Os because of the structural anomalies attributed to topological transitions in the Fermi surface for valence electrons in the hexagonal close-packed phase. We report on measurements of structural parameters and equation of state on Os metal to a pressure of 207 GPa at ambient temperature using platinum as a pressure standard. We also obtained angle-dispersive X-ray diffraction data at a synchrotron source with closely spaced pressure intervals to observe any discontinuities or anomalies in the axial c/a ratio at high pressures. Rietveld refinementsmore » of X-ray diffraction data show a slowly varying axial ratio (c/a) with a broad minimum at 75 GPa. Our data do not provide any evidence of anomalous behavior in the c/a ratio in Os at 25 or 150 GPa as have been reported in previous studies. These experimental results are in agreement with theoretical calculations that do not predict any anomalous behavior in c/a ratio in Os under extreme conditions. We present an equation of state for Os to 207 GPa (V/V 0 = 0.761) at ambient temperature and compare our results with the previously published data.« less

High-pressure structural parameters and equation of state of osmium to 207 GPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perreault, Christopher S.; Velisavljevic, Nenad; Vohra, Yogesh K.

We studied the most incompressible transition metal osmium (Os) under high pressure. There is significant interest in Os because of the structural anomalies attributed to topological transitions in the Fermi surface for valence electrons in the hexagonal close-packed phase. We report on measurements of structural parameters and equation of state on Os metal to a pressure of 207 GPa at ambient temperature using platinum as a pressure standard. We also obtained angle-dispersive X-ray diffraction data at a synchrotron source with closely spaced pressure intervals to observe any discontinuities or anomalies in the axial c/a ratio at high pressures. Rietveld refinementsmore » of X-ray diffraction data show a slowly varying axial ratio (c/a) with a broad minimum at 75 GPa. Our data do not provide any evidence of anomalous behavior in the c/a ratio in Os at 25 or 150 GPa as have been reported in previous studies. These experimental results are in agreement with theoretical calculations that do not predict any anomalous behavior in c/a ratio in Os under extreme conditions. We present an equation of state for Os to 207 GPa (V/V 0 = 0.761) at ambient temperature and compare our results with the previously published data.« less

Superconducting and normal-state properties of the layered boride OsB2

NASA Astrophysics Data System (ADS)

Singh, Yogesh; Niazi, A.; Vannette, M. D.; Prozorov, R.; Johnston, D. C.

2007-12-01

OsB2 crystallizes in an orthorhombic structure (Pmmn) which contains alternate boron and osmium layers stacked along the c axis. The boron layers consist of puckered hexagons as opposed to the flat graphite-like boron layers in MgB2 . OsB2 is reported to become superconducting below 2.1K . We report results of the dynamic and static magnetic susceptibilities, electrical resistivity, Hall effect, heat capacity, and penetration depth measurements on arc-melted polycrystalline samples of OsB2 to characterize its superconducting and normal-state properties. These measurements confirmed that OsB2 becomes a bulk superconductor below Tc=2.1K . Our results indicate that OsB2 is a moderate-coupling type-II superconductor with an electron-phonon coupling constant λep≈0.4-0.5 , a small Ginzburg-Landau parameter κ˜1-2 , and an upper critical magnetic field Hc2(0.5K)˜420Oe for an unannealed sample and Hc2(1K)˜330Oe for an annealed sample. The temperature dependence of the superfluid density ns(T) for the unannealed sample is consistent with an s -wave superconductor with a slightly enhanced zero temperature gap Δ(0)=1.9kBTc and a zero temperature London penetration depth λ(0)=0.38(2)μm . The ns(T) data for the annealed sample show deviations from the predictions of the single-band s -wave BCS model. The magnetic, transport, and thermal properties in the normal state of isostructural and isoelectronic RuB2 , which is reported to become superconducting below 1.6K , are also reported.

Osmium isotope perturbations during the Pliensbachian-Toarcian (Early Jurassic): Relationships between volcanism, weathering, and climate change

NASA Astrophysics Data System (ADS)

Percival, Lawrence; Cohen, Anthony; Davies, Marc; Dickson, Alexander; Jenkyns, Hugh; Hesselbo, Stephen; Mather, Tamsin; Xu, Weimu; Storm, Marisa

2016-04-01

The Mesozoic Era marked a time of greenhouse conditions on Earth, punctuated by a number of abrupt perturbations to the carbon cycle, such as Ocean Anoxic Events (OAEs). OAEs are typically marked in the stratigraphic record by the appearance of organic-rich shales, and excursions in carbon-isotope ratios registered in carbonates and organic matter. A range of geochemical evidence indicates changes to global temperatures, typically featuring abrupt warming possibly caused by CO2 emissions resulting from Large Igneous Province (LIP) volcanism. A warmer atmosphere is thought to have led to changes in the global hydrological cycle, which would likely have enhanced global weathering rates. The Toarcian OAE (T-OAE) is inferred, from osmium isotope ratios in organic-rich mudrocks from Yorkshire and western North America, to have been a time of such increased weathering rates. However, it is likely that the sediments at these locations were deposited in relatively hydrographically restricted environments, potentially more susceptible to the influence of local input; consequently, they may not offer the best representation of the global seawater Os-isotope composition at that time. In this study, we have measured the osmium isotope composition of siciliclastic mudrocks in a core from the Mochras borehole (Llanbedr Farm, Cardigan Bay Basin, Wales), which constitutes a sedimentary record for a fully open-marine seaway that connected Tethys to the Boreal ocean during the Toarcian. We analysed samples from strata including both the T-OAE and preceding Pliensbachian-Toarcian boundary (Pl-To), both of which record multiple geochemical excursions and records of elevated extinction amongst benthic fauna. We find that the latest Pliensbachian records seawater 187Os/188Os of ~0.35-0.4, rising to ~0.5 at the Pl-To boundary, before a further rise to ~0.7 during the T-OAE. We conclude that such increases in radiogenic Os flux to the ocean system resulted from enhanced continental

Extreme mechanical properties of materials under extreme pressure and temperature conditions (Invited)

NASA Astrophysics Data System (ADS)

Kavner, A.; Armentrout, M. M.; Xie, M.; Weinberger, M.; Kaner, R. B.; Tolbert, S. H.

2010-12-01

A strong synergy ties together the high-pressure subfields of mineral physics, solid-state physics, and materials engineering. The catalog of studies measuring the mechanical properties of materials subjected to large differential stresses in the diamond anvil cell demonstrates a significant pressure-enhancement of strength across many classes of materials, including elemental solids, salts, oxides, silicates, and borides and nitrides. High pressure techniques—both radial diffraction and laser heating in the diamond anvil cell—can be used to characterize the behavior of ultrahard materials under extreme conditions, and help test hypotheses about how composition, structure, and bonding work together to govern the mechanical properties of materials. The principles that are elucidated by these studies can then be used to help design engineering materials to encourage desired properties. Understanding Earth and planetary interiors requires measuring equations of state of relevant materials, including oxides, silicates, and metals under extreme conditions. If these minerals in the diamond anvil cell have any ability to support a differential stress, the assumption of quasi-hydrostaticity no longer applies, with a resulting non-salubrious effect on attempts to measure equation of state. We illustrate these applications with the results of variety of studies from our laboratory and others’ that have used high-pressure radial diffraction techniques and also laser heating in the diamond anvil cell to characterize the mechanical properties of a variety of ultrahard materials, especially osmium metal, osmium diboride, rhenium diboride, and tungsten tetraboride. We compare ambient condition strength studies such as hardness testing with high-pressure studies, especially radial diffraction under differential stress. In addition, we outline criteria for evaluating mechanical properties of materials at combination high pressures and temperatures. Finally, we synthesize our

On the transferability of electron density in binary vanadium borides VB, V3B4 and VB2.

PubMed

Terlan, Bürgehan; Akselrud, Lev; Baranov, Alexey I; Borrmann, Horst; Grin, Yuri

2015-12-01

Binary vanadium borides are suitable model systems for a systematic analysis of the transferability concept in intermetallic compounds due to chemical intergrowth in their crystal structures. In order to underline this structural relationship, topological properties of the electron density in VB, V3B4 and VB2 reconstructed from high-resolution single-crystal X-ray diffraction data as well as derived from quantum chemical calculations, are analysed in terms of Bader's Quantum Theory of Atoms in Molecules [Bader (1990). Atoms in Molecules: A Quantum Theory, 1st ed. Oxford: Clarendon Press]. The compounds VB, V3B4 and VB2 are characterized by a charge transfer from the metal to boron together with two predominant atomic interactions, the shared covalent B-B interactions and the polar covalent B-M interactions. The resembling features of the crystal structures are well reflected by the respective B-B interatomic distances as well as by ρ(r) values at the B-B bond critical points. The latter decrease with an increase in the corresponding interatomic distances. The B-B bonds show transferable electron density properties at bond critical points depending on the respective bond distances.

A negative excursion at 14-16 Ma in seawater osmium isotope record: Implications for paleoceanographic studies using Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Goto, K. T.; Tejada, M. L. G.; Suzuki, K.

2017-12-01

Osmium isotope stratigraphy is a recently proposed method to determine the depositional age of Fe-Mn crusts [1, 2]. Seawater Os isotope (187Os/188Os) is roughly determined by the balance of riverine Os inputs with radiogenic value (187Os/188Os = 1.4), and mantle-derived and extra-terrestrial Os inputs with non-radiogenic value (187Os/188Os = 0.12) [3]. Secular variation of global seawater Os isotope (seawater Os isotope curve) has been reconstructed by the analysis of pelagic sediments and exhibits large variations ranging from 0.2 to 1.0 with several negative excursions [3]. Hence, the depositional age of Fe-Mn crusts can be approximately estimated by fitting their Os isotope depth profiles to the seawater Os isotope curve (Osmium isotope stratigraphy). However, this method allows multiple interpretations which are partly due to the lack of high-resolution seawater Os isotope curve [1, 2]. For example, the available seawater Os isotope curve does not exhibit negative anomaly during the Miocene, which contrasts with Os isotope records of Fe-Mn crusts [4]. In the present study, we obtained a high-resolution Os isotope record of Miocene seawater using hemipelagic sediments from IODP Expedition 351 SiteU1438. We found a small negative Os isotope anomaly as low as 0.7 from sediments deposited at 14-16 Ma. The magnitude of this anomaly is similar to those reported from Fe-Mn crusts. Although the extrapolation of Be-10 ages for Fe-Mn crust indicate a younger age for the anomaly ( 11 Ma) [4], we could not find any discernable isotope anomaly at 11 Ma. Our finding is consistent with the timing of major eruption of the Columbia River flood basalts (CFRB) which could provide non-radiogenic Os to seawater at 14-16 Ma [5]. Hence, we suggest that the observed isotope anomaly reflect eruption and subsequent weathering of the CFRB. As the similar Os isotope anomaly is commonly found from Fe-Mn crusts, the Os isotope anomaly at 14-16 Ma could be used as a key event to constrain

Towards understanding the mechanism of rhenium and osmium precipitation in tungsten and its implication for tungsten-based alloys

NASA Astrophysics Data System (ADS)

Li, Yu-Hao; Zhou, Hong-Bo; Deng, Huiqiu; Lu, Gang; Lu, Guang-Hong

2018-07-01

Using a first-principles method in combination with thermodynamic models, we investigate the interaction between rhenium/osmium (Re/Os) and defects to explore the mechanism of radiation-induced Re/Os precipitation in tungsten (W). We demonstrate that radiation-induced defects play a key role in the solute precipitation in W, especially for self-interstitial atoms (SIAs). The presence of SIAs can significantly reduce the total nucleation free energy change of Re/Os, and thus facilitate the nucleation of Re/Os in W. Further, SIA is shown to be easily trapped by Re/Os once overcoming a low energy barrier, forming a W-Re/Os mixed dumbbell. Such W-Re/Os dumbbell forms a high stable Re/Os-Re/Os dumbbell structure with the substitutional Re/Os atoms, which can serve as a trapping centre for subsequent interstitial-Re/Os, leading to the growth of Re/Os-rich clusters. Consequently, an interstitial-mediated migration and aggregation mechanism for Re/Os precipitation in W has been proposed. Our results reveale that the alloying elements-defects interaction has significantly effect on their behaviors under irradiation, which should be considered in the design of W-based alloys for future fusion devices.

Osmium isotope variations in the oceans recorded by Fe-Mn crusts

USGS Publications Warehouse

Burton, K.W.; Bourdon, B.; Birck, J.-L.; Allegre, C.J.; Hein, J.R.

1999-01-01

This study presents osmium (Os) isotope data for recent growth surfaces of hydrogenetic ferromanganese (Fe-Mn) crusts from the Pacific, Atlantic and Indian Oceans. In general, these data indicate a relatively uniform Os isotopic composition for modern seawater, but suggest that North Atlantic seawater is slightly more radiogenic than that of the Pacific and Indian Oceans. The systematic difference in the Os isotopic composition between the major oceans probably reflects a greater input of old continental material with a high Re/Os ratio in the North Atlantic Ocean, consistent with the distribution of Nd and Pb isotopes. This spatial variation in the Os isotope composition in seawater is consistent with a residence time for Os of between 2 and 60 kyr. Indian Ocean samples show no evidence of a local source of radiogenic Os, which suggests that the present-day riverine input from the Himalaya-Tibet region is not a major source for Os. Recently formed Fe-Mn crusts from the TAG hydrothermal field in the North Atlantic yield an Os isotopic composition close to that of modern seawater, which indicates that, in this area, the input of unradiogenic Os from the hydrothermal alteration of oceanic crust is small. However, some samples from the deep Pacific (???4 km) possess a remarkably unradiogenic Os isotope composition (187Os/186Os ratios as low as 4.3). The compositional control of Os incorporation into the crusts and mixing relationships suggest that this unradiogenic composition is most likely due to the direct incorporation of micrometeoritic or abyssal peridotite particles, rather than indicating the presence of an unradiogenic deep-water mass. Moreover, this unradiogenic signal appears to be temporary, and local, and has had little apparent effect on the overall evolution of seawater. These results confirm that input of continental material through erosion is the dominant source of Os in seawater, but it is not clear whether global Os variations are due to the input

Residency of rhenium and osmium in a heavy crude oil

NASA Astrophysics Data System (ADS)

DiMarzio, Jenna M.; Georgiev, Svetoslav V.; Stein, Holly J.; Hannah, Judith L.

2018-01-01

Rhenium-osmium (Re-Os) isotope geochemistry is an emerging tool for the study of oil formation and migration processes, and a new technology for petroleum exploration. Little is known, however, about the residency of Re and Os within asphaltene and maltene sub-fractions of crude oil. This information is crucial for understanding the 187Re-187Os radiometric clock held in petroleum systems and for interpreting geochronology for key processes such as oil formation, migration, and biodegradation. In this study, a heavy crude oil was separated into soluble (maltene, MALT) and insoluble (asphaltene, ASPH) fractions using n-heptane as the asphaltene-precipitating agent. The asphaltenes were separated sequentially into sub-fractions using two different solvent pairs (heptane-dichloromethane and acetone-toluene), and the bulk maltenes were separated into saturate, aromatic, and resin (SAR) fractions using open column chromatography. Each asphaltene and maltene sub-fraction was analyzed for Re and Os. The asphaltene sub-fractions and the bulk ASPH, MALT, and crude oil were analyzed for a suite of trace metals by ICP-MS. Our results show that Re and Os concentrations co-vary between the asphaltene sub-fractions, and that both elements are found mostly in the more polar and aromatic sub-fractions. Significant Re and Os are also present in the aromatic and resin fractions of the maltenes. However, each asphaltene and maltene sub-fraction has a distinct isotopic composition, and sub-fractions are not isochronous. This suggests that asphaltene sub-fractionation separates Re-Os complexes to the point where the isotopic integrity of the geochronometer is compromised. The mobility of individual Re and Os isotopes and the decoupling possibilities between radiogenic 187Os produced from 187Re remain elusive, but their recognition in this study is a critical first step. Re and Os correlate strongly with Mo and Cd in the asphaltene sub-fractions, suggesting that these metals occupy

Electron transfer across multiple hydrogen bonds: the case of ureapyrimidinedione-substituted vinyl ruthenium and osmium complexes.

PubMed

Pichlmaier, Markus; Winter, Rainer F; Zabel, Manfred; Zális, Stanislav

2009-04-08

Ruthenium and osmium complexes 2a,b and 3a,b featuring the N-4,6-dioxo-5,5-dibutyl- or the N-4,6-dioxo-5,5-di-(2-propenyl)-1,4,5,6-tetrahydropyrimidin-2-yl-N'(4-ethenylphenyl)-urea ligand dimerize by a self-complementary quadruply hydrogen-bonding donor/donor/acceptor/acceptor (DDAA) motif. We provide evidence that the dimeric structures are maintained in nonpolar solvents and in 0.1 M NBu(4)PF(6)/CH(2)Cl(2) supporting electrolyte solution. All complexes are reversibly oxidized in two consecutive two-electron oxidations (DeltaE(1/2) approximately = 500 mV) without any discernible potential splitting for the oxidation of the individual hydrogen-bridged redox active moieties. IR and UV/vis/NIR spectroelectrochemistry show a one-step conversion of the neutral to the dication without any discernible features of an intermediate monooxidized radical cation. Oxidation-induced IR changes of the NH and CO groups that are involved in hydrogen bonding are restricted to the styryl-bonded urea NH function. IR band assignments are aided by quantum chemical calculations. Our experimental findings clearly show that, at least in the present systems, the ureapyrimidinedione (Upy) DDAA hydrogen-bonding motif does not support electron transfer. The apparent reason is that neither of the hydrogen-bonding functionalities contributes to the occupied frontier levels. This results in nearly degenerate pairs of MOs representing the in-phase and out-of-phase combinations of the individual monomeric building blocks.

Coronary artery wall imaging in mice using osmium tetroxide and micro-computed tomography (micro-CT)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pai, Vinay M.; Kozlowski, Megan; Donahue, Danielle

2012-05-10

The high spatial resolution of micro-computed tomography (micro-CT) is ideal for 3D imaging of coronary arteries in intact mouse heart specimens. Previously, micro-CT of mouse heart specimens utilized intravascular contrast agents that hardened within the vessel lumen and allowed a vascular cast to be made. However, for mouse coronary artery disease models, it is highly desirable to image coronary artery walls and highlight plaques. For this purpose, we describe an ex vivo contrast-enhanced micro-CT imaging technique based on tissue staining with osmium tetroxide (OsO{sub 4}) solution. As a tissue-staining contrast agent, OsO{sub 4} is retained in the vessel wall andmore » surrounding tissue during the fixation process and cleared from the vessel lumens. Its high X-ray attenuation makes the artery wall visible in CT. Additionally, since OsO{sub 4} preferentially binds to lipids, it highlights lipid deposition in the artery wall. We performed micro-CT of heart specimens of 5- to 25-week-old C57BL/6 wild-type mice and 5- to 13-week-old apolipoprotein E knockout (apoE{sup -/-}) mice at 10 {mu}m resolution. The results show that walls of coronary arteries as small as 45 {mu}m in diameter are visible using a table-top micro-CT scanner. Similar image clarity was achieved with 1/2000th the scan time using a synchrotron CT scanner. In 13-week-old apoE mice, lipid-rich plaques are visible in the aorta. Our study shows that the combination of OsO{sub 4} and micro-CT permits the visualization of the coronary artery wall in intact mouse hearts.« less

Novel Routes for Sintering of Ultra-high Temperature Ceramics and their Properties

DTIC Science & Technology

2014-10-31

UHTCs charge (zirconium and hafnium borides , SiC) with additives (chromium carbide, nickel, chromium, etc.), which activate sintering process, is...temperature phases in a form of carboborides of zirconium and bi borides of zirconium or chromium. Elevation of densification rate of sintered borides is...superplasticity under the slip mechanism of zirconium boride and silica carbide grains on grain boundary interlayers with nanocrystalline grains of carbon

Detection of basal acetylcholine release in the microdialysis of rat frontal cortex by high-performance liquid chromatography using a horseradish peroxidase-osmium redox polymer electrode with pre-enzyme reactor.

PubMed

Kato, T; Liu, J K; Yamamoto, K; Osborne, P G; Niwa, O

1996-06-28

To determine the basal acetylcholine level in the dialysate of rat frontal cortex, a horseradish peroxidase-osmium redox polymer-modified glassy carbon electrode (HRP-GCE) was employed instead of the conventional platinum electrode used in high-performance liquid chromatography-electrochemical detection (HPLC-ED). In initial experiments, an oxidizable unknown compound interfered with the detection of basal acetylcholine release on HPLC-HRP-GCE. An immobilized peroxidase-choline oxidase precolumn (pre-reactor) was included in the HPLC system, to eliminate the interference from the unknown compound. This combination could detect less than 10 fmol of standard acetylcholine and basal acetylcholine levels in the dialysate from a conventional concentric design microdialysis probe, without the use of cholinesterase inhibitor, and may facilitate physiological investigation of cholinergic neuronal activity in the central nervous system.

Osmium isotope and highly siderophile element systematics of the lunar crust

NASA Astrophysics Data System (ADS)

Day, James M. D.; Walker, Richard J.; James, Odette B.; Puchtel, Igor S.

2010-01-01

Coupled 187Os/ 188Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for pristine lunar crustal rocks 60025, 62255, 65315 (ferroan anorthosites, FAN) and 76535, 78235, 77215 and a norite clast in 15455 (magnesian-suite rocks, MGS). Osmium isotopes permit more refined discrimination than previously possible of samples that have been contaminated by meteoritic additions and the new results show that some rocks, previously identified as pristine, contain meteorite-derived HSE. Low HSE abundances in FAN and MGS rocks are consistent with derivation from a strongly HSE-depleted lunar mantle. At the time of formation, the lunar floatation crust, represented by FAN, had 1.4 ± 0.3 pg g - 1 Os, 1.5 ± 0.6 pg g - 1 Ir, 6.8 ± 2.7 pg g - 1 Ru, 16 ± 15 pg g - 1 Pt, 33 ± 30 pg g - 1 Pd and 0.29 ± 0.10 pg g - 1 Re (˜ 0.00002 × CI) and Re/Os ratios that were modestly elevated ( 187Re/ 188Os = 0.6 to 1.7) relative to CI chondrites. MGS samples are, on average, characterised by more elevated HSE abundances (˜ 0.00007 × CI) compared with FAN. This either reflects contrasting mantle-source HSE characteristics of FAN and MGS rocks, or different mantle-crust HSE fractionation behaviour during production of these lithologies. Previous studies of lunar impact-melt rocks have identified possible elevated Ru and Pd in lunar crustal target rocks. The new results provide no supporting evidence for such enrichments. If maximum estimates for HSE in the lunar mantle are compared with FAN and MGS averages, crust-mantle concentration ratios ( D-values) must be ≤ 0.3. Such D-values are broadly similar to those estimated for partitioning between the terrestrial crust and upper mantle, with the notable exception of Re. Given the presumably completely different mode of origin for the primary lunar floatation crust and tertiary terrestrial continental crust, the potential similarities in crust-mantle HSE partitioning for the Earth and Moon are

Osmium isotope and highly siderophile element systematics of the lunar crust

USGS Publications Warehouse

Day, J.M.D.; Walker, R.J.; James, O.B.; Puchtel, I.S.

2010-01-01

Coupled 187Os/188Os and highly siderophile element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for pristine lunar crustal rocks 60025, 62255, 65315 (ferroan anorthosites, FAN) and 76535, 78235, 77215 and a norite clast in 15455 (magnesian-suite rocks, MGS). Osmium isotopes permit more refined discrimination than previously possible of samples that have been contaminated by meteoritic additions and the new results show that some rocks, previously identified as pristine, contain meteorite-derived HSE. Low HSE abundances in FAN and MGS rocks are consistent with derivation from a strongly HSE-depleted lunar mantle. At the time of formation, the lunar floatation crust, represented by FAN, had 1.4 ?? 0.3 pg g- 1 Os, 1.5 ?? 0.6 pg g- 1 Ir, 6.8 ?? 2.7 pg g- 1 Ru, 16 ?? 15 pg g- 1 Pt, 33 ?? 30 pg g- 1 Pd and 0.29 ?? 0.10 pg g- 1 Re (??? 0.00002 ?? CI) and Re/Os ratios that were modestly elevated (187Re/188Os = 0.6 to 1.7) relative to CI chondrites. MGS samples are, on average, characterised by more elevated HSE abundances (??? 0.00007 ?? CI) compared with FAN. This either reflects contrasting mantle-source HSE characteristics of FAN and MGS rocks, or different mantle-crust HSE fractionation behaviour during production of these lithologies. Previous studies of lunar impact-melt rocks have identified possible elevated Ru and Pd in lunar crustal target rocks. The new results provide no supporting evidence for such enrichments. If maximum estimates for HSE in the lunar mantle are compared with FAN and MGS averages, crust-mantle concentration ratios (D-values) must be ??? 0.3. Such D-values are broadly similar to those estimated for partitioning between the terrestrial crust and upper mantle, with the notable exception of Re. Given the presumably completely different mode of origin for the primary lunar floatation crust and tertiary terrestrial continental crust, the potential similarities in crust-mantle HSE partitioning for the Earth and Moon are somewhat

An XPS study of the adherence of refractory carbide, silicide, and boride RF-sputtered wear-resistant coatings. [X-ray Photoelectron Spectroscopy of steel surfaces

NASA Technical Reports Server (NTRS)

Brainard, W. A.; Wheeler, D. R.

1978-01-01

Radio frequency sputtering was used to deposit refractory carbide, silicide, and boride coatings on 440-C steel substrates. Both sputter etched and pre-oxidized substrates were used and the films were deposited with and without a substrate bias. The composition of the coatings was determined as a function of depth by X-ray photoelectron spectroscopy combined with argon ion etching. Friction and wear tests were conducted to evaluate coating adherence. In the interfacial region there was evidence that bias may produce a graded interface for some compounds. Biasing, while generally improving bulk film stoichiometry, can adversely affect adherence by removing interfacial oxide layers. Oxides of all film constituents except carbon and iron were present in all cases but the iron oxide coverage was only complete on the preoxidized substrates. The film and iron oxides were mixed in the MoSi2 and Mo2C films but layered in the Mo2B5 films. In the case of mixed oxides, preoxidation enhanced film adherence. In the layered case it did not.

Coronary artery wall imaging in mice using osmium tetroxide and micro-computed tomography (micro-CT).

PubMed

Pai, Vinay M; Kozlowski, Megan; Donahue, Danielle; Miller, Elishiah; Xiao, Xianghui; Chen, Marcus Y; Yu, Zu-Xi; Connelly, Patricia; Jeffries, Kenneth; Wen, Han

2012-05-01

The high spatial resolution of micro-computed tomography (micro-CT) is ideal for 3D imaging of coronary arteries in intact mouse heart specimens. Previously, micro-CT of mouse heart specimens utilized intravascular contrast agents that hardened within the vessel lumen and allowed a vascular cast to be made. However, for mouse coronary artery disease models, it is highly desirable to image coronary artery walls and highlight plaques. For this purpose, we describe an ex vivo contrast-enhanced micro-CT imaging technique based on tissue staining with osmium tetroxide (OsO(4) ) solution. As a tissue-staining contrast agent, OsO(4) is retained in the vessel wall and surrounding tissue during the fixation process and cleared from the vessel lumens. Its high X-ray attenuation makes the artery wall visible in CT. Additionally, since OsO(4) preferentially binds to lipids, it highlights lipid deposition in the artery wall. We performed micro-CT of heart specimens of 5- to 25-week-old C57BL/6 wild-type mice and 5- to 13-week-old apolipoprotein E knockout (apoE(-/-) ) mice at 10 μm resolution. The results show that walls of coronary arteries as small as 45 μm in diameter are visible using a table-top micro-CT scanner. Similar image clarity was achieved with 1/2000th the scan time using a synchrotron CT scanner. In 13-week-old apoE mice, lipid-rich plaques are visible in the aorta. Our study shows that the combination of OsO(4) and micro-CT permits the visualization of the coronary artery wall in intact mouse hearts. Published 2012. This article is a US Government work and is in the public domain in the USA. Journal of Anatomy © 2012 Anatomical Society.

Seawater osmium isotope evidence for a middle Miocene flood basalt event in ferromanganese crust records

USGS Publications Warehouse

Klemm, V.; Frank, M.; Levasseur, S.; Halliday, A.N.; Hein, J.R.

2008-01-01

Three ferromanganese crusts from the northeast, northwest and central Atlantic were re-dated using osmium (Os) isotope stratigraphy and yield ages from middle Miocene to the present. The three Os isotope records do not show evidence for growth hiatuses. The reconstructed Os isotope-based growth rates for the sections older than 10??Ma are higher than those determined previously by the combined beryllium isotope (10Be/9Be) and cobalt (Co) constant-flux methods, which results in a decrease in the maximum age of each crust. This re-dating does not lead to significant changes to the interpretation of previously determined radiogenic isotope neodymium, lead (Nd, Pb) time series because the variability of these isotopes was very small in the records of the three crusts prior to 10??Ma. The Os isotope record of the central Atlantic crust shows a pronounced minimum during the middle Miocene between 15 and 12??Ma, similar to a minimum previously observed in two ferromanganese crusts from the central Pacific. For the other two Atlantic crusts, the Os isotope records and their calibration to the global seawater curve for the middle Miocene are either more uncertain or too short and thus do not allow for a reliable identification of an isotopic minimum. Similar to pronounced minima reported previously for the Cretaceous/Tertiary and Eocene/Oligocene boundaries, possible interpretations for the newly identified middle Miocene Os isotope minimum include changes in weathering intensity and/or a meteorite impact coinciding with the formation of the No??rdlinger Ries Crater. It is suggested that the eruption and weathering of the Columbia River flood basalts provided a significant amount of the unradiogenic Os required to produce the middle Miocene minimum. ?? 2008 Elsevier B.V.

Analysis of Deformation Substructures in a Notched LCF Sample Under Dwell Condition in a Ni-Based Superalloy (PREPRINT)

DTIC Science & Technology

2012-08-01

interior, and carbides and borides at the grain boundaries. Blocky carbide particles can also be seen in the grain interior (Figure 1b). The borides ...can be seen distributed (b) higher magnification image of a typical grain boundary decorated with carbide and boride particles. Bi-modal distribution

Re-Os isotopic systematics in chromitites from the Stillwater Complex, Montana, USA

NASA Astrophysics Data System (ADS)

Marcantonio, Franco; Zindler, Alan; Reisberg, Laurie; Mathez, E. A.

1993-08-01

New Re-Os isotopic data on chromitites of the Stillwater Complex demonstrate isotopic equilibrium between cumulate chromite and whole rock. Initial osmium isotopic ratios for the chromitites, chosen for their freshness, are consistent with derivation from a mantle-derived magma that suffered little or no interaction with the continental crust prior to crystallization. Molybdenite, separated from a sample of the G-chromitite, yields a Re-Os age of 2740 Ma, indistinguishable from the age of the intrusion. The presence of molybdenite documents rhenium, and probably osmium, mobilization by hydrothermal fluids that permeated the intrusion shortly after crystallization. Initial osmium isotopic variability observed in chromitites and other rocks from the Stillwater Complex could result from interaction with these fluids. In this context, there is no compelling reason to call on assimilation of crust by mantle-derived magma to explain the osmium or neodymium isotopic variability. Although osmium isotopic systematics have been affected by hydrothermal processes, Re-Os results demonstrate that more than 95 percent of the osmium, and by inference other PGEs in the Stillwater Complex, derive from the mantle.

Methods of repairing a substrate

NASA Technical Reports Server (NTRS)

Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

2011-01-01

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium boride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Future Directions for Selected Topics in Physics and Materials Science

DTIC Science & Technology

2012-07-12

referred to as lightides (e.g. borides , nitrides, phosphides) • Materials for energy conversion, energy storage, energy transport and energy production...Distributed nanosystems and sensors • Strategy for multilayered combinatorics • lightides ( borides , nitrides, phosphides, • New applications for...Strategy for multilayered combinatorics Lightides ( borides , nitrides, phosphides) • Energy conversion, .storage and production • Precision control

Homogeneous dihydroxylation of olefins catalyzed by OsO(4)(2-) immobilized on a dendritic backbone with a tertiary nitrogen at its core position.

PubMed

Fujita, Ken-Ichi; Inoue, Kensuke; Tsuchimoto, Teruhisa; Yasuda, Hiroyuki

2012-01-01

OsO(4)(2-) immobilized on a poly(benzyl ether) dendrimer with a tertiary nitrogen at its core position efficiently catalyzed the homogeneous dihydroxylation of olefins with a low level of osmium leaching. The dendritic osmium catalyst could be applied to the wide range of olefins. Furthermore, the dendritic osmium catalyst was recovered by reprecipitation and then reused up to five times.

Influence of laser alloying with boron and niobium on microstructure and properties of Nimonic 80A-alloy

NASA Astrophysics Data System (ADS)

Makuch, N.; Piasecki, A.; Dziarski, P.; Kulka, M.

2015-12-01

Ni-base superalloys were widely used in aeronautics, chemical and petrochemical industries due to their high corrosion resistance, high creep and rupture strength at high temperature. However, these alloys were not considered for applications in which conditions of appreciable mechanical wear were predominant. The diffusion boriding provided suitable protection against wear. Unfortunately, this process required long duration and high temperature. In this study, instead of the diffusion process, the laser alloying with boron and niobium was used in order to produce the hard and wear resistant layer on Nimonic 80A-alloy. The laser-alloying was carried out as a two-step process. First, the external cylindrical surface of specimens was pre-placed with a paste containing boron and niobium. Then, the pre-placed coating and the thin surface layer of the substrate were re-melted by a laser beam. The high laser beam power (P=1.56 kW) and high averaging irradiance (E=49.66 kW/cm2) provided the thick laser re-melted zone. The laser-borided layers were significantly thicker (470 μm) in comparison with the layers obtained as a consequence of the diffusion boriding. Simultaneously, the high overlapping of multiple laser tracks (86%) caused that the laser-alloyed layer was uniform in respect of the thickness. The produced layer consisted of nickel borides (Ni3B, Ni2B, Ni4B3, NiB), chromium borides (CrB, Cr2B), niobium borides (NbB2, NbB) and Ni-phase. The presence of hard borides caused the increase in microhardness up to 1000 HV in the re-melted zone. However, the measured values were lower than those-characteristic of niobium borides, chromium borides and nickel borides. The presence of the soft Ni-phase in re-melted zone was the reason for such a situation. After laser alloying, the significant increase in abrasive wear resistance was also observed. The mass wear intensity factor, as well as the relative mass loss of the laser-alloyed specimens, was over 10 times smaller in

Kinetic Investigation and Wear Properties of Fe2B Layers on AISI 12L14 Steel

NASA Astrophysics Data System (ADS)

Keddam, M.; Ortiz-Dominguez, M.; Elias-Espinosa, M.; Arenas-Flores, A.; Zuno-Silva, J.; Zamarripa-Zepeda, D.; Gomez-Vargas, O. A.

2018-03-01

In the current study, the powder-pack boriding was applied to the AISI 12L14 steel in the temperature range 1123 K to 1273 K for an exposure time between 2 and 8 hours. The produced boride layer was composed of Fe2B with a sawtooth morphology. A diffusion model based on the integral method was applied to investigate the growth kinetics of Fe2B layers. As a main result, the boron diffusion coefficients in Fe2B were estimated by considering the principle of mass balance at the (Fe2B/substrate) interface with an inclusion of boride incubation times. The value of activation energy for boron diffusion in AISI 12L14 steel was estimated as 165 kJ mol-1 and compared with other values of activation energy found in the literature. An experimental validation of the present model was made by using four different boriding conditions. Furthermore, the Rockwell-C adhesion test was employed to assess the cohesion of boride layers to the base metal. The scratch and pin-on-disc tests were also carried out to analyze the effect of boriding on wear behavior of AISI 12L14 steel.

Microstructure Evolution and Composition Control during the Processing of Thin-gage Metallic Foil (Preprint)

DTIC Science & Technology

2012-02-01

the presence of somewhat randomly-distributed carbides and borides (white particles in BSE images), this grain size was comparable to that observed...pinned by carbide/ boride particles (imaging white in Figure 8c). The very fine gamma-prime precipitates likely produced during magnetron sputtering...sputtered material. First, the carbide/ boride particles were nucleated and hence located preferentially at the grain boundaries in the sputtered

Novel Routes to Tune Thermal Conductivities and Thermoelectric Properties of Materials

DTIC Science & Technology

2012-11-15

expand the possibilities of borides as functional compou nds. A series of indium-free novel TCO compounds with novel crystal structures, has...powerful methods for modification were demonstrated in the borides , silicides and oxides. Introduction: The goal of this project is to...the possibility to modify the crystal structures can expand the possibilities of borides as functional compounds. A series of indium-free novel TCO

Alloying-Element Loss during High-Temperature Processing of a Nickel-Base Superalloy (Preprint)

DTIC Science & Technology

2013-01-01

precipitates, and the fine white/gray particles are carbides and borides . ............................................. 23 Figure 2. Aluminum...comparable size, and submicron carbides and borides . A fifteen-minute heat treatment at the subsolvus temperature used in the present work (i.e...precipitates, and ~0.3 volume pct. of carbides and borides with an average diameter of ~0.3 m (Figure 1) [5, 6]. B. Procedures To establish the

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mbarki, Mohammed; Touzani, Rachid St.; Rehorn, Christian W.G.

The new ternary transition metal-rich borides Ta{sub 2}OsB{sub 2} and TaRuB have been successfully synthesized by arc-melting the elements in a water-cooled crucible under an argon atmosphere. The crystal structures of both compounds were solved by single-crystal X-ray diffraction and their metal compositions were confirmed by EDX analysis. It was found that Ta{sub 2}OsB{sub 2} and TaRuB crystallize in the tetragonal Nb{sub 2}OsB{sub 2} (space group P4/mnc, no. 128) and the orthorhombic NbRuB (space group Pmma, no. 51) structure types with lattice parameters a=5.878(2) Å, c=6.857(2) Å and a=10.806(2) Å, b=3.196(1) Å, c=6.312(2) Å, respectively. Furthermore, crystallographic, electronic and bondingmore » characteristics have been studied by density functional theory (DFT). Electronic structure relaxation has confirmed the crystallographic parameters while COHP bonding analysis indicates that B{sub 2}-dummbells are the strongest bonds in both compounds. Moreover, the formation of osmium dumbbells in Ta{sub 2}OsB{sub 2} through a Peierls distortion along the c-axis, is found to be the origin of superstructure formation. Magnetic susceptibility measurements reveal that the two phases are Pauli paramagnets, thus confirming the theoretical DOS prediction of metallic character. Also hints of superconductivity are found in the two phases, however lack of single phase samples has prevented confirmation. Furthermore, the thermodynamic stability of the two modifications of AMB (A=Nb, Ta; M =Ru, Os) are studied using DFT, as new possible phases containing either B{sub 4}- or B{sub 2}-units are predicted, the former being the most thermodynamically stable modification. - Graphical abstract: The two new ternary tantalum borides, Ta{sub 2}OsB{sub 2} and TaRuB, have been discovered. Their crystal structures contain boron dumbbells, which are the strongest bonds. Peirls distortion is found responsible for Os{sub 2}-dumbbells formation in Ta{sub 2}OsB{sub 2}. Ta{sub 2}Os

9,10-phenanthrenesemiquinone radical complexes of ruthenium(III), osmium(III) and rhodium(III) and redox series.

PubMed

Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Weyhermüller, Thomas; Ghosh, Prasanta

2013-05-14

Reactions of 9,10-phenanthrenequinone (PQ) in toluene with [M(II)(PPh3)3X2] at 298 K afford green complexes, trans-[M(PQ)(PPh3)2X2] (M = Ru, X = Cl, 1; M = Os, X = Br, 2) in moderate yields. Reaction of anhydrous RhCl3 with PQ and PPh3 in boiling ethanol affords the dark brown paramagnetic complex, cis-[Rh(PQ)(PPh3)2Cl2] (3) in good yields. Diffusion of iodine solution in n-hexane to the trans-[Os(PQ) (PPh3)2(CO)(Br)] solution in CH2Cl2 generates the crystals of trans-[Os(PQ)(PPh3)2(CO)(Br)](+)I3(-), (4(+))I3(-)), in lower yields. Single crystal X-ray structure determinations of 1·2toluene, 2·CH2Cl2 and 4(+)I3(-), UV-vis/NIR absorption spectra, EPR spectra of 3, electrochemical activities and DFT calculations on 1, 2, trans-[Ru(PQ)(PMe3)2Cl2] (1Me), trans-[Os(PQ)(PMe3)2Br2] (2Me), cis-[Rh(PQ)(PMe3)2Cl2] (3Me) and their oxidized and reduced analogues including trans-[Os(PQ)(PMe3)2(CO)(Br)](+) (4Me(+)) substantiated that 1-3 are the 9,10-phenanthrenesemiquinone radical (PQ(˙-)) complexes of ruthenium(III), osmium(III) and rhodium(III) and are defined as trans/cis-[M(III)(PQ(˙-))(PPh3)2X2] with a minor contribution of the resonance form trans/cis-[M(II)(PQ)(PPh3)2X2]. Two comparatively longer C-O (1.286(4) Å) and the shorter C-C lengths (1.415(7) Å) of the OO-chelate of 1·2toluene and 2·CH2Cl2 and the isotropic fluid solution EPR signal at g = 1.999 of 3 are consistent with the existence of the reduced PQ(˙-) ligand in 1-3 complexes. Anisotropic EPR spectra of the frozen glasses (g11 = g22 = 2.0046 and g33 = 1.9874) and solids (g11 = g22 = 2.005 and g33 = 1.987) instigate the contribution of the resonance form, cis-[Rh(II)(PQ)(PPh3)2Cl2] in 3. DFT calculations established that the closed shell singlet (CSS) solutions of 1Me and 2Me are unstable due to open shell singlet (OSS) perturbation. However, the broken symmetry (BS) (1,1) Ms = 0 solutions of 1Me and 2Me are respectively 22.6 and 24.2 kJ mole(-1) lower in energy and reproduced the experimental bond

Accelerator Production and Separations for High Specific Activity Rhenium-186

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jurisson, Silvia S.; Wilbur, D. Scott

2016-04-01

Tungsten and osmium targets were evaluated for the production of high specific activity rhenium-186. Rhenium-186 has potential applications in radiotherapy for the treatment of a variety of diseases, including targeting with monoclonal antibodies and peptides. Methods were evaluated using tungsten metal, tungsten dioxide, tungsten disulfide and osmium disulfide. Separation of the rhenium-186 produced and recycling of the enriched tungsten-186 and osmium-189 enriched targets were developed.

Heavy metal staining, a comparative assessment of gadolinium chloride and osmium tetroxide for inner ear labyrinthine contrast enhancement using X-ray microtomography.

PubMed

Wong, Christopher C; Curthoys, Ian S; O'Leary, Stephen J; Jones, Allan S

2013-01-01

The use of both gadolinium chloride (GdCl(3)) and osmium tetroxide (OsO(4)) allowed for the visualization of the membranous labyrinth and other intralabyrinthine structures, at different intensities, as compared with the control sample. This initial comparison shows the advantages of GdCl(3) in radiological assessments and OsO(4) in more detailed anatomical studies and pathways of labyrinthine pathogenesis using X-ray microtomography (microCT). To assess an improved OsO(4) staining protocol and compare the staining affinities against GdCl(3). Guinea pig temporal bones were stained with either GdCl(3) (2% w/v) for 7 days or OsO(4) (2% w/v) for 3 days, and scanned in a microCT system. The post-scanned datasets were then assessed in a 3D rendering program. The enhanced soft tissue contrast as presented in the temporal bones stained with either GdCl(3) or OsO(4) allowed for the membranous labyrinth to be visualized throughout the whole specimen. GdCl(3)-stained specimens presented more defined contours of the bone profile in the radiographs, while OsO(4)-stained specimens provided more anatomical detail of individual intralabyrinthine structures, hence allowing spatial relationships to be visualized with ease in a 3D rendering context and 2D axial slice images.

Finding the Stable Structures of WxN1-x with an ab-initio High-Throughput Approach

DTIC Science & Technology

2014-03-13

cubic boron nitride[4], carbonitrides,[5] and transition metal borides .[6, 7] Over the past several years there has been considerable theoretical...include ionic and covalent structures which seem chemically similar to W-N. These include borides , carbides, oxides, and other nitrides. In this paper we...metallic alloys, [23–27] we extended it to include over fifty new structures. These include nitrides, oxides, borides , and carbides. The important

On the Correlation between Morphology of alpha and Its Crystallographic Orientation Relationship with TiB and Beta in Boron Containing Ti-5Al-5Mo-5V-3Cr-0.5Fe Alloy (Preprint)

DTIC Science & Technology

2012-01-01

submitted to Metallurgical Transactions. This document contains color. 14. ABSTRACT While the role of borides on the microstructure of titanium...Ohio, U.S.A. Abstract While the role of borides on the microstructure of titanium alloys has been discussed in many previous reports, this paper...morphology of  precipitates nucleating from boride precipitates present in the  matrix of a titanium alloy; and (b) to investigate the role of presence or

High Energy Advanced Thermal Storage for Spacecraft Solar Thermal Power and Propulsion Systems

DTIC Science & Technology

2011-10-12

Vol. 108, No. 6, June 1961, pp. 568-572. 38. Storms, E. and Mueller, B., "Phase Relations and Thermodynamic Properties of Transition Metal Borides ...T., and Naka, S., "Formation Process of Tungsten Borides by Solid State Reaction Between Tungsten and Amorphous Boron," Journal of Materials...Molybdenum- Borides ," Journal of Metals, September 1952, pp. 983-988. 41. Ellis, R.C., “Various Preparations of Elemental Boron,” Proceedings of the 1st

Finding the Stable Structures of N1-xWx with an Ab Initio High-Throughput Approach

DTIC Science & Technology

2015-05-26

W. These include borides , carbides, oxides, and other nitrides. We also invented many structures to mimic the random pattern of vacancies on both the...structures. These include nitrides, oxides, borides , and carbides, as well as supercells of standard structures with atoms removed to mimic the random patter...1930). [15] R. Kiessling and Y. H. Liu, Thermal stability of the chromium, iron, and tungsten borides in streaming ammonia and the existence of a new

Molten Boron Phase-Change Thermal Energy Storage to Augment Solar Thermal Propulsion Systems

DTIC Science & Technology

2011-07-13

Thermodynamic Properties of Transition Metal Borides . I. The Molybdenum-boron system and Elemental Boron," Journal of Physical Chemistry, Vol. 81...February 1977, pp. 318-324. 38Itoh, H., Matsudaira, T., and Naka, S., "Formation Process of Tungsten Borides by Solid State Reaction Between Tungsten...Molybdenum-Boron and Some Properties of The Molybdenum- Borides ," Journal of Metals, September 1952, pp. 983-988. 40Stout, N. D., Mar, R. W., and Boo, W. O

Probing the superconducting ground state of the rare-earth ternary boride superconductors R RuB2 (R = Lu,Y) using muon-spin rotation and relaxation

NASA Astrophysics Data System (ADS)

Barker, J. A. T.; Singh, R. P.; Hillier, A. D.; Paul, D. McK.

2018-03-01

The superconductivity in the rare-earth transition-metal ternary borides R RuB2 (where R =Lu and Y) has been investigated using muon-spin rotation and relaxation. Measurements made in zero field suggest that time-reversal symmetry is preserved upon entering the superconducting state in both materials; a small difference in depolarization is observed above and below the superconducting transition in both compounds, however, this has been attributed to quasistatic magnetic fluctuations. Transverse-field measurements of the flux-line lattice indicate that the superconductivity in both materials is fully gapped, with a conventional s -wave pairing symmetry and BCS-like magnitudes for the zero-temperature gap energies. The electronic properties of the charge carriers in the superconducting state have been calculated, with effective masses m*/me=9.8 ±0.1 and 15.0 ±0.1 in the Lu and Y compounds, respectively, with superconducting carrier densities ns=(2.73 ±0.04 ) ×1028m-3 and (2.17 ±0.02 ) ×1028m-3 . The materials have been classified according to the Uemura scheme for superconductivity, with values for Tc/TF of 1 /(414 ±6 ) and 1 /(304 ±3 ) , implying that the superconductivity may not be entirely conventional in nature.

A study on the formation of solid state nanoscale materials using polyhedral borane compounds

NASA Astrophysics Data System (ADS)

Romero, Jennifer V.

The formation of boron containing materials using a variety of methods was explored. The pyrolysis of a metal boride precursor solution can be accomplished using a one-source method by combining TiCl4, B10H 14 and CH3CN in one reaction vessel and pyrolyzing it at temperatures above 900 °C. Amorphous dark blue colored films were obtained after the pyrolysis reactions. Well-defined spherical shaped grains or particles were observed by SEM. The amorphous films generated contained titanium, however, the determination of the boron content of the films was inconclusive. This one pot method making metal boride thin films has the advantage of being able to dictate the stoichiometry of the reactants. Another part of this work represents the first report of both the use of metal boride materials and the use of a titanium-based compound for the formation of nanotubes. This method provides a facile method for generating well-formed boron-containing carbon nanotubes in a "one-pot" process through an efficient aerosol process. The formation of metal boride corrosion resistant layers was also explored. It was shown that metallic substrates can be effectively boronized using paste mixtures containing boron carbide and borax. The formation of a Fe4B 2 iron boride phase was achieved, however, this iron boride phase does not give enough corrosion protection. The formation of a corrosion resistant metal boride coating with strong adhesion was accomplished by boronization of a thermal sprayed nickel layer on the surface of steel. Surfactants were explored as possible nanoreactors in which metal boride nanoparticles could be formed to use as nanotube growth catalyst via room temperature reaction. Different surfactants were used, but none of them successfully generated very well dispersed metal boride nanoparticles. Nanoparticles with varying shapes and sizes were generated which were highly amorphous. The carboxylic acid derivative of closo-C2B 10 cages was explored as a ligand in the

Non-invasive localization of organic matter in soil aggregates using SR-μCT

NASA Astrophysics Data System (ADS)

Peth, Stephan; Mordhorst, Anneka; Chenu, Claire; Uteau Puschmann, Daniel; Garnier, Patricia; Nunan, Naoise; Pot, Valerie; Beckmann, Felix; Ogurreck, Malte

2014-05-01

Knowledge of the location of soil organic matter (SOM) and its spatial association to soil structure is an important step in improving modeling approaches for simulating organic matter turnover processes. Advanced models for carbon mineralization are able to account for the 3D distribution of SOM which is assumed to influence mineralisation. However, their application is still limited by the fact that no method exists to non-invasively determine the 3D spatial distribution of SOM in structured soils. SR-based X-ray microtomography (SR-µCT) is an advanced and promising tool in gaining knowledge on the 3-dimensional organization of soil phases (minerals, organic matter, water, air) which on a voxel level could be implemented into spatially explicit models. However, since the contrast of linear attenuation coefficients of soil organic matter on the one hand and mineral components and water on the other hand are relatively low, especially when materials are finely dispersed, organic matter within the soil pore space is often not resolved in ordinary X-ray absorption contrast imaging. To circumvent this problem we have developed a staining procedure for organic matter using Osmium-tetroxide since Osmium is an element with an absorption edge at a higher X-ray energy level. Osmium is known from transmission electron microscopy analysis (TEM) to stain organic matter specifically and irreversibly while having an absorption edge at approximately 74 keV. We report on the application of a novel Osmium vapor staining method to analyze differences in organic matter content and identify small scale spatial distribution of SOM in soil aggregates. To achieve this we have taken soil aggregate samples (6-8 mm across) obtained from arable soils differing in soil management. Aggregate samples were investigated by synchrotron-based X-ray microtomography (SR-µCT) after staining the sample with Osmium-tetroxide (OsO4) vapor. We utilized the monochromatic X-ray beam to locate osmium

Reactivity of cytosine and thymine in single-base-pair mismatches with hydroxylamine and osmium tetroxide and its application to the study of mutations.

PubMed Central

Cotton, R G; Rodrigues, N R; Campbell, R D

1988-01-01

The chemical reactivity of thymine (T), when mismatched with the bases cytosine, guanine, and thymine, and of cytosine (C), when mismatched with thymine, adenine, and cytosine, has been examined. Heteroduplex DNAs containing such mismatched base pairs were first incubated with osmium tetroxide (for T and C mismatches) or hydroxylamine (for C mismatches) and then incubated with piperidine to cleave the DNA at the modified mismatched base. This cleavage was studied with an internally labeled strand containing the mismatched T or C, such that DNA cleavage and thus reactivity could be detected by gel electrophoresis. Cleavage at a total of 13 T and 21 C mismatches isolated (by at least three properly paired bases on both sides) single-base-pair mismatches was identified. All T or C mismatches studied were cleaved. By using end-labeled DNA probes containing T or C single-base-pair mismatches and conditions for limited cleavage, we were able to show that cleavage was at the base predicted by sequence analysis and that mismatches in a length of DNA could be readily detected by such an approach. This procedure may enable detection of all single-base-pair mismatches by use of sense and antisense probes and thus may be used to identify the mutated base and its position in a heteroduplex. Images PMID:3260032

Dislocation Decorrelation and Relationship to Deformation Microtwins during Creep of a Gamma’ Precipitate Strengthened Ni-based Superalloy

DTIC Science & Technology

2011-11-01

Deformation is highly localized around stress concentrators such as carbides, borides and serrated grain boundaries, which act as sources of a/2h110i...highly localized around stress concentrators such as carbides, borides and serrated grain boundaries, which act as sources of a/2h110i matrix-type...phase at different thicknesses. 7328 R.R. Unocic et al. / Acta Materialia 59 (2011) 7325–7339 the image. A number of carbide and/or boride phases are

Synthesis and Characterization of YB4 Ceramics

DTIC Science & Technology

2011-06-24

capa bility at temperatures above 2000°C1 with adequate mechani cal properties and oxidation resistance. Refractory metal borides based on HfB2 and ZrB2...increase in the oxidation resistance was accomplished by the addition of the Group IV VI transition metal borides , which was the result of phase...metal borides for use as materials for ultra high temper ature (UHT) applications. However, for instance, yttrium tet raboride, YB4, appears promising as

Complete titanium substitution by boron in a tetragonal prism: exploring the complex boride series Ti(3-x)Ru(5-y)Ir(y)B(2+x) (0 ≤ x ≤ 1 and 1 < y < 3) by experiment and theory.

PubMed

Fokwa, Boniface P T; Hermus, Martin

2011-04-18

Polycrystalline samples and single crystals of four members of the new complex boride series Ti(3-x)Ru(5-y)Ir(y)B(2+x) (0 ≤ x ≤ 1 and 1 < y < 3) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The new silvery phases were structurally characterized by powder and single-crystal X-ray diffraction as well as energy- and wavelength-dispersive X-ray spectroscopy analyses. They crystallize with the tetragonal Ti(3)Co(5)B(2) structure type in space group P4/mbm (No. 127). Tetragonal prisms of Ru/Ir atoms are filled with titanium in the boron-poorest phase (Ti(3)Ru(2.9)Ir(2.1)B(2)). Gradual substitution of titanium by boron then results in the successive filling of this site by a Ti/B mixture en route to the complete boron occupation, leading to the boron-richest phase (Ti(2)Ru(2.8)Ir(2.2)B(3)). Furthermore, both ruthenium and iridium share two sites in these structures, but a clear Ru/Ir site preference is found. First-principles density functional theory calculations (Vienna ab initio simulation package) on appropriate structural models (using a supercell approach) have provided more evidence on the stability of the boron-richest and -poorest phases, and the calculated lattice parameters corroborate very well with the experimentally found ones. Linear muffin-tin orbital atomic sphere approximation calculations further supported these findings through crystal orbital Hamilton population bonding analyses, which also show that the Ru/Ir-B and Ru/Ir-Ti heteroatomic interactions are mainly responsible for the structural stability of these compounds. Furthermore, some stable and unstable phases of this complex series could be predicted using the rigid-band model. According to the density of states analyses, all phases should be metallic conductors, as was expected from these metal-rich borides.

Fabrication and Characterization of Plasma Electrolytic Borocarburized Layers on Q235 Low-Carbon Steel at Different Discharge Voltages

NASA Astrophysics Data System (ADS)

Wang, Bin; Wu, Jie; Jin, Xiaoyue; Wu, Xiaoling; Wu, Zhenglong; Xue, Wenbin

The influence of applied voltage on the plasma electrolytic borocarburizing (PEB/C) layer of Q235 low-carbon steel in high-concentration borax solution was investigated. XRD and XPS spectra of PEB/C layer confirmed that the modified boride layer mainly consisted of Fe2B phase, and the FeB phase only exists in the loose top layer. The applied voltage on Q235 steel played a key role in determining the properties of hardened layers. The thickness and microhardness of boride layers increased with the increase of the applied voltage, which led to superior corrosion and wear resistances of Q235 low-carbon steel. The diffusion coefficient (D) of boride layer at 280, 300 and 330V increased with borocarburizing temperature and ranged from 0.062×10-12m2/s to 0.462×10-12m2/s. The activation energy (Q) of boride layer growth during PEB/C treatment was only 52.83kJṡmol-1, which was much lower than that of the conventional boriding process.

Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component

NASA Technical Reports Server (NTRS)

Riedell, James A. (Inventor); Easler, Timothy E. (Inventor)

2009-01-01

A precursor of a ceramic adhesive suitable for use in a vacuum, thermal, and microgravity environment. The precursor of the ceramic adhesive includes a silicon-based, preceramic polymer and at least one ceramic powder selected from the group consisting of aluminum oxide, aluminum nitride, boron carbide, boron oxide, boron nitride, hafnium boride, hafnium carbide, hafnium oxide, lithium aluminate, molybdenum silicide, niobium carbide, niobium nitride, silicon boride, silicon carbide, silicon oxide, silicon nitride, tin oxide, tantalum boride, tantalum carbide, tantalum oxide, tantalum nitride, titanium boride, titanium carbide, titanium oxide, titanium nitride, yttrium oxide, zirconium diboride, zirconium carbide, zirconium oxide, and zirconium silicate. Methods of forming the ceramic adhesive and of repairing a substrate in a vacuum and microgravity environment are also disclosed, as is a substrate repaired with the ceramic adhesive.

Effects of Tungsten Addition on the Microstructure and Corrosion Resistance of Fe-3.5B Alloy in Liquid Zinc

PubMed Central

Liu, Xin; Wang, Mengmeng; Yin, Fucheng; Ouyang, Xuemei; Li, Zhi

2017-01-01

The effects of tungsten addition on the microstructure and corrosion resistance of Fe-3.5B alloys in a liquid zinc bath at 520 °C were investigated by means of scanning electron microscopy, X-ray diffraction and electron probe micro-analysis. The microstructure evolution in different alloys is analyzed and discussed using an extrapolated Fe-B-W ternary phase diagram. Experimental results show that there are three kinds of borides, the reticular (Fe, W)2B, the rod-like (Fe, W)3B and flower-like FeWB. The addition of tungsten can refine the microstructure and improve the stability of the reticular borides. Besides, it is beneficial to the formation of the metastable (Fe, W)3B phase. The resultant Fe-3.5B-11W (wt %) alloy possesses excellent corrosion resistance to liquid zinc. When tungsten content exceeds 11 wt %, the formed flower-like FeWB phase destroys the integrity of the reticular borides and results in the deterioration of the corrosion resistance. Also, the corrosion failure resulting from the spalling of borides due to the initiation of micro-cracks in the grain boundary of borides is discussed in this paper. PMID:28772759

Non-Contact Tabletop Mechanical Testing of Ultra-High Temperature Ceramics

DTIC Science & Technology

2012-05-01

class of refractory materials including transition metal borides , carbides and nitrides e.g. ZrB2l HfB2) ZrC, HfC, TaC, HfN and ZrN. They recently...ike oxidizing atmospheres, at very high temperatures Refractory borides like ZrB2 and HfB2 have extremely high melting temperatures (over 3000°C...But borides are very poor in oxidation resistance, due to the nature of thär oxides Non-protective ZrCfe or Hf02 and volatile liquid B203. Addition

Development of high temperature stable Ohmic and Schottky contacts on n-gallium nitride

NASA Astrophysics Data System (ADS)

Khanna, Rohit

In this work the effort was made to towards develop and investigate high temperature stable Ohmic and Schottky contacts for n type GaN. Various borides and refractory materials were incorporated in metallization scheme to best attain the desired effect of minimal degradation of contacts when placed at high temperatures. This work focuses on achieving a contact scheme using different borides which include two Tungsten Borides (namely W2B, W2B 5), Titanium Boride (TiB2), Chromium Boride (CrB2) and Zirconium Boride (ZrB2). Further a high temperature metal namely Iridium (Ir) was evaluated as a potential contact to n-GaN, as part of continuing improved device technology development. The main goal of this project was to investigate the most promising boride-based contact metallurgies on GaN, and finally to fabricate a High Electron Mobility Transistor (HEMT) and compare its reliability to a HEMT using present technology contact. Ohmic contacts were fabricated on n GaN using borides in the metallization scheme of Ti/Al/boride/Ti/Au. The characterization of the contacts was done using current-voltage measurements, scanning electron microscopy (SEM) and Auger Electron Spectroscopy (AES) measurements. The contacts formed gave specific contact resistance of the order of 10-5 to 10-6 Ohm-cm2. A minimum contact resistance of 1.5x10-6 O.cm 2 was achieved for the TiB2 based scheme at an annealing temperature of 850-900°C, which was comparable to a regular ohmic contact of Ti/Al/Ni/Au on n GaN. When some of borides contacts were placed on a hot plate or in hot oven for temperature ranging from 200°C to 350°C, the regular metallization contacts degraded before than borides ones. Even with a certain amount of intermixing of the metallization scheme the boride contacts showed minimal roughening and smoother morphology, which, in terms of edge acuity, is crucial for very small gate devices. Schottky contacts were also fabricated and characterized using all the five boride

Osmium mass balance in peridotite and the effects of mantle-derived sulphides on basalt petrogenesis

NASA Astrophysics Data System (ADS)

Harvey, J.; Dale, C. W.; Gannoun, A.; Burton, K. W.

2011-10-01

Analyses of enriched mantle (EM)-basalts, using lithophile element-based isotope systems, have long provided evidence for discrete mantle reservoirs with variable composition. Upon partial melting, the mantle reservoir imparts its isotopic fingerprint upon the partial melt produced. However, it has increasingly been recognised that it may not be simple to delimit these previously well-defined mantle reservoirs; the "mantle zoo" may contain more reservoirs than previously envisaged. Here we demonstrate that a simple model with varying contributions from two populations of compositionally distinct mantle sulphides can readily account for the observed heterogeneities in Os isotope systematics of such basalts without additional mantle reservoirs. Osmium elemental and isotopic analyses of individual sulphide grains separated from spinel lherzolites from Kilbourne Hole, New Mexico, USA demonstrate that two discrete populations of mantle sulphide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os] and low [Re] with unradiogenic, typically sub-chondritic 187Os/ 188Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulphides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic 187Os/ 188Os ([Os] typically ⩽ 1-2 ppm, 187Os/ 188Os ⩽ 0.3729; this study). This population is thought to represent metasomatic sulphide. Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulphide ([Os] ⩽ 37 ppm; this study). During the early stages of partial melting, supra-chondritic interstitial sulphides are mobilised and incorporated into the melt, adding their radiogenic 187Os/ 188Os signature. Only when

Effect of mechanical activation on jell boronizing treatment of the AISI 4140

NASA Astrophysics Data System (ADS)

Yılmaz, S. O.; Karataş, S.

2013-06-01

The article presents the effect of mechanical activation on the growth kinetics of boride layer of boronized AISI 4140 steel. The samples were boronized by ferroboron + (SiO2-Na2O) powders for 873-1173 K temperature and 2, 4, 6 and 8 h times, respectively. The morphology and types of borides formed on the surface of AISI 4140 steel substrate were analyzed. Layer growth kinetics were analyzed by measuring the extent of penetration of FeB and Fe2B sublayers as function of treatment time and temperature in the range of 873-1173 K. High diffusivity was obtained by creating a large number of defects through mechanical activation in the form of nanometer sized crystalline particles through the repeated fracturing and cold-welding of the powder particles, and a depth of 100 μm was found in the specimen borided by the 2 h MA powders, for 4 h and 1073 K, where 2000-2350 HV were measured. Consequently, the application conditions of boronizing were improved by usage of mechanical activation. The preferred Fe2B boride without FeB could be formed in the boride layer under 973 K boronizing temperature by mechanically activated by ferroboron + sodium silicate powder mixture due to the decrease of the activation energy.

Theoretical and Experimental Investigations on the Mechanism of Carbothermal Reduction of Zirconia (Preprint)

DTIC Science & Technology

2012-08-01

Properties. Abyss Books, Washington, D.C., 2002. 2. G. Montel, A. Lebugle and H. Pastor. "Manufacture of Materials Containing Refractory Borides ...and ZrO2," International Journal of Refractory Metals and Hard Materials, 17, 235-43 (1999). 10. A.W. Weimer, Carbide, nitride and boride

Yttria Nanoparticle Reinforced Commercially Pure (CP) Titanium

DTIC Science & Technology

2011-09-01

nanoparticles as well as titanium boride (TiB) reinforcements were produced through gas atomization. After consolidation and extrusion, room temperature...pure FE iron O oxygen Ti titanium TiB titanium boride TYS tensile yield strength UTS ultimate tensile strength wt% weight percent Y2O3

Directionally Solidified Eutectic Ceramics for Multifunctional Aerospace Applications

DTIC Science & Technology

2013-01-01

eutectic materials development through a new initiative entitled Boride Eutectic Project. These results first time organize and populate materials...property databases, and utilize an iterative feedback routine to constantly improve the design process of the boride eutectics LaB6-MeB2 (Me = Zr, Hf, Ti

Taguchi Analysis on the Effect of Process Parameters on Densification During Spark Plasma Sintering of HfB2-20SiC (Preprint)

DTIC Science & Technology

2011-11-01

30 kN pressure and heating rate of 100 K/min. Introduction Boride , carbides and nitrides of the group IVB and VB transition metals are considered...10. Sciti D., Silvestroni L., Nygren M. Spark plasma sintering of Zr- and Hf- borides with decreasing amounts of MoSi2 as sintering aid Journal of

Structure of the nucleoid in cells of Streptococcus faecalis.

PubMed Central

Daneo-Moore, L; Dicker, D; Higgins, M L

1980-01-01

The structure of the nucleoid of Streptococcus faecalis (ATCC 9790) was examined and compared in the unfixed and fixed states by immersive refractometry and electron microscopy. It appears from these studies that the nucleoid structure is much more centralized in unfixed chloramphenicol-treated (stationary-phase) cells than it is in cells in the exponential phase of growth. The more dispersed configuration of the exponential-phase nucleoid could be preserved by fixation in glutaraldehyde, but not in Formalin or in osmium tetroxide. One important factor in explaining these differences in preservation is that glutaraldehyde (but not Formalin or osmium tetroxide) can rapidly cross-link the amino groups of macromolecules in cells. It was also observed that osmium tetroxide resulted in a preferential breakdown of nascent ribonucleic acid. These results are interpreted as indicating that glutaraldehyde is able to stabilize the exponential-phase nucleoid before it assumes the more central appearance seen in osmium tetroxide- and Formalin-fixed cells. These results are discussed in terms of the proposed organization of the exponential-phase nucleoid in unfixed cells. Images PMID:6767695

Demonstration of Shear Localization in Ultrafine Grained Tungsten Alloys via Powder Metallurgy Processing Route

DTIC Science & Technology

2012-09-01

of a di-tungsten boride (W2B) phase was not detected in the nW-B sample, but the low concentration of boron may have made this phase undetectable by...Split Hopkinson Bar UFG ultrafine grained W2B di-tungsten boride XRD x-ray diffraction NO. OF NO. OF COPIES ORGANIZATION COPIES

Adhesive and Cohesive Strength in FeB/Fe2B Systems

NASA Astrophysics Data System (ADS)

Meneses-Amador, A.; Blancas-Pérez, D.; Corpus-Mejía, R.; Rodríguez-Castro, G. A.; Martínez-Trinidad, J.; Jiménez-Tinoco, L. F.

2018-05-01

In this work, FeB/Fe2B systems were evaluated by the scratch test. The powder-pack boriding process was performed on the surface of AISI M2 steel. The mechanical parameters, such as yield stress and Young's modulus of the boride layer, were obtained by the instrumented indentation technique. Residual stresses produced on the boride layer were estimated by using the x-ray diffraction (XRD) technique. The scratch test was performed in order to evaluate the cohesive/adhesive strength of the FeB/Fe2B coating. In addition, a numerical evaluation of the scratch test on boride layers was performed by the finite element method. Maximum principal stresses were related to the failure mechanisms observed by the experimental scratch test. Shear stresses at the interfaces of the FeB/Fe2B/substrate system were also evaluated. Finally, the results obtained provide essential information about the effect of the layer thickness, the residual stresses, and the resilience modulus on the cohesive/adhesive strength in FeB/Fe2B systems.

DNA/nickel oxide nanoparticles/osmium(III)-complex modified electrode toward selective oxidation of l-cysteine and simultaneous detection of l-cysteine and homocysteine.

PubMed

Sharifi, Ensiyeh; Salimi, Abdollah; Shams, Esmaeil

2012-08-01

The modification of glassy carbon (GC) electrode with electrodeposited nickel oxide nanoparticles (NiOxNPs) and deoxyribonucleic acid (DNA) is utilized as a new efficient platform for entrapment of osmium (III) complex. Surface morphology and electrochemical properties of the prepared nanocomposite modified electrode (GC/DNA/NiOxNPs/Os(III)-complex) were investigated by FESEM, cyclic voltammetry and electrochemical impedance spectroscopy techniques. Cyclic voltammetric results indicated the excellent electrocatalytic activity of the resulting electrode toward oxidation of l-cysteine (CySH) at reduced overpotential (0.1 V vs. Ag/AgCl). Using chronoamperometry to CySH detection, the sensitivity and detection limit of the biosensor are obtained as 44 μA mM(-1) and 0.07 μM with a concentration range up to 1000 μM. The electrocatalytic activity of the modified electrode not only for oxidation of low molecular-mass biothiols derivatives such as, glutathione, l-cystine, l-methionine and electroactive biological species ( dopamine, uric acid, glucose) is negligible but also for very similar biothiol compound (homocysteine) no recognizable response is observed at the applied potential window. Furthermore, the simultaneous voltammetric determination of l-cysteine and homocysteine compounds without any separation or pretreatment process was reported for the first time in this work. Finally, the applicability of sensor for the analysis of CySH concentration in complex serum samples was successfully demonstrated. Highly selectivity, excellent electrocatalytic activity and stability, remarkable antifouling property toward thiols and their oxidation products, as well as the ability for simultaneous detection of l-cysteine and homocysteine are remarkably advantageous of the proposed DNA based biosensor. Copyright © 2012 Elsevier B.V. All rights reserved.

Silicon carbide sintered body manufactured from silicon carbide powder containing boron, silicon and carbonaceous additive

NASA Technical Reports Server (NTRS)

Tanaka, Hidehiko

1987-01-01

A silicon carbide powder of a 5-micron grain size is mixed with 0.15 to 0.60 wt% mixture of a boron compound, i.e., boric acid, boron carbide (B4C), silicon boride (SiB4 or SiB6), aluminum boride, etc., and an aluminum compound, i.e., aluminum, aluminum oxide, aluminum hydroxide, aluminum carbide, etc., or aluminum boride (AlB2) alone, in such a proportion that the boron/aluminum atomic ratio in the sintered body becomes 0.05 to 0.25 wt% and 0.05 to 0.40 wt%, respectively, together with a carbonaceous additive to supply enough carbon to convert oxygen accompanying raw materials and additives into carbon monoxide.

Synthesis, crystal structure investigation and magnetism of the complex metal-rich boride series Crx(Rh1-yRuy)7-xB3 (x=0.88-1; y=0-1) with Th7Fe3-type structure

NASA Astrophysics Data System (ADS)

Misse, Patrick R. N.; Mbarki, Mohammed; Fokwa, Boniface P. T.

2012-08-01

Powder samples and single crystals of the new complex boride series Crx(Rh1-yRuy)7-xB3 (x=0.88-1; y=0-1) have been synthesized by arc-melting the elements under purified argon atmosphere on a water-cooled copper crucible. The products, which have metallic luster, were structurally characterized by single-crystal and powder X-ray diffraction as well as EDX measurements. Within the whole solid solution range the hexagonal Th7Fe3 structure type (space group P63mc, no. 186, Z=2) was identified. Single-crystal structure refinement results indicate the presence of chromium at two sites (6c and 2b) of the available three metal Wyckoff sites, with a pronounced preference for the 6c site. An unexpected Rh/Ru site preference was found in the Ru-rich region only, leading to two different magnetic behaviors in the solid solution: The Rh-rich region shows a temperature-independent (Pauli) paramagnetism whereas an additional temperature-dependent paramagnetic component is found in the Ru-rich region.

Organization of actin in the leading edge of cultured cells: influence of osmium tetroxide and dehydration on the ultrastructure of actin meshworks

PubMed Central

1981-01-01

The ordered structure of the leading edge (lamellipodium) of cultured fibroblasts is readily revealed in cells extracted briefly in Triton X- 100-glutaraldehyde mixtures, fixed further in glutaraldehyde, and then negatively stained for electron microscopy. By this procedure, the leading edge regions show a highly organised, three-dimensional network of actin filaments together with variable numbers of radiating actin filament bundles or microspikes. The use of Phalloidin after glutaraldehyde fixation resulted in a marginal improvement in filament order. Processing of the cytoskeletons though the additional steps generally employed for conventional electron microscopy resulted in a marked deterioration or complete disruption of the order of the actin filament networks. In contrast, the actin filaments of the stress fiber bundles were essentially unaffected. Thus, postfixation in osmium tetroxide (1% for 7 min at room temperature) transformed the networks to a reticulum of kinked fibers, resembling those produced by the exposure of muscle F-actin to OsO4 in vitro (P. Maupin-Szamier and T. D. Pollard. 1978. J. Cell Biol. 77:837--852). While limited exposure to OsO4 (0.2+ for 20 min at 0 degrees C) obviated this destruction, dehydration in acetone or ethanol, with or without post-osmication, caused a further and unavoidable disordering and aggregation of the meshwork filaments. The meshwork regions of the leading edge then showed a striking resemblance to the networks hitherto described in critical point-dried preparations of cultured cells. I conclude that much of the "microtrabecular lattice" described by Wolosewick and Porter (1979. J. Cell Biol. 82:114--139) in the latter preparations constitutes actin meshworks and actin filament arrays, with their associated components, that have been distorted and aggregated by the preparative procedures employed. PMID:6799521

mer, fac, and Bidentate Coordination of an Alkyl-POP Ligand in the Chemistry of Nonclassical Osmium Hydrides.

PubMed

Esteruelas, Miguel A; García-Yebra, Cristina; Martín, Jaime; Oñate, Enrique

2017-01-03

Nonclassical and classical osmium polyhydrides containing the diphosphine 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant(P i Pr 2 ) 2 ), coordinated in κ 3 -mer, κ 3 -fac, and κ 2 -P,P fashions, have been isolated during the cyclic formation of H 2 by means of the sequential addition of H + and H - or H - and H + to the classical trihydride OsH 3 Cl{xant(P i Pr 2 ) 2 } (1). This complex adds H + to form the compressed dihydride dihydrogen complex [OsCl(H···H)(η 2 -H 2 ){xant(P i Pr 2 ) 2 }] + (2). Under argon, cation 2 loses H 2 and the resulting unsaturated fragment dimerizes to give [(Os(H···H){xant(P i Pr 2 ) 2 }) 2 (μ-Cl) 2 ] 2+ (3). During the transformation the phosphine changes its coordination mode from mer to fac. The benzofuran counterpart of 1, OsH 3 Cl{dbf(P i Pr 2 ) 2 } (4; dbf(P i Pr 2 ) 2 = 4,6-bis(diisopropylphosphino)dibenzofuran), also adds H + to afford the benzofuran counterpart of 2, [OsCl(H···H)(η 2 -H 2 ){xant(P i Pr 2 ) 2 }] + (5), which in contrast to the latter is stable and does not dimerize. Acetonitrile breaks the chloride bridge of 3 to form the dihydrogen [OsCl(η 2 -H 2 )(CH 3 CN){xant(P i Pr 2 ) 2 }] + (6), regenerating the mer coordination of the diphosphine. The hydride ion also breaks the chloride bridge of 3. The addition of KH to 3 leads to 1, closing a cycle for the formation of H 2 . Complex 1 reacts with a second hydride ion to give OsH 4 {xant(P i Pr 2 ) 2 } (7) as consequence of the displacement of the chloride. Similarly to the latter, the oxygen atom of the mer-coordinated diphosphine of 7 has a tendency to be displaced by the hydride ion. Thus, the addition of KH to 7 yields [OsH 5 {xant(P i Pr 2 ) 2 }] - (8), containing a κ 2 -P,P-diphosphine. Complex 8 is easily protonated to afford OsH 6 {xant(P i Pr 2 ) 2 } (9), which releases H 2 to regenerate 7, closing a second cycle for the formation of molecular hydrogen.

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

1994-01-01

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also

Search for New Superconductors for Energy and Power Applications

DTIC Science & Technology

2014-10-21

superconductors, borides , carbides, silicides, and chalcogenides. In addition, a number of thin film systems have been explored: A15s, superlattices, arrays of...YBa2Cu3O7 Bi2Se3 Eu-Si-C ErRh4B4 Bi2Sr2CaCu2O8 (UD, OD) Sb2Se3 V-Si-C (Ga,Mn)As CuO ZrSe2 Sm-Si-C Hf(FeCo)P Y1-xCaxCrO3 Fe-Te-Se BORIDES Hf-Fe-C-P...Physics, Warsaw, Poland Table III New superconductors, discovered by UCSD MURI team. BORIDES Tc (K) Nb0.9Zr0.1B 11.2 ZrNbxB 9.0 ZrVxB 9.0

Platinum- and membrane-free swiss-roll mixed-reactant alkaline fuel cell.

PubMed

Aziznia, Amin; Oloman, Colin W; Gyenge, Előd L

2013-05-01

Eliminating the expensive and failure-prone proton exchange membrane (PEM) together with the platinum-based anode and cathode catalysts would significantly reduce the high capital and operating costs of low-temperature (<373 K) fuel cells. We recently introduced the Swiss-roll mixed-reactant fuel cell (SR-MRFC) concept for borohydride-oxygen alkaline fuel cells. We now present advances in anode electrocatalysis for borohydride electrooxidation through the development of osmium nanoparticulate catalysts supported on porous monolithic carbon fiber materials (referred to as an osmium 3D anode). The borohydride-oxygen SR-MRFC operates at 323 K and near atmospheric pressure, generating a peak power density of 1880 W m(-2) in a single-cell configuration by using an osmium-based anode (with an osmium loading of 0.32 mg cm(-2)) and a manganese dioxide gas-diffusion cathode. To the best of our knowledge, 1880 W m(-2) is the highest power density ever reported for a mixed-reactant fuel cell operating under similar conditions. Furthermore, the performance matches the highest reported power densities for conventional dual chamber PEM direct borohydride fuel cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

REDUCTION OF INORGANIC COMPOUNDS WITH MOLECULAR HYDROGEN BY MICROCOCCUS LACTILYTICUS I.

PubMed Central

Woolfolk, C. A.; Whiteley, H. R.

1962-01-01

Woolfolk, C. A. (University of Washington, Seattle) and H. R. Whiteley. Reduction of inorganic compounds with molecular hydrogen by Micrococcus lactilyticus. I. Stoichiometry with compounds of arsenic, selenium, tellurium, transition and other elements. J. Bacteriol. 84:647–658. 1962.—Extracts of Micrococcus lactilyticus (Veillonella alcalescens) oxidize molecular hydrogen at the expense of certain compounds of arsenic, bismuth, selenium, tellurium, lead, thallium, vanadium, manganese, iron, copper, molybdenum, tungsten, osmium, ruthenium, gold, silver, and uranium, as well as molecular oxygen. Chemical and manometric data indicate that the following reductions are essentially quantitative: arsenate to arsenite, pentavalent and trivalent bismuth to the free element, selenite via elemental selenium to selenide, tellurate and tellurite to tellurium, lead dioxide and manganese dioxide to the divalent state, ferric to ferrous iron, osmium tetroxide to osmate ion, osmium dioxide and trivalent osmium to the metal, uranyl uranium to the tetravalent state, vanadate to the level of vanadyl, and polymolybdate ions to molybdenum blues with an average valence for molybdenum of +5. The results of a study of certain other hydrogenase-containing bacteria with respect to their ability to carry out some of the same reactions are also presented. PMID:14001842

The role of nonmagnetic d{sup 0} vs. d{sup 10}B-type cations on the magnetic exchange interactions in osmium double perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Hai L., E-mail: Hai.Feng@cpfs.mpg.de; Yamaura, Kazunari; Tjeng, Liu Hao

Polycrystalline samples of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were synthesized by solid state reactions. They adopt the cubic double perovskite structures (space group, Fm-3m) with ordered B and Os arrangements. Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) show antiferromagnetic transitions at 93 K, 69 K, and 28 K, respectively. The Weiss-temperatures are −590 K for Ba{sub 2}ScOsO{sub 6}, −571 K for Ba{sub 2}YOsO{sub 6}, and −155 K for Ba{sub 2}InOsO{sub 6}. Sc{sup 3+} and Y{sup 3+} have the open-shell d{sup 0} electronic configuration, while In{sup 3+} has the closed-shell d{sup 10}. This indicates that a d{sup 0} B-typemore » cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. Comparison of Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) to their Sr and Ca analogues shows that the structural distortions weaken the overall magnetic exchange interactions. - Graphical abstract: Magnetic properties of osmium double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. Comparison of Ba{sub 2}BOsO{sub 6}indicates that a d{sup 0} B-type cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. - Highlights: • Magnetic properties of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. • A d{sup 0}B-type cation induces stronger magnetic interactions than a d{sup 10}. • Structural distortions weaken the overall Os{sup 5+}-Os{sup 5+} magnetic interactions.« less

Glucose Electrodes Based on Cross-Linked (Os(bpy)2CI)+/2+ Complexed Poly(1-Vinylimidazole) Films

DTIC Science & Technology

1993-05-24

oxidase (GOX) through covalent bonding in the cross-linking step, glucose was electrooxidized at 250 mV (SCE). The characteristics of these... electrooxidation currents were independent of the polymers’ osmium content in the studied (3 - 10 osmium S_ _ centers per monomer unit ) range, Electrodes...glucose was electrooxidized at 250 mV (SCE). The characteristics of these electrodes depended on the GOX concentration, film thickness, 02

Phase identification in boron-containing powder metallurgy steel using EBSD in combination with EPMA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Ming-Wei, E-mail: mwwu@ntut.edu.tw; Cai, Wen-Zhang

2016-03-15

Boron (B) is extensively used to induce liquid phase sintering (LPS) in powder metallurgy (PM) steels and thereby increase the densification. The alloying elements in B-containing PM steels affect the boride phase, stability of the boride, the temperature of liquid formation, and the progress of LPS. However, the boride phase has not been systematically identified yet. The main objective of this study was to clarify the influences of alloying elements, including C, Cr, and Ni, on the boride phases using electron backscatter diffraction (EBSD) in combination with electron probe microanalysis (EPMA). Network structures consisting of ferrite, Fe{sub 2}B boride, andmore » Fe{sub 3}C carbide were extensively observed in the Fe–0.4B–0.5C steel. The portions of Fe{sub 2}B were sufficiently larger than those of Fe{sub 3}C, and Fe{sub 3}C was mostly distributed at the interfaces between ferrite and Fe{sub 2}B. Adding 1.5 wt.% Cr or 1.8 wt.% Ni to Fe–0.4B–0.5C steel completely changes the Fe{sub 2}B and Fe{sub 3}C phases to a M{sub 3}(B,C) phase, where M represents the metallic elements, including Fe, Cr, Mo, and Ni. Furthermore, Cr, Mo, B, and C atoms tend to concentrate on the M{sub 3}(B,C) phase, but Ni atoms do not. - Highlights: • Network structures consisting of ferrite, Fe{sub 2}B boride, and Fe{sub 3}C carbide were extensively observed in the Fe–0.4B–0.5C steel. • Adding 1.5 wt.% Cr or 1.8 wt.% Ni to Fe–0.4B–0.5C steel completely transforms the Fe{sub 2}B and Fe{sub 3}C phases to a M{sub 3}(B,C) phase. • Cr, Mo, B, and C atoms tend to concentrate on the M{sub 3}(B,C) phase, but Ni atoms do not.« less

Method of boronizing transition metal surfaces

DOEpatents

Koyama, Koichiro; Shimotake, Hiroshi.

1983-08-16

A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB[sub 2], or CrB[sub 2]. A transition metal to be coated is immersed in the melt at a temperature of no more than 700 C and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface. 4 figs.

Method of boronizing transition metal surfaces

DOEpatents

Koyama, Koichiro; Shimotake, Hiroshi

1983-01-01

A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB.sub.2, or CrB.sub.2. A transition metal to be coated is immersed in the melt at a temperature of no more than 700.degree. C. and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface.

Rhenium - osmium heterogeneity of enriched mantle basalts explained by composition and behaviour of mantle-derived sulfides

NASA Astrophysics Data System (ADS)

Harvey, J.; Dale, C. W.; Gannoun, A.; Burton, K. W.

2010-12-01

Analyses of enriched mantle (EM) -basalts, using lithophile element-based isotope systems have long provided evidence for discrete, but variable mantle reservoirs [1]. Upon partial melting, the isotopic fingerprint of each reservoir is imparted upon the partial melt produced. However, recent work involving the Re-Os isotope systematics of EM-basalts [2] suggests that it may not be so simple to delimit these previously well defined mantle reservoirs; the “mantle zoo” [3] may contain more reservoirs than previously envisaged. However, a simple model, with varying contributions from two populations of compositionally distinct mantle sulfides can readily account for the observed heterogeneities in Re-Os isotope systematics of such basalts without additional mantle reservoirs. Rhenium-osmium elemental and isotopic analyses of individual sulfide grains separated from spinel lherzolites from Kilbourne Hole, NM, USA demonstrate that two discrete populations of mantle sulfide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os], low [Re] with unradiogenic, typically sub-chondritic, 187Os/188Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulfides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic, 187Os/188Os ([Os] typically ≤ 1-2 ppm, 187Os/188Os ≤ 0.3729; this study). This population is thought to represent metasomatic sulfide (e.g. [4,5]). Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulfide ([Os] ≤ 37 ppm, this study). During the early stages of partial melting, supra-chondritic interstitial sulfides are mobilized and incorporated into the melt, adding their radiogenic

Scanning electron microscopy of hepatic ultrastructure: secondary, backscattered, and transmitted electron imaging.

PubMed

Miyai, K; Abraham, J L; Linthicum, D S; Wagner, R M

1976-10-01

Several methods of tissue preparation and different modes of operation of the scanning electron microscope were used to study the ultrastructure of rat liver. Rat livers were perfusion fixed with buffered 2 per cent paraformaldehyde or a mixture of 1.5 per cent paraformaldehyde and 1 per cent glutaraldehyde and processed as follows. Tissue blocks were postfixed in buffered 2 per cent osmium tetroxide followed sequentially by the ligand-mediated osmium binding technique, dehydration and cryofracture in ethanol, and critical point drying. They were then examined without metal coating in the scanning electron microscope operating in the secondary electron and backscattered electron modes. Fifty-micrometer sections were cut with a tissue sectioner, stained with lead citrate, postfixed with osmium, dehydrated, critical point dried, and examined in the secondary electron and back-scattered electron modes. Frozen sections (0.25 to 0.75 mum. thick) were cut by the method of Tokuyasu (Toluyasu KT: J Cell Biol 57:551, 1973) and their scanning transmission electron microscope images were examined either with a scanning transmission electron microscope detector or with a conversion stub using the secondary electron detector. Secondary electron images of the liver prepared by ligand-mediated osmium binding and subsequent cryofracture revealed such intracellular structures as cisternae of the endoplasmic reticulum, lysosomes, mitochondria, lipid droplets, nucleolus and nuclear chromatin, as well as the usual surface morphology, Lipocytes in the perisinusoidal space were readily identified. Backscattered electron images. Unembedded frozen sections had little drying artifact and were virtually free of freezing damage. The scanning transmission electron microscope image revealed those organelles visualized by the secondary electron mode in the ligand-mediated osmium binding-treated tissue.

Superplastic behavior of two ultrahigh boron steels

NASA Astrophysics Data System (ADS)

Jiménez, J. A.; González-Doncel, G.; Acosta, P.; Ruano, O. A.

1994-06-01

The high-temperature deformation behavior of two ultrahigh boron steels containing 2.2 pct and 4.9 pct B was investigated. Both alloys were processed via powder metallurgy involving gas atomization and hot isostatic pressing (hipping) at various temperatures. After hipping at 700 °C, the Fe-2.2 pct B alloy showed a fine microstructure consisting of l- µm grains and small elongated borides (less than 1 µm) . At 1100 °C, a coarser microstructure with rounded borides was formed. This alloy was superplastic at 850 °C with stress exponents of about two and tensile elongations as high as 435 pct. The microstructure of the Fe-4.9 pct B alloy was similar to that of the Fe-2.2 pct B alloy showing, in addition, coarse borides. This alloy also showed low stress exponent values but lacked high tensile elongation (less than 65 pct), which was attributed to the presence of stress accumulation at the interface between the matrix and the large borides. A change in the activation energy value at the α-γ transformation temperature was seen in the Fe-2.2 pct B alloy. The plastic flow data were in agreement with grain boundary sliding and slip creep models.

Investigation of the structure and properties of boron-containing coatings obtained by electron-beam treatment

NASA Astrophysics Data System (ADS)

Krivezhenko, Dina S.; Drobyaz, Ekaterina A.; Bataev, Ivan A.; Chuchkova, Lyubov V.

2015-10-01

An investigation of surface-hardened materials obtained by cladding with an electron beam injected into the air atmosphere was carried out. Structural investigations of coatings revealed that an increase in boron carbide concentration in a saturating mixture contributed to a rise of a volume fraction of iron borides in coatings. The maximum hardened depth reached 2 mm. Hardened layers were characterized by the formation of heterogeneous structure which consisted of iron borides and titanium carbides distributed uniformly in the eutectic matrix. Areas of titanium boride conglomerations were detected. It was found that an increase in the boron carbide content led to an enhancement in hardness of the investigated materials. Friction testing against loosely fixed abrasive particles showed that electron-beam cladding of powder mixtures containing boron carbides, titanium, and iron in air atmosphere allowed enhancing a resistance of materials hardened in two times.

Multifunctional Ceramic Nanostructured Coatings

DTIC Science & Technology

2010-12-01

silicon carbide composites // J. Europ. Cer. Soc. − 2004. − Vol. 24. − P. 2169−2179. 22. Yu. P. Udalov, E. E. Valova, S. S. Ordanian. Fabrication and...by the titanium and tungsten borides and carbides . The analysis was done using the X-ray and electron-optical methods. This information expands our...coating compositions should be based on limited solubility materials. Such systems include carbides , nitrides, borides and silicides based on

Oceanic mantle rocks reveal evidence for an ancient, 1.2-1.3 Ga global melting event

NASA Astrophysics Data System (ADS)

Dijkstra, A. H.; Sergeev, D.; McTaminey, L.; Dale, C. W.; Meisel, T. C.

2011-12-01

It is now increasingly being recognized that many oceanic peridotites are refertilized harzburgites, and that the refertilization often masks an extremely refractory character of the original mantle rock 'protolith'. Oceanic peridotites are, when the effects of melt refertilization are undone, often too refractory to be simple mantle melting residues after the extraction of mid-ocean ridge basalts at a spreading center. Rhenium-osmium isotope analysis is a powerful method to look through the effects of refertilization and to obtain constraints on the age of the melting that produced the refractory mantle protolith. Rhenium-depletion model ages of such anomalously refractory oceanic mantle rocks - found as abyssal peridotites or as mantle xenoliths on ocean islands - are typically >1 Ga, i.e., much older than the ridge system at which they were emplaced. In my contribution I will show results from two case studies of refertilized anciently depleted mantle rocks (Macquarie Island 'abyssal' peridotites and Lanzarote mantle xenoliths). Interestingly, very refractory oceanic mantle rocks from sites all around the world show recurring evidence for a Mesoproterozoic (~1.2-1.3 Ga) melting event [1]. Therefore, oceanic mantle rocks seem to preserve evidence for ancient melting events of global significance. Alternatively, such mantle rocks may be samples of rafts of ancient continental lithospheric mantle. Laser-ablation osmium isotope 'dating' of large populations of individual osmium-bearing alloys from mantle rocks is the key to better constrain the nature and significance of these ancient depletion events. Osmium-bearing alloys form when mantle rocks are melted to high-degrees. We have now extracted over >250 detrital osmium alloys from placer gold occurrences in the river Rhine. These alloys are derived from outcrops of ophiolitic mantle rocks in the Alps, which include blocks of mantle rocks emplaced within the Tethys Ocean, and ultramafic lenses of unknown

Pressed boride cathodes

NASA Technical Reports Server (NTRS)

Wolski, W.

1985-01-01

Results of experimental studies of emission cathodes made from lanthanum, yttrium, and gadolinium hexaborides are presented. Maximum thermal emission was obtained from lanthanum hexaboride electrodes. The hexaboride cathodes operated stably under conditions of large current density power draw, at high voltages and poor vacuum. A microtron electron gun with a lanthanum hexaboride cathode is described.

Homo- and Heterobimetallic Ruthenium(II) and Osmium(II) Complexes Based on a Pyrene-Biimidazolate Spacer as Efficient DNA-Binding Probes in the Near-Infrared Domain.

PubMed

Mardanya, Sourav; Karmakar, Srikanta; Mondal, Debiprasad; Baitalik, Sujoy

2016-04-04

We report in this work a new family of homo- and heterobimetallic complexes of the type [(bpy)2M(Py-Biimz)M'(II)(bpy)2](2+) (M = M' = Ru(II) or Os(II); M = Ru(II) and M' = Os(II)) derived from a pyrenyl-biimidazole-based bridge, 2-imidazolylpyreno[4,5-d]imidazole (Py-BiimzH2). The homobimetallic Ru(II) and Os(II) complexes were found to crystallize in monoclinic form with space group P21/n. All the complexes exhibit strong absorptions throughout the entire UV-vis region and also exhibit luminescence at room temperature. For osmium-containing complexes (2 and 3) both the absorption and emission band stretched up to the NIR region and thus afford more biofriendly conditions for probable applications in infrared imaging and phototherapeutic studies. Detailed luminescence studies indicate that the emission originates from the respective (3)MLCT excited state mainly centered in the [M(bpy)2](2+) moiety of the complexes and is only slightly affected by the pyrene moiety. The bimetallic complexes show two successive one-electron reversible metal-centered oxidations in the positive potential window and several reduction processes in the negative potential window. An efficient intramolecular electronic energy transfer is found to occur from the Ru center to the Os-based component in the heterometallic dyad. The binding studies of the complexes with DNA were thoroughly studied through different spectroscopic techniques such as UV-vis absorption, steady-state and time-resolved emission, circular dichroism, and relative DNA binding study using ethidium bromide. The intercalative mode of binding was suggested to be operative in all cases. Finally, computational studies employing DFT and TD-DFT were also carried out to interpret the experimentally observed absorption and emission bands of the complexes.

PHYSICAL STUDIES OF PHOSPHOLIPIDS

PubMed Central

Chapman, D.; Fluck, D. J.

1966-01-01

On heating pure, fully saturated 2,3-diacyl-DL-phosphatidyl-ethanolamines and 2,3-diacylphosphatidyl-cholines (lecithins) in water to the transition temperature at which large endothermic heat changes occur, they are observed, by light microscopy, to form myelin figures. This result is discussed in terms of the large difference in the transition temperature for "melting" of the hydrocarbon chains of unsaturated and saturated phospholipids and is illustrated by means of differential thermal analysis (D.T.A.) curves. These structures have been examined by electron microscopy after negative staining and after reaction with osmium tetroxide. Typical phospholipid lamella structures are seen in the phosphatidylcholines after negative staining, and in the phosphatidyl-ethanolamines after both negative staining and osmium fixation. The distances across these lamellae have been measured. Some preliminary investigations of the nature of the osmium tetroxide reaction with the phosphatidyl-ethanolamines have been made. PMID:4165077

Investigation of the structure and properties of boron-containing coatings obtained by electron-beam treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Krivezhenko, Dina S., E-mail: dinylkaa@yandex.ru; Drobyaz, Ekaterina A., E-mail: ekaterina.drobyaz@yandex.ru; Bataev, Ivan A., E-mail: ivanbataev@ngs.ru

2015-10-27

An investigation of surface-hardened materials obtained by cladding with an electron beam injected into the air atmosphere was carried out. Structural investigations of coatings revealed that an increase in boron carbide concentration in a saturating mixture contributed to a rise of a volume fraction of iron borides in coatings. The maximum hardened depth reached 2 mm. Hardened layers were characterized by the formation of heterogeneous structure which consisted of iron borides and titanium carbides distributed uniformly in the eutectic matrix. Areas of titanium boride conglomerations were detected. It was found that an increase in the boron carbide content led to anmore » enhancement in hardness of the investigated materials. Friction testing against loosely fixed abrasive particles showed that electron-beam cladding of powder mixtures containing boron carbides, titanium, and iron in air atmosphere allowed enhancing a resistance of materials hardened in two times.« less

Thermodynamical and thermoelectric properties of boron doped YPd{sub 3} and YRh{sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dwivedi, Shalini; Sharma, Yamini, E-mail: sharma.yamini62@gmail.com; Sharma, Ramesh

2016-05-23

The structural, electronic, thermal, and optical properties of borides of cubic non-magnetic YX{sub 3} (X=Rh, Pd) compounds and their borides which crystallize in the AuCu{sub 3} structure have been studied using the density functional theory (DFT). The flat bands in the vicinity of E{sub F} which are associated with superconductivity appear in YPd{sub 3} and YRh{sub 3} band structures. However, the B s-states enhance the flat band only in YRh{sub 3}B. The optical properties clearly show that boron insertion modifies the absorption and transmittance. The YX{sub 3} alloys and their borides exhibit valuable changes in the thermopower and ZT. Itmore » is observed that the properties of the Y-X intermetallics change significantly for the Y-Rh and Y-Pd alloys and the presence of single boron atom modifies the properties to a great extent.« less

Analysis of boron carbides' electronic structure

NASA Technical Reports Server (NTRS)

Howard, Iris A.; Beckel, Charles L.

1986-01-01

The electronic properties of boron-rich icosahedral clusters were studied as a means of understanding the electronic structure of the icosahedral borides such as boron carbide. A lower bound was estimated on bipolaron formation energies in B12 and B11C icosahedra, and the associated distortions. While the magnitude of the distortion associated with bipolaron formation is similar in both cases, the calculated formation energies differ greatly, formation being much more favorable on B11C icosahedra. The stable positions of a divalent atom relative to an icosahedral borane was also investigated, with the result that a stable energy minimum was found when the atom is at the center of the borane, internal to the B12 cage. If incorporation of dopant atoms into B12 cages in icosahedral boride solids is feasible, novel materials might result. In addition, the normal modes of a B12H12 cluster, of the C2B10 cage in para-carborane, and of a B12 icosahedron of reduced (D sub 3d) symmetry, such as is found in the icosahedral borides, were calculated. The nature of these vibrational modes will be important in determining, for instance, the character of the electron-lattice coupling in the borides, and in analyzing the lattice contribution to the thermal conductivity.

Electrochemical Corrosion Behavior of Spray-Formed Boron-Modified Supermartensitic Stainless Steel

NASA Astrophysics Data System (ADS)

Zepon, Guilherme; Nogueira, Ricardo P.; Kiminami, Claudio S.; Botta, Walter J.; Bolfarini, Claudemiro

2017-04-01

Spray-formed boron-modified supermartensitic stainless steel (SMSS) grades are alloys developed to withstand severe wear conditions. The addition of boron to the conventional chemical composition of SMSS, combined with the solidification features promoted by the spray forming process, leads to a microstructure composed of low carbon martensitic matrix reinforced by an eutectic network of M2B-type borides, which considerably increases the wear resistance of the stainless steel. Although the presence of borides in the microstructure has a very beneficial effect on the wear properties of the alloy, their effect on the corrosion resistance of the stainless steel was not comprehensively evaluated. The present work presents a study of the effect of boron addition on the corrosion resistance of the spray-formed boron-modified SMSS grades by means of electrochemical techniques. The borides fraction seems to have some influence on the repassivation kinetics of the spray-formed boron-modified SMSS. It was shown that the Cr content of the martensitic matrix is the microstructural feature deciding the corrosion resistance of this sort of alloys. Therefore, if the Cr content in the alloy is increased to around 14 wt pct to compensate for the boron consumed by the borides formation, the corrosion resistance of the alloy is kept at the same level of the alloy without boron addition.

Phase equilibrium in system Ti-Si-C-B and synthesis of MAX phase layers in vacuum under the influence of electron beam

NASA Astrophysics Data System (ADS)

Smirnyagina, N. N.; Khaltanova, V. M.; Dasheev, D. E.; Lapina, A. E.

2017-05-01

Composite layers on the basis of carbides and borides the titan and silicon on titanic alloy VТ-1 are generated at diffused saturation by electron beam treatment in vacuum. Formation in a composite of MAX phase Ti3SiC2 is shown. Thermodynamic research of phase equilibrium in systems Ti-Si-C and Ti-B-C in the conditions of high vacuum is executed. The thermodynamics, formation mechanisms of superfirm layers borides and carbides of the titan and silicon are investigated.

The effect of melt refining upon inclusions in aluminum

NASA Astrophysics Data System (ADS)

Simensen, C. J.

1982-03-01

A series of aluminum melts has been refined with respect to inclusions by use of ALCOA 469, FILD, or SNIF. The content and size distribution of inclusions in the original-and the refined melts-have been measured by use of neutron activation (oxygen content), gas chromatography (carbide content), sedimentation analysis, and dissolution of metal in hydrochloric acid and subsequent analysis of oxides by means of a Coulter Counter. All the units tested have a beneficial effect and decrease the inclusion content, but the number of analyses are too few to make general conclusions. However, for melts cleaned by use of SNIF, it was found that oxides larger than 50 μm in cross section and borides larger than 20 μm in diameter were removed, while the smaller borides were agglomerated only. The effect of FILD and ALCOA 469 upon the melt tested was removal of borides larger than 5-10 μ m and oxides larger than 15μm in diameter, respectively.

Interfacial reactions in borsic/Ti-3Al-2-1/2V composite

NASA Technical Reports Server (NTRS)

Rao, V. B.; Houska, C. R.; Unnam, J.; Brewer, W. D.; Tenney, D. R.

1979-01-01

The paper provides a detailed X-ray characterization of a borsic/Ti-3Al-2-1/2V composite, and to correlate the relative intensities of the reaction products with the mechanical properties. Based on X-ray integrated intensity data two stages of interface reactions were identified: during the first stage there is a simultaneous interdiffusion of Si, C, and Ti atoms at the filament/matrix interface resulting in the formation of Ti5Si3, TiSi and small amounts of TiSi2 and TiC. The second stage is associated with considerable TiSi2 and boride formation. It appears that the alpha-phase of Ti is more reactive in forming silicides and borides than the beta-phase. The silicide intensities and the reaction zone thicknesses are shown to be directly related to the reduction of the ultimate tensile strength by thermal degradation, and the results indicate that silicide reaction products are as detrimental to strength as the borides.

Microstructure and High Temperature Mechanical Property of Fe-Cr-B Based Metal/Ceramic Composite Manufactured by Metal Injection Molding Process

NASA Astrophysics Data System (ADS)

Lee, Kee-Ahn; Gwon, Jin-Han; Yoon, Tae-Sik

2018-03-01

This study investigated the microstructure and the room and high temperature mechanical properties of Fe-Cr-B alloy manufactured by metal injection molding. In addition, hot isostatic pressing was performed to increase the density of the material, and a comparison of properties was made. Microstructural observation confirmed a bi-continuous structure composed of a three-dimensional network of α-Fe phase and (Cr,Fe)2B phase. The HIPed specimen featured a well-formed adhesion between the α-Fe phase and boride, and the number of fine pores was significantly reduced. The tensile results confirmed that the HIPed specimen (RT to 900 °C) had higher strengths compared to the as-sintered specimen, and the change of elongation starting from 700 °C was significantly greater in the HIPed specimen. Fractography suggested that cracks propagated mostly along the interface between the α-Fe matrix and boride in the as-sintered specimen, while direct fracture of boride was observed in addition to interface separation in the HIPed specimen.

Influence of heat treatment on microstructure and hot crack susceptibility of laser-drilled turbine blades made from Rene 80

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osterle, W.; Krause, S.; Moelders, T.

2008-11-15

Turbine components from conventionally cast nickel-base alloy Rene 80 show different hot cracking susceptibilities depending on their heat treatment conditions leading to slightly different microstructures. Electron probe micro-analysis, focused ion beam technique and analytical transmission electron microscopy were applied to reveal and identify grain boundary precipitates and the {gamma}-{gamma}'-microstructure. The distribution of borides along grain boundaries was evaluated statistically by quantitative metallography. The following features could be correlated with an increase of cracking susceptibility: i) Increasing grain size, ii) increasing fraction of grain boundaries with densely spaced borides, iii) lack of secondary {gamma}'-particles in matrix channels between the coarse cuboidalmore » {gamma}'-precipitates. The latter feature seems to be responsible for linking-up of cracked grain boundary precipitates which occurred as an additional cracking mechanism after one heat treatment, whereas decohesion at the boride-matrix-interface in the heat affected zone of laser-drilled holes was observed for both heat treatments.« less

Magnetic properties and magnetic hardening mechansim of Pt-Co-B alloys

NASA Technical Reports Server (NTRS)

Qiu, Ning; Flanagan, F.; Wittig, James E.

1994-01-01

The intrinsic coercivity is found to be maximized in the Pt42Co45B13 ternary alloy which is undercooled and rapidly solidified (quenched using a 70 m/s wheel speed after undercooling), and then annealed (800 C for 2400 min). The same alloy, processed at slower cooling rates and annealed in the same way, has a much larger scale microstructure and a much lower resulting magnetic coercivity. The microstructure which would optimize the coercitvity of this coercivity of this ternary alloy is a completely ordered L1(sub zero) Pt-Co matrix with a submicron magnetic single-domion Co-boride precipitate. The L1(sub zero) phase is highly anistropic magnetically while the Co-boride precipate is somewhat less so. Annealing treatments designed to produced single-domain Co-boride precipitates enhance the coercivity. This suggests that the refined microstructures is responsible for the high coercivities found in the rapidly solidified and annealed alloy. The magnetic domain wall thickness for a Co-boride precipitate is determined from both experimental observation and theoretical calculation in order to evaluate its influence on the coercivity of the alloy. The effects of the pinning of domain walls and the barrier to the nucleation of reverse domains on the coercivity are discussed. Both microstrucutral analysis and theoretical calculation indicate that the high coercivities in the Pt42Co45B13 alloy are due to the difficult nucleation of reverse magnetic domains.

Improving hardness and toughness of boride composites based on aluminum magnesium boride

NASA Astrophysics Data System (ADS)

Peters, Justin Steven

The search for new super-hard materials has usually focused on strongly bonded, highly symmetric crystal structures similar to diamond. The two hardest single-phase materials, diamond and cubic boron nitride (cBN), are metastable, and both must be produced at high temperatures and pressures, which makes their production costly. In 2000, a superhard composite based on a low-symmetry, boron-rich compound was reported. Since then, many advances have been made in the study of this AlMgB14--TiB2 composite. The composite has been shown to exhibit hardness greater than either of its constituent phases, relying on its sub-micron microstructure to provide hardening and strengthening mechanisms. With possible hardness around 40 GPa, an AlMgB 14--60 vol% TiB2 approaches the hardness of cBN, yet is amenable to processing under ambient pressure conditions. There are interesting aspects of both the AlMgB14 and TiB 2 phases. AlMgB14 is comprised of a framework of boron, mostly in icosahedral arrangements. It is part of a family of 12 known compounds with the same boron lattice, with the metal atoms replaced by Li, Na, Y or a number of Lanthanides. Another peculiar trait of this family of compounds is that every one contains a certain amount of intrinsic vacancies on one or both of the metal sites. These vacancies are significant, ranging from 3 to 43% of sites depending on the composition. TiB2 is a popular specialty ceramic material due to its high hardness, moderate toughness, good corrosion resistance, and high thermal and electrical conductivity. The major drawback is the difficulty of densification of pure TiB2 ceramics. A combination of sintering aids, pressure, and temperatures of 1800°C are often required to achieve near full density articles. The AlMgB14--TiB2 composites can achieve 99% density from hotpressing at 1400°C. This is mostly due to the preparation of powders by a high-energy milling technique known as mechanical alloying. The resulting fine powders have high activity, and Fe from wear debris acts as a sintering aid. Mechanical alloying improves the sinterability of the composite material, it has the same effect on pure TiB2. TiB 2 processed by high-energy milling has been found to achieve 99% theoretical density at 1400°C with the addition of ˜1 wt% Fe. Both the AlMgB14--TiB2 composites and pure TiB2 produced from these methods have enhanced mechanical properties due to their fine microstructures. These materials show exceptional promise in the field of wear resistance. This includes cutting tools, erosion resistant coatings, and low-friction sliding contacts to name a few. Under certain wear conditions, the composite material can show performance on par with that of current high-end cBN and WC materials tailored for wear resistance. The composite material also exhibits low reactivity with Ti alloys, a pre-requisite for effective machining of these alloys, a trait that few hard materials possess.

Microstructure of Vacuum-Brazed Joints of Super-Ni/NiCr Laminated Composite Using Nickel-Based Amorphous Filler Metal

NASA Astrophysics Data System (ADS)

Ma, Qunshuang; Li, Yajiang; Wu, Na; Wang, Juan

2013-06-01

Vacuum brazing of super-Ni/NiCr laminated composite and Cr18-Ni8 stainless steel was carried out using Ni-Cr-Si-B amorphous filler metal at 1060, 1080, and 1100 °C, respectively. Microstructure and phase constitution were investigated by means of optical and scanning electron microscopy, energy-dispersive spectroscopy, x-ray diffraction, and micro-hardness tester. When brazed at 1060-1080 °C, the brazed region can be divided into two distinct zones: isothermally solidified zone (ISZ) consisting of γ-Ni solid solution and athermally solidified zone (ASZ) consisting of Cr-rich borides. Micro-hardness of the Cr-rich borides formed in the ASZ was as high as 809 HV50 g. ASZ decreased with increase of the brazing temperature. Isothermal solidification occurred sufficiently at 1100 °C and an excellent joint composed of γ-Ni solid solution formed. The segregation of boron from ISZ to residual liquid phase is the reason of Cr-rich borides formed in ASZ. The formation of secondary precipitates in diffusion-affected zone is mainly controlled by diffusion of B.

The Quantitative Significance of Nondestructive Evaluation of Graphite and Ceramic Materials.

DTIC Science & Technology

NONDESTRUCTIVE TESTING), (* GRAPHITE , (*BORIDES, NONDESTRUCTIVE TESTING), (*REFRACTORY MATERIALS, NONDESTRUCTIVE TESTING), DEFECTS(MATERIALS), TENSILE PROPERTIES, RADIOGRAPHY, ULTRASONIC PROPERTIES, DENSITY.

Electrically conductive containment vessel for molten aluminum

DOEpatents

Holcombe, C.E.; Scott, D.G.

1984-06-25

The present invention is directed to a containment vessel which is particularly useful in melting aluminum. The vessel of the present invention is a multilayered vessel characterized by being electrically conductive, essentially nonwettable by and nonreactive with molten aluminum. The vessel is formed by coating a tantalum substrate of a suitable configuration with a mixture of yttria and particulate metal 10 borides. The yttria in the coating inhibits the wetting of the coating while the boride particulate material provides the electrical conductivity through the vessel. The vessel of the present invention is particularly suitable for use in melting aluminum by ion bombardment.

Electrically conductive containment vessel for molten aluminum

DOEpatents

Holcombe, Cressie E.; Scott, Donald G.

1985-01-01

The present invention is directed to a containment vessel which is particularly useful in melting aluminum. The vessel of the present invention is a multilayered vessel characterized by being electrically conductive, essentially nonwettable by and nonreactive with molten aluminum. The vessel is formed by coating a tantalum substrate of a suitable configuration with a mixture of yttria and particulate metal borides. The yttria in the coating inhibits the wetting of the coating while the boride particulate material provides the electrical conductivity through the vessel. The vessel of the present invention is particularly suitable for use in melting aluminum by ion bombardment.

Brazing Inconel 625 Using Two Ni/(Fe)-Based Amorphous Filler Foils

NASA Astrophysics Data System (ADS)

Chen, Wen-Shiang; Shiue, Ren-Kae

2012-07-01

For MBF-51 filler, the brazed joint consists of interfacial grain boundary borides, coarse Nb6Ni16Si7, and Ni/Cr-rich matrix. In contrast, the VZ-2106 brazed joint is composed of interfacial Nb6Ni16Si7 precipitates as well as grain boundary borides, coarse Nb6Ni16Si7, and Ni/Cr/Fe-rich matrix. The maximum tensile strength of 443 MPa is obtained from the MBF-51 brazed specimen. The tensile strengths of VZ-2106 brazed joints are approximately 300 MPa. Both amorphous filler foils demonstrate potential in brazing IN-625 substrate.

High-Temperature Syntheses of New, Thermally-Stable Chemical Compounds.

DTIC Science & Technology

SYNTHESIS(CHEMISTRY), HEAT RESISTANT PLASTICS, NITRILES, FLUORINE COMPOUNDS, COMPLEX COMPOUNDS, NITROGEN, SULFIDES, ORGANOMETALLIC COMPOUNDS, ORGANOBORANES, BORIDES, SPINEL, CARBIDES, NITRIDES, SILICIDES .

Redox polymer mediation for enzymatic biofuel cells

NASA Astrophysics Data System (ADS)

Gallaway, Joshua

Mediated biocatalytic cathodes prepared from the oxygen-reducing enzyme laccase and redox-conducting osmium hydrogels were characterized for use as cathodes in enzymatic biofuel cells. A series of osmium-based redox polymers was synthesized with redox potentials spanning the range from 0.11 V to 0.85 V (SHE), and the resulting biocatalytic electrodes were modeled to determine reaction kinetic constants using the current response, measured osmium concentration, and measured apparent electron diffusion. As in solution-phase systems, the bimolecular rate constant for mediation was found to vary greatly with mediator potential---from 250 s-1M-1 when mediator and enzyme were close in potential to 9.4 x 10 4 s-1M-1 when this overpotential was large. Optimum mediator potential for a cell operating with a non-limiting platinum anode and having no mass transport limitation from bulk solution was found to be 0.66 V (SHE). Redox polymers were synthesized under different concentrations, producing osmium variation. An increase from 6.6% to 7.2% osmium increased current response from 1.2 to 2.1 mA/cm2 for a planar film in 40°C oxygen-saturated pH 4 buffer, rotating at 900 rpm. These results translated to high surface area electrodes, nearly doubling current density to 13 mA/cm2, the highest to date for such an electrode. The typical fungal laccase from Trametes versicolor was replaced by a bacterially-expressed small laccase from Streptomyces coelicolor, resulting in biocatalytic films that reduced oxygen at increased pH, with full functionality at pH 7, producing 1.5 mA/cm 2 in planar configuration. Current response was biphasic with pH, matching the activity profile of the free enzyme in solution. The mediated enzyme electrode system was modeled with respect to apparent electron diffusion, mediator concentration, and transport of oxygen from bulk solution, all of which are to some extent controlled by design. Each factor was found to limit performance in certain circumstances

Catalytic asymmetric dihydroxylation of olefins with reusable OsO(4)(2-) on ion-exchangers: the scope and reactivity using various cooxidants.

PubMed

Choudary, Boyapati M; Chowdari, Naidu S; Jyothi, Karangula; Kantam, Mannepalli L

2002-05-15

Exchanger-OsO(4) catalysts are prepared by an ion-exchange technique using layered double hydroxides and quaternary ammonium salts covalently bound to resin and silica as ion-exchangers. The ion-exchangers with different characteristics and opposite ion selectivities are specially chosen to produce the best heterogeneous catalyst that can operate using the various cooxidants in the asymmetric dihydroxylation reaction. LDH-OsO(4) catalysts composed of different compositions are evaluated for the asymmetric dihydroxylation of trans-stilbene. Resin-OsO(4) and SiO(2)-OsO(4) designed to overcome the problems associated with LDH-OsO(4) indeed show consistent activity and enantioselectivity in asymmetric dihydroxylation of olefins using K(3)Fe(CN)(6) and molecular oxygen as cooxidants. Compared to the Kobayashi heterogeneous systems, resin-OsO(4) is a very efficient catalyst for the dihydroxylation of a wide variety of aromatic, aliphatic, acyclic, cyclic, mono-, di-, and trisubstituted olefins to afford chiral vicinal diols with high yields and enantioselectivities irrespective of the cooxidant used. Resin-OsO(4) is recovered quantitatively by a simple filtration and reused for a number of cycles with consistent activity. The high binding ability of the heterogeneous osmium catalyst enables the use of an equimolar ratio of ligand to osmium to give excellent enantioselectives in asymmetric dihydroxylation in contrast to the homogeneous osmium system in which excess molar quantities of the expensive chiral ligand to osmium are invariably used. The complexation of the chiral ligand (DHQD)(2)PHAL, having very large dimension, a prerequisite to obtain higher ee, is possible only with the OsO(4)(2-) located on the surface of the supports.

Lithium dendrite and solid electrolyte interphase investigation using OsO4

NASA Astrophysics Data System (ADS)

Zier, Martin; Scheiba, Frieder; Oswald, Steffen; Thomas, Jürgen; Goers, Dietrich; Scherer, Torsten; Klose, Markus; Ehrenberg, Helmut; Eckert, Jürgen

2014-11-01

Osmium tetroxide (OsO4) staining, commonly used to enhance scattering contrast in electron microscopy of biologic tissue and polymer blends, has been adopted for studies of graphite anodes in lithium-ion batteries. OsO4 shows a coordinated reaction with components of the solid electrolyte interphase (SEI) and lithium dendrites, thereby increasing material contrast for scanning electron microscopy investigations. Utilizing the high affinity of lithium metal to react with osmium tetroxide it was possible to localize even small lithium deposits on graphite electrodes. In spite of their reaction with the OsO4 fume, the lithium dendrite morphology remains almost untouched by the staining procedure, offering information on the dendrite growth process. Correlating the quantity of osmium detected with the amount of residual ("dead") lithium of a discharged electrode, it was possible to obtain a practical measure for lithium plating and stripping efficiencies. EDX mappings allowed for a localization of electrochemically stripped lithium dendrites by their residual stained SEI shells. Cross sections, prepared by focused ion beam (FIB) of cycled graphite electrodes treated with OsO4, revealed important information about deposition and distribution of metallic lithium and the electrolyte reduction layer across the electrode.

The causes for geographical variations in OS187/OS186 at the Cretaceous-Tertiary boundary

NASA Technical Reports Server (NTRS)

Turekian, K. K.; Esser, B. K.; Ravizza, G. E.

1988-01-01

Researchers at Yale has approached the problem of the osmium isotopic composition of marine deposits formed in contact with both oxidized and reduced bottom waters. The measured (187) Os/(186) Os ratios of modern bulk sediment can be explained using mixing equations involving continental detrital, volcaniclastic, cosmogenic and hydrogeneous components. These studies show that sediments deposited under reducing marine conditions contain a hydrogenous component which is enriched in Re and has a radiogenic (187) Os/(186) Os ratio. The presence of such a hydrogenous component in the marine fish clay at Stevns Klint can account for the elevation of its (187) Os/(186) Os ration above the expected meteoritic value. Mass balance considerations require the Re/Os ratio of the phase precipitated from the terminal Cretaceous sea at Stevns Klint to have been about one tenth the value observed in contemporary deposits in the Black Sea, assuming Re has not been lost (or Os gained) subsequent to precipitation. In continental sections, the elevation of the (187) Os/(186) Os ratio in boundary layers may be due to precipitation from continental waters of crustally-derived radiogenic osmium either contemporaneous with the meteoritic (or mantle) osmium deposition or later during diagenesis.

OsN2: Crystal structure and electronic properties

NASA Astrophysics Data System (ADS)

Montoya, Javier A.; Hernandez, Alexander D.; Sanloup, Chrystèle; Gregoryanz, Eugene; Scandolo, Sandro

2007-01-01

Osmium nitride belongs to a family of nitrides synthesized recently at high pressures from their parent elements. Here we show, based on first-principles calculations, that the crystal structure of osmium nitride is isostructural to marcasite. Excellent agreement is obtained between the authors' results and x-ray, Raman, and compressibility measurements. In the OsN2 marcasite structure single-bonded N2 units occupy the interstitial sites of the Os close-packed lattice, giving rise to a metallic compound. A comparison between the formation energies of OsN2 and PtN2 explains the similar thermodynamic conditions of formation reported experimentally for the two compounds.

Evaluation of the rhenium-osmium geochronometer in the Phosphoria petroleum system, Bighorn Basin of Wyoming and Montana, USA

USGS Publications Warehouse

Lillis, Paul G.; Selby, David

2013-01-01

Rhenium-osmium (Re-Os) geochronometry is applied to crude oils derived from the Permian Phosphoria Formation of the Bighorn Basin in Wyoming and Montana to determine whether the radiogenic age reflects the timing of petroleum generation, timing of migration, age of the source rock, or the timing of thermochemical sulfate reduction (TSR). The oils selected for this study are interpreted to be derived from the Meade Peak Phosphatic Shale and Retort Phosphatic Shale Members of the Phosphoria Formation based on oil-oil and oil-source rock correlations utilizing bulk properties, elemental composition, δ13C and δ34S values, and biomarker distributions. The δ34S values of the oils range from -6.2‰ to +5.7‰, with oils heavier than -2‰ interpreted to be indicative of TSR. The Re and Os isotope data of the Phosphoria oils plot in two general trends: (1) the main trend (n = 15 oils) yielding a Triassic age (239 ± 43 Ma) with an initial 187Os/188Os value of 0.85 ± 0.42 and a mean square weighted deviation (MSWD) of 1596, and (2) the Torchlight trend (n = 4 oils) yielding a Miocene age (9.24 ± 0.39 Ma) with an initial 187Os/188Os value of 1.88 ± 0.01 and a MSWD of 0.05. The scatter (high MSWD) in the main-trend regression is due, in part, to TSR in reservoirs along the eastern margin of the basin. Excluding oils that have experienced TSR, the regression is significantly improved, yielding an age of 211 ± 21 Ma with a MSWD of 148. This revised age is consistent with some studies that have proposed Late Triassic as the beginning of Phosphoria oil generation and migration, and does not seem to reflect the source rock age (Permian) or the timing of re-migration (Late Cretaceous to Eocene) associated with the Laramide orogeny. The low precision of the revised regression (±21 Ma) is not unexpected for this oil family given the long duration of generation from a large geographic area of mature Phosphoria source rock, and the possible range in the initial 187Os/188Os

Osmium-Iridium Correlation and Osmium Isotopic Composition in Some Geological Boundaries and Meteorites

NASA Astrophysics Data System (ADS)

Liu, Y. Z.; Wang, J. X.; Mao, X. Y.; Chai, C. F.

1992-07-01

Since the pioneering study of Alvarez et al. on K/T boundary event, Ir has long been considered to be the main indicator of extraterrestrial materials in boundaries, while little work about Os and its isotopic composition have been done. In this work a sophisticated radiochemical separation procedure together with neutron activation analsis (NAA) method was established for the determination of Os in some geological boundaries (P epsilon/epsilon, K/T, D/C, O/S, P/T). Combined with our early work--determination of Ir abundances [1], the sources of boundary events were deciphered by using the Os/Ir ratios. Simultaneously ^184Os/^190Os ratios in K/T boundaries, as well as inclusions of Allende chondrite and acid-insoluble residues of iron meteorites (Nandan, Jianshi, Longchang) were determined to search for the Os isotopic composition anomalies resulted from the extrasolar components by RNAA. The results show that the Os abundances exhibit a positive correlation with the Ir abundances for overall K/T boundary samples, but only the Os/Ir ratios of K/T boundaries, with the average of 0.98 +- 0.55, are in excellent agreement with 1.01 of the solar system [2], Accordingly, it provides new evidence for an extraterrestrial source of the K/T event. The results of ^184Os/^190Os ratios, with uncertainties of less than 1%, indicate there is no remarkable ^184Os/^190Os ratio anomaly in the K/T boundary samples, which implies the impacting matter may be from the solar system not the extrasolar, while no anomaly exists in the inclusions of Allende chondrite and acid-insoluble residues of iron meteorites, which disagree with the results obtained by Goel [3]. REFERENCES [1] Chai Chifang (1988) Isotopenpraxis 24, pp. 257-272. [2] Anders E. and Grevesse N. (l989) Geochim. Cosmochim. Acta 53, 197-214. [3] Goel P.S.(1987) Proc. Indian Acad. Sci. (Earth Planet. Sci), 96, pp. 81-102.

New examples of ternary rare-earth metal boride carbides containing finite boron carbon chains: The crystal and electronic structure of RE15B6C20 (RE=Pr, Nd)

NASA Astrophysics Data System (ADS)

Babizhetskyy, Volodymyr; Mattausch, Hansjürgen; Simon, Arndt; Hiebl, Kurt; Ben Yahia, Mouna; Gautier, Régis; Halet, Jean-François

2008-08-01

The ternary rare-earth metal boride carbides RE15B6C20 (RE=Pr, Nd) were synthesized by co-melting the elements. They exist above 1270 K. Their crystal structures were determined from single-crystal X-ray diffraction data. Both crystallize in the space group P1¯, Z=1, a=8.3431(8) Å, b=9.2492(9) Å, c=8.3581(8) Å, α=84.72(1)°, β=89.68(1)°, γ =84.23(1)° (R1=0.041 (wR2=0.10) for 3291 reflections with Io>2σ(Io)) for Pr15B6C20, and a=8.284(1) Å, b=9.228(1) Å, c=8.309(1) Å, α=84.74(1)°, β=89.68(1)°, γ=84.17(2)° (R1=0.033 (wR2=0.049) for 2970 reflections with Io>2σ(Io)) for Nd15B6C20. Their structure consists of a three-dimensional framework of rare-earth metal atoms resulting from the stacking of slightly corrugated and distorted square nets, leading to cavities filled with unprecedented B2C4 finite chains, disordered C3 entities and isolated carbon atoms, respectively. Structural and theoretical analyses suggest the ionic formulation (RE3+)15([B2C4]6-)3([C3]4-)2(C4-)2·11ē. Accordingly, density functional theory calculations indicate that the compounds are metallic. Both structural arguments as well as energy calculations on different boron vs. carbon distributions in the B2C4 chains support the presence of a CBCCBC unit. Pr15B6C18 exhibits antiferromagnetic order at TN=7.9 K, followed by a meta-magnetic transition above a critical external field B>0.03 T. On the other hand, Nd15B6C18 is a ferromagnet below TC≈40 K.

The complex metal-rich boride Ti1+xRh2-x+yIr3-yB3 (x=0.68, y=1.06) with a new structure type containing B4 zigzag fragments: Synthesis, crystal chemistry and theoretical calculations

NASA Astrophysics Data System (ADS)

Goerens, Christian; Fokwa, Boniface P. T.

2012-08-01

Polycrystalline samples and single crystals of the new complex boride Ti1+xRh2-x+yIr3-yB3 (x=0.68; y=1.06) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere and characterized by X-Ray diffraction as well as EDX measurements. The crystal structure was refined on the basis of single crystal data. The new phase, which represents a new structure type containing trans zigzag B4 fragments as well as isolated boron atoms crystallizes in the orthorhombic space group Pbam (Nr. 55) with the lattice parameters a=8.620(1) Å, b=14.995(2) Å and c=3.234(1) Å. First-principles density functional theory calculations using the Vienna ab-initio simulation package (VASP) were performed on an appropriate structural model (using a supercell approach) and the experimental crystallographic data could be reproduced accurately. Based on this model, the density of states and crystal orbital Hamilton population (for bonding analysis) were calculated, using the linear muffin-tin orbital atomic sphere approximation (LMTO-ASA) method. According to these calculations, this metal-rich compound should be metallic, as expected. Furthermore, very strong boron-boron interactions are observed in the trans zigzag B4 fragment, which induce a clear differentiation of two types of metal-boron contacts with different strength. The observed three-dimensional metal-metal interaction is in good agreement with the predicted metallic behavior.

Transient episodes of mild environmental oxygenation and oxidative continental weathering during the late Archean

PubMed Central

Kendall, Brian; Creaser, Robert A.; Reinhard, Christopher T.; Lyons, Timothy W.; Anbar, Ariel D.

2015-01-01

It is not known whether environmental O2 levels increased in a linear fashion or fluctuated dynamically between the evolution of oxygenic photosynthesis and the later Great Oxidation Event. New rhenium-osmium isotope data from the late Archean Mount McRae Shale, Western Australia, reveal a transient episode of oxidative continental weathering more than 50 million years before the onset of the Great Oxidation Event. A depositional age of 2495 ± 14 million years and an initial 187Os/188Os of 0.34 ± 0.19 were obtained for rhenium- and molybdenum-rich black shales. The initial 187Os/188Os is higher than the mantle/extraterrestrial value of 0.11, pointing to mild environmental oxygenation and oxidative mobilization of rhenium, molybdenum, and radiogenic osmium from the upper continental crust and to contemporaneous transport of these metals to seawater. By contrast, stratigraphically overlying black shales are rhenium- and molybdenum-poor and have a mantle-like initial 187Os/188Os of 0.06 ± 0.09, indicating a reduced continental flux of rhenium, molybdenum, and osmium to seawater because of a drop in environmental O2 levels. Transient oxygenation events, like the one captured by the Mount McRae Shale, probably separated intervals of less oxygenated conditions during the late Archean. PMID:26702438

Sodium bicarbonate secretion indicated by ultrastructural cytochemical localization of HCO3(-), Cl-, and Na+ ions on rat bile duct brush cells.

PubMed

Ogata, Takuro

2005-12-01

Brush cells are widely distributed in the digestive and respiratory apparatus, but their function is still unknown. Because brush cells (BC) are found in organs secreting NaHCO3, it was hypothesized that these cells may secrete NaHCO3. To test this possibility, rat common bile duct epithelia were examined by ultrastructural cytochemical methods for localizing HCO3(-), Cl-, and Na+ ions. All three ion precipitates were few in or on BCs of rats without stimulation. Lead carbonate precipitates, which localized HCO3(-) ions by the lead nitrate-osmium method, increased markedly on the surface of the microvilli (MV) of BCs after secretin or meal stimulation, but similar precipitates were few on the luminal surface of principal cells (PCs). Silver chloride precipitates, which indicate the presence of Cl- ions by the silver-osmium method, increased in the apical cytoplasm and in MV of BCs after secretin or meal stimulation, but they were few in PCs. Sodium pyroantimonate precipitates, which localize Na+ ions by the potassium pyroantimonate-osmium method, increased on the surface of the MV, along the basolateral membrane, and in the apical cytoplasm of BCs after secretin or meal stimulation, but they were few in PCs. These results strongly suggest that BCs may be a significant source of NaHCO3 secretion.

B Layers and Adhesion on Armco Iron Substrate

NASA Astrophysics Data System (ADS)

Elias-Espinosa, M.; Ortiz-Domínguez, M.; Keddam, M.; Flores-Rentería, M. A.; Damián-Mejía, O.; Zuno-Silva, J.; Hernández-Ávila, J.; Cardoso-Legorreta, E.; Arenas-Flores, A.

2014-08-01

In this work, a kinetic model was suggested to evaluate the boron diffusion coefficient in the Fe2B layers grown on the Armco iron substrate by the powder-pack boriding. This thermochemical treatment was carried out in the temperature range of 1123-1273 K for treatment times ranging from 2 to 8 h. The boron diffusion coefficient in the Fe2B layers was estimated by solving the mass balance equation at the (Fe2B/substrate) interface with an inclusion of boride incubation time. To validate the present model, the simulated value of Fe2B layer thickness was compared with the experimental value obtained at 1253 K for a treatment time of 5 h. The morphology of Fe2B layers was observed by SEM and optical microscopy. Metallographic studies showed that the boride layer has a saw-tooth morphology in all the samples. The layer thickness measurements were done with the help of MSQ PLUS software. The Fe2B phase was identified by x-ray diffraction method. Finally, the adherence of Fe2B layers on the Armco iron substrate was qualitatively evaluated by using the Daimler-Benz Rockwell-C indentation technique. In addition, the estimated value of boron activation energy was compared to the literature data.

Corrosion and wear behaviors of boronized AISI 316L stainless steel

NASA Astrophysics Data System (ADS)

Kayali, Yusuf; Büyüksaǧiş, Aysel; Yalçin, Yılmaz

2013-09-01

In this study, the effects of a boronizing treatment on the corrosion and wear behaviors of AISI 316L austenitic stainless steel (AISI 316L) were examined. The corrosion behavior of the boronized samples was studied via electrochemical methods in a simulation body fluid (SBF) and the wear behavior was examined using the ball-on-disk wear method. It was observed that the boride layer that formed on the AISI 316L surface had a flat and smooth morphology. Furthermore, X-ray diffraction analyses show that the boride layer contained FeB, Fe2B, CrB, Cr2B, NiB, and Ni2B phases. Boride layer thickness increased with an increasing boronizing temperature and time. The boronizing treatment also increased the surface hardness of the AISI 316L. Although there was no positive effect of the coating on the corrosion resistance in the SBF medium. Furthermore, a decrease in the friction coefficient was recorded for the boronized AISI 316L. As the boronizing temperature increased, the wear rate decreased in both dry and wet mediums. As a result, the boronizing treatment contributed positively to the wear resistance by increasing the surface hardness and by decreasing the friction coefficient of the AISI 316L.

Etude des mecanismes de formation des microstructures lors du brasage isotherme de superalliages a base de nickel

NASA Astrophysics Data System (ADS)

Ruiz-Vargas, Jose

This thesis reports theoretical and experimental investigations carried out to understand the mechanisms of microstructure formation during isothermal brazing, produced by brazing Inconel 625 and MC2 nickel-based superalloys with filler metal BNi-2. Firstly, studies were made on pure Ni to interpret microstructure's formation with simplified alloy chemistry. Microstructure formation have been studied when varying time at constant temperature (isothermal kinetics), but also when varying temperature for constant hold time (isochronal kinetics). The chemical composition and crystallography of the present phases have been identified, with the following results : (i) the fraction of dissolved base metal has been found proportional to the initial thickness of the brazing alloy, so that the composition of the liquid remains homogeneous with a precise initial equilibrium composition during the whole brazing process, (ii) the melting of the joint occurs in two steps : at lower temperature, it involves only partially melting, and boron diffusion in pure Ni leads to the precipitation of fine Ni3B borides at the interface ; in a second stage, at higher temperature, melting is complete and thermodynamic equilibrium requires significant dissolution of nickel, which also involves the dissolution of part of borides already formed. Secondly, nickel plating technique was used on Inconel 625 nickel-based superalloy. A thin layer of Ni with varying thickness, has been electrodeposited to observe the gradual dissolution of Inconel and microstructural features formation due to the presence of superalloy alloying elements. It has been observed that the nickel coating does not prevent precipitation in the base metal as boron diffuse rapidly through the coating width. In the intermediate nickel plating width, fragile precipitates of nickel borides have been observed, because the contribution of Inconel alloying elements to the melt was very limited. In absence of nickel plating on the

Plasma enhanced chemical vapor deposition of metalboride interfacial layers as diffusion barriers for nanostructured diamond growth on cobalt containing alloys CoCrMo and WC-Co

NASA Astrophysics Data System (ADS)

Johnston, Jamin M.

This work is a compilation of theory, finite element modeling and experimental research related to the use of microwave plasma enhanced chemical vapor deposition (MPECVD) of diborane to create metal-boride surface coatings on CoCrMo and WC-Co, including the subsequent growth of nanostructured diamond (NSD). Motivation for this research stems from the need for wear resistant coatings on industrial materials, which require improved wear resistance and product lifetime to remain competitive and satisfy growing demand. Nanostructured diamond coatings are a promising solution to material wear but cannot be directly applied to cobalt containing substrates due to graphite nucleation. Unfortunately, conventional pre-treatment methods, such as acid etching, render the substrate too brittle. Thus, the use of boron in a MPECVD process is explored to create robust interlayers which inhibit carbon-cobalt interaction. Furthermore, modeling of the MPECVD process, through the COMSOL MultiphysicsRTM platform, is performed to provide insight into plasma-surface interactions using the simulation of a real-world apparatus. Experimental investigation of MPECVD boriding and NSD deposition was conducted at surface temperatures from 700 to 1100 °C. Several well-adhered metal-boride surface layers were formed: consisting of CoB, CrB, WCoB, CoB and/or W2CoB2. Many of the interlayers were shown to be effective diffusion barriers against elemental cobalt for improving nucleation and adhesion of NSD coatings; diamond on W2CoB2 was well adhered. However, predominantly WCoB and CoB phase interlayers suffered from diamond film delamination. Metal-boride and NSD surfaces were evaluated using glancing-angle x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), cross-sectional scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), micro-Raman spectroscopy, nanoindentation, scratch testing and epoxy pull testing. COMSOL MultiphysicsRTM was used to construct a

(Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5}, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salamakha, Leonid P.; Sologub, Oksana, E-mail: oksana.sologub@univie.ac.at; Stöger, Berthold

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt{sub 1−x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.33) forms a B-filled β-Mn-type structure (space group P4{sub 1}32; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt{sub 9}Cu{sub 3}B{sub 5} (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt{sub 9}Zn{submore » 3}B{sub 5–δ}-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt{sub 6}] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt{sub 6}] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt{sub 6}] and [Pt{sub 6}] trigonal prisms, rotated perpendicularly to the central one. There is no B–B contact as well as Cu–B contact in the structure. The relationships of Pt{sub 9}Cu{sub 3}B{sub 5} structure with the structure of Ti{sub 1+x}Os{sub 2−x}RuB{sub 2} as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ{sub 0}H{sub C2}(0){sup WHH} of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt{sub 9}Cu{sub 3}B{sub 5} (Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure) from electrical resistivity measurements. - Highlights: • First two copper platinum borides, (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu

Ultrastructural histochemical investigations of "dense deposit disease". Pathogenetic approach to a special type of mesangiocapillary glomerulonephritis.

PubMed

Muda, A O; Barsotti, P; Marinozzi, V

1988-01-01

Dense deposit disease is characterized by the presence of intramembranous dense deposits; their constituents are unknown but immunological and biochemical studies have demonstrated that they contain no gamma-globulins or any other plasma protein. In order to clarify the nature of the dense deposits better, we investigated their most distinctive character, (marked electron-density) by means of ultrastructural histochemistry techniques using thin sections from Formaldehyde fixed, OsO4 postfixed and Epon embedded specimens collected for diagnostic electron microscopy. The dense deposits have a higher osmium affinity than the lamina densa of normal basement membranes, and the electron-density is strictly osmium-dependent suggesting the presence of a lipid component. Further data, obtained using an extraction method for lipids, seems to confirm our hypothesis.

Lithium Borides - High Energy Materials

DTIC Science & Technology

2000-02-28

1993. 99, 7983. (32) Pulay P.; Hamilton. T. P. J. Chem. Phys. 1988, 88. 4926 . (33) Frisch. M. J.: Trucks. G. W.; Schlegel. H. B.: Gill, P. M. W...25] P.V. Sudhakar, K. Lammertsma, J. Chem. Phys. 99 (1993) 7929. [26] M.J. van der Woerd, K. Lammertsma, B.J. Duke, H.F. Schaefer , III, J

Ternary boride product and process

NASA Technical Reports Server (NTRS)

Clougherty, Edward V. (Inventor)

1976-01-01

A hard, tough, strong ceramic body is formed by hot pressing a mixture of a powdered metal and a powdered metal diboride. The metal employed is zirconium, titanium or hafnium and the diboride is the diboride of a different member of the same group of zirconium, titanium or hafnium to form a ternary composition. During hot pressing at temperatures above about 2,000.degree.F., a substantial proportion of acicular ternary monoboride is formed.

The Chelyabinsk Fall Highly Siderophile Element Abundance and 187Os/188Os Composition and Comparison with Ordinary and Carbonaceous Chondrites

NASA Astrophysics Data System (ADS)

Day, J. M. D.; Corder, C. A.; Dhaliwal, J. K.; Liu, Y.; Taylor, L. A.

2014-09-01

New osmium isotope and highly siderophile element abundance data are presented for the Chelyabinsk ordinary chondrite fall (February 2013) and placed into context with new data for ordinary and carbonaceous chondrites.

Direct synthesis of magnesium borohydride

DOEpatents

Ronnebro, Ewa Carin Ellinor [Kennewick, WA; Severa, Godwin [Honolulu, HI; Jensen, Craig M [Kailua, HI

2012-04-03

A method is disclosed for directly preparing an alkaline earth metal borohydride, i.e. Mg(BH.sub.4).sub.2, from the alkaline earth metal boride MgB.sub.2 by hydrogenating the MgB.sub.2 at an elevated temperature and pressure. The boride may also be doped with small amounts of a metal chloride catalyst such as TiCl.sub.3 and/or NiCl.sub.2. The process provides for charging MgB.sub.2 with high pressure hydrogen above at least 70 MPa while simultaneously heating the material to about 350.degree. C. to about 400.degree. C. The method is relatively simple and inexpensive and provides a reversible hydride compound having a hydrogen capacity of at least 11 wt %.

Ternary ceramic thermal spraying powder and method of manufacturing thermal sprayed coating using said powder

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vogli, Evelina; Sherman, Andrew J.; Glasgow, Curtis P.

The invention describes a method for producing ternary and binary ceramic powders and their thermal spraying capable of manufacturing thermal sprayed coatings with superior properties. Powder contain at least 30% by weight ternary ceramic, at least 20% by weight binary molybdenum borides, at least one of the binary borides of Cr, Fe, Ni, W and Co and a maximum of 10% by weight of nano and submicro-sized boron nitride. The primary crystal phase of the manufactured thermal sprayed coatings from these powders is a ternary ceramic, while the secondary phases are binary ceramics. The coatings have extremely high resistance againstmore » corrosion of molten metal, extremely thermal shock resistance and superior tribological properties at low and at high temperatures.« less

Reactions of technetium hexafluoride with nitric acid, nitrosyl fluoride, and nitryl fluoride

NASA Technical Reports Server (NTRS)

Holloway, J. H.; Selig, H.

1970-01-01

Stoichiometry of technetium hexafluoride reactions is studied. Magnetic properties and infrared spectra of reaction products are studied and compared with those of analogous complexes of the hexafluorides of tungsten, rhenium, and osmium.

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and...

Thermal analysis, phase equilibria, and superconducting properties in magnesium boride and carbon doped magnesium boride

NASA Astrophysics Data System (ADS)

Bohnenstiehl, Scot David

In this work, the low temperature synthesis of MgB2 from Mg/B and MgH2/B powder mixtures was studied using Differential Scanning Calorimetry (DSC). For the Mg/B powder mixture, two exothermic reaction events were observed and the first reaction event was initiated by the decomposition of Mg(OH)2 on the surface of the magnesium powder. For the MgH 2/B powder mixture, there was an endothermic event at ˜375 °C (the decomposition of MgH2 into H2 and Mg) and an exothermic event ˜600 °C (the reaction of Mg and B). The Kissinger analysis method was used to estimate the apparent activation energy of the Mg and B reaction using DSC data with different furnace ramp rates. The limitations of MgB2 low temperature synthesis led to the development of a high pressure induction furnace that was constructed using a pressure vessel and an induction heating power supply. The purpose was to not only synthesize more homogeneous MgB2 samples, but also to determine whether MgB2 melts congruently or incongruently. A custom implementation of the Smith Thermal Analysis method was developed and tested on aluminum and AlB2, the closest analogue to MgB2. Measurements on MgB2 powder and a high purity Mg/B elemental mixture confirmed that MgB2 melts incongruently and decomposes into a liquid and MgB4 at ˜1445 °C at 10 MPa via peritectic decomposition. Another measurement using a Mg/B elemental mixture with impure boron suggested that ˜0.7 wt% carbon impurity in the boron raised the incongruent melting temperature to ˜1490-1500 °C. Lastly, the solubility limit for carbon in MgB2 was studied by making samples from B4C and Mg at 1530 °C, 1600 °C and 1700 °C in the high pressure furnace. All three samples had three phases: Mg, MgB2C2, and carbon doped MgB2. The MgB 2C2 and carbon doped MgB2 grain size increased with temperature and the 1700 °C sample had needle-like grains for both phases. The presence of the ternary phase, MgB2C2, suggested that the maximum doping limit for carbon in MgB2 had been reached. The 1530 °C sample was characterized by Electron Probe Microanalysis at the University of Oregon and the average carbon concentration was estimated to be ˜5.9 at%. Further investigation using TEM found MgO inclusions in the 1530 °C sample which were not detected with X-ray diffraction.

Microstructural characterization of Ni-based self-fluxing alloy after selective surface-engineering using diode laser

NASA Astrophysics Data System (ADS)

Chun, Eun-Joon; Park, Changkyoo; Nishikawa, Hiroshi; Kim, Min-Su

2018-06-01

The microstructural characterization of thermal-sprayed Ni-based self-fluxing alloy (Metco-16C®) after laser-assisted homogenization treatment was performed. To this end, a high-power diode laser system was used. This supported the real-time control of the target homogenization temperature at the substrate surface. Non-homogeneities of the macrosegregation of certain elements (C and Cu) and the local concentration of Cr-based carbides and borides in certain regions in the as-sprayed state could be enhanced with the application of homogenization. After homogenization at 1423 K, the hardness of the thermal-sprayed layer was found to have increased by 1280 HV from the as-sprayed state (750 HV). At this homogenization temperature, the microstructure of the thermal-sprayed layer consisted of a lamellar structuring of the matrix phase (austenite and Ni3Si) with fine (<5 μm) carbides and borides (the rod-like phase of Cr5B3, the lumpy phase of M23C6, and the extra-fine phase of M7C3). Despite the formation of several kinds of carbides and borides during homogenization at 1473 K, the lowest hardness level was found to be less than that of the as-sprayed state, because of the liquid-state homogenization treatment without formation of lamellar structuring between austenite and Ni3Si.

Visualization of predentine matrix components and endocytic structures in rat incisor odontoblasts with tannic acid.

PubMed

Goldberg, M; Septier, D

1989-12-01

Rat incisor odontoblasts and predentine fixed with tannic acid-glutaraldehyde-osmium tetroxide (Tago) were compared with those obtained by prior incubation in tannic acid-Ringer before conventional fixation with glutaraldehyde-osmium-tetroxide (Tari) The Tago method allowed visualization of complex glycoconjugates along the plasma membrane, in the pericellular spaces and in the intercellular predentine matrix. The non-collagenous proteins, proteoglycans and lipids were seen as granules and thin filaments located between the collagen fibers and at their surface. The collagen fibers themselves were also stained. The Tari method which was used to visualize exocytosis, mainly revealed endocytosis in the form of large intracellular vacuoles containing tannic acid and stained proteoglycans. It is suggested that tannic acid-Ringer incubation prior to fixation increases the endocytosis of the matrix components, which acculumates in these large vesicles.

Determination of osmium concentrations and (187)Os/(188)Os of crude oils and source rocks by coupling high-pressure, high-temperature digestion with sparging OsO(4) into a multicollector inductively coupled plasma mass spectrometer.

PubMed

Sen, Indra S; Peucker-Ehrenbrink, Bernhard

2014-03-18

The (187)Os/(188)Os ratio that is based on the β(-)-decay of (187)Re to (187)Os (t1/2 = 41.6 billion years) is widely used to investigate petroleum system processes. Despite its broad applicability to studies of hydrocarbon deposits worldwide, a suitable matrix-matched reference material for Os analysis does not exist. In this study, a method that enables Os isotope measurement of crude oil with in-line Os separation and purification from the sample matrix is proposed. The method to analyze Os concentration and (187)Os/(187)Os involves sample digestion under high pressure and high temperature using a high pressure asher (HPA-S, Anton Paar), sparging of volatile osmium tetroxide from the sample solution, and measurements using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This methods significantly reduced the total procedural time compared to conventional Carius tube digestion followed by Os separation and purification using solvent extraction, microdistillation and N-TIMS analysis. The method yields Os concentration (28 ± 4 pg g(-1)) and (187)Os/(188)Os (1.62 ± 0.15) of commercially available crude oil reference material NIST 8505 (1 S.D., n = 6). The reference material NIST 8505 is homogeneous with respect to Os concentration at a test portion size of 0.2 g. Therefore, (187)Os/(188)Os composition and Os concentration of NIST 8505 can serve as a matrix-matched reference material for Os analysis. Data quality was assessed by repeated measurements of the USGS shale reference material SCo-1 (sample matrix similar to petroleum source rock) and the widely used Liquid Os Standard solution (LOsSt). The within-laboratory reproducibility of (187)Os/(188)Os for a 5 pg of LOsSt solution, analyzed with this method over a period of 12 months was ∼1.4% (1 S.D., n = 26), respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corbea, Javier Jesus Concepcion; Chen, Zoufeng; Jurss, Jonah Wesley

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ceramic fibers from Si-B-C polymer precursors

NASA Technical Reports Server (NTRS)

Riccitiello, S. R.; Hsu, M. S.; Chen, T. S.

1993-01-01

Non-oxide ceramics such as silicon carbide (SiC), silicon nitride (Si3N4), and silicon borides (SiB4, SiB6) have thermal stability, oxidation resistance, hardness, and varied electrical properties. All these materials can be prepared in a fiber form from a suitable polymer precursor. The above mentioned fibers, when tested over a temperature range from 25 to 1400 C, experience degradation at elevated temperatures. Past work in ceramic materials has shown that the strength of ceramics containing both carbides and borides is sustained at elevated temperatures, with minimum oxidation. The work presented here describes the formation of ceramic fibers containing both elements, boron and silicon, prepared via the polymer precursor route previously reported by the authors, and discusses the fiber mechanical properties that are retained over the temperature range studied.

Design of Wear-Resistant Austenitic Steels for Selective Laser Melting

NASA Astrophysics Data System (ADS)

Lemke, J. N.; Casati, R.; Lecis, N.; Andrianopoli, C.; Varone, A.; Montanari, R.; Vedani, M.

2018-03-01

Type 316L stainless steel feedstock powder was modified by alloying with powders containing carbide/boride-forming elements to create improved wear-resistant austenitic alloys that can be readily processed by Selective Laser Melting. Fe-based alloys with high C, B, V, and Nb contents were thus produced, resulting in a microstructure that consisted of austenitic grains and a significant amount of hard carbides and borides. Heat treatments were performed to modify the carbide distribution and morphology. Optimal hard-phase spheroidization was achieved by annealing the proposed alloys at 1150 °C for 1 hour followed by water quenching. The total increase in hardness of samples containing 20 pct of C/B-rich alloy powder was of 82.7 pct while the wear resistance could be increased by a factor of 6.

Paleogene Seawater Osmium Isotope Records

NASA Astrophysics Data System (ADS)

Rolewicz, Z.; Thomas, D. J.; Marcantonio, F.

2012-12-01

Paleoceanographic reconstructions of the Late Cretaceous and early Cenozoic require enhanced geographic coverage, particularly in the Pacific, in order to better constrain meridional variations in environmental conditions. The challenge with the existing inventory of Pacific deep-sea cores is that they consist almost exclusively of pelagic clay with little existing age control. Pelagic clay sequences are useful for reconstructions of dust accumulation and water mass composition, but accurate correlation of these records to other sites requires improved age control. Recent work indicates that seawater Os isotope analyses provide useful age control for red clay sequences. The residence time of Os in seawater is relatively long compared to oceanic mixing, therefore the global seawater 187Os/188Os composition is practically homogeneous. A growing body of Late Cretaceous and Cenozoic data has constrained the evolution of the seawater Os isotopic composition and this curve is now a viable stratigraphic tool, employed in dating layers of Fe-Mn crusts (e.g., Klemm et al., 2005). Ravizza (2007) also demonstrated that the seawater Os isotopic composition can be extracted reliably from pelagic red clay sediments by analyzing the leached oxide minerals. The drawback to using seawater Os isotope stratigraphy to date Paleogene age sediments is that the compilation of existing data has some significant temporal gaps, notably between ~38 and 55 Ma. To improve the temporal resolution of the seawater Os isotope curve, we present new data from Ocean Drilling Program (ODP) Site 865 in the equatorial Pacific. Site 865 has excellent biostratigraphic age control over the interval ~38-55Ma. Preliminary data indicate an increase in the seawater composition from 0.427 at 53.4 Ma to 0.499 by 43 Ma, consistent with the apparent trend in the few existing data points. We also analyzed the Os isotopic composition recorded by oxide minerals at Integrated Ocean Drilling Program (IODP) Site U1370 to construct an age model for this predominantly pelagic clay section. The 187Os/188Os values generally increase from 0.312 at 64.46 mbsf to 0.531 at 28.26 mbsf. The low value recorded at 64.46 likely reflects the Os isotope minimum recorded across the K/Pg boundary, while the uppermost value likely correlates to the E/O interval. Comparison of the Os-derived ages with a crude linearly interpolated sedimentation rate age model reveals variations in sediment accumulation rate between 0.86 and 1.5 m/Myr.

Osmium Isotope Systematics of Ureilites

NASA Technical Reports Server (NTRS)

Rankenburg, K.; Brandon, A. d.; Humayun, M.

2007-01-01

The Os-187/Os-188 for twenty-two ureilite whole rock samples, including monomict, augite-bearing, and polymict lithologies, were examined in order to constrain the provenance and subsequent magmatic processing of the ureilite parent body (or bodies). The Re/Os ratios of most ureilites show evidence for a recent disturbance, probably related to Re mobility during weathering, and no meaningful chronological information can be extracted from the present data set. The ureilite Os-187/Os-188 ratios span a range from 0.11739 to 0.13018, with an average of 0.1258+/-0.0023 (1(sigma)), similar to typical carbonaceous chondrites, and distinct from ordinary or enstatite chondrites. The similar mean of Os-187/Os-188 measured for the ureilites and carbonaceous chondrites suggests that the ureilite parent body probably formed within the same region of the solar nebula as carbonaceous chondrites. From the narrow range of the 187Os/188Os distribution in ureilite meteorites it is further concluded that Re was not significantly fractionated from Os during planetary differentiation and was not lost along with the missing ureilitic melt component. The lack of large Re/Os fractionations requires that Re/Os partitioning was controlled by a metal phase, and thus metal had to be stable throughout the interval of magmatic processing on the ureilite parent body.

Osmium isotopes and mantle convection.

PubMed

Hauri, Erik H

2002-11-15

The decay of (187)Re to (187)Os (with a half-life of 42 billion years) provides a unique isotopic fingerprint for tracing the evolution of crustal materials and mantle residues in the convecting mantle. Ancient subcontinental mantle lithosphere has uniquely low Re/Os and (187)Os/(188)Os ratios due to large-degree melt extraction, recording ancient melt-depletion events as old as 3.2 billion years. Partial melts have Re/Os ratios that are orders of magnitude higher than their sources, and the subduction of oceanic or continental crust introduces into the mantle materials that rapidly accumulate radiogenic (187)Os. Eclogites from the subcontinental lithosphere have extremely high (187)Os/(188)Os ratios, and record ages as old as the oldest peridotites. The data show a near-perfect partitioning of Re/Os and (187)Os/(188)Os ratios between peridotites (low) and eclogites (high). The convecting mantle retains a degree of Os-isotopic heterogeneity similar to the lithospheric mantle, although its amplitude is modulated by convective mixing. Abyssal peridotites from the ocean ridges have low Os isotope ratios, indicating that the upper mantle had undergone episodes of melt depletion prior to the most recent melting events to produce mid-ocean-ridge basalt. The amount of rhenium estimated to be depleted from the upper mantle is 10 times greater than the rhenium budget of the continental crust, requiring a separate reservoir to close the mass balance. A reservoir consisting of 5-10% of the mantle with a rhenium concentration similar to mid-ocean-ridge basalt would balance the rhenium depletion of the upper mantle. This reservoir most likely consists of mafic oceanic crust recycled into the mantle over Earth's history and provides the material that melts at oceanic hotspots to produce ocean-island basalts (OIBs). The ubiquity of high Os isotope ratios in OIB, coupled with other geochemical tracers, indicates that the mantle sources of hotspots contain significant quantities (greater than 10%) of lithologically distinct mafic material which represents ancient oceanic lithosphere cycled through the convecting mantle on a time-scale of 800 million years or more.

NEUTRONIC REACTOR FUEL COMPOSITION

DOEpatents

Thurber, W.C.

1961-01-10

Uranium-aluminum alloys in which boron is homogeneously dispersed by adding it as a nickel boride are described. These compositions have particular utility as fuels for neutronic reactors, boron being present as a burnable poison.

Synthesis of pentafluorides

DOEpatents

Asprey, L.B.; Paine, R.T. Jr.

1975-12-30

The reactions of uranium, molybdenum, rhenium, osmium and iridium hexafluorides with hydrogen gas in the presence of ultraviolet radiation or with silicon powder in an anhydrous HF slurry provide especially useful, high yield syntheses of pure pentafluorides.

Thermophysical and Electronic Properties Information Analysis Center (TEPIAC): A Continuing Systematic Program on Tables of Thermophysical and Electronic Properties of Materials.

DTIC Science & Technology

1977-02-01

oxides and their mixtures, arsenides, borides, bromides , carbides , chlorides , fluoride s, nitride s, phosphides, silicides , sulfides , tellurides...ivity of alkali elements (lithium , sodium , potassium , rubi- dium , ces ium , and francium) and contains recomme nded reference values generated

Tungsten isotope evidence that mantle plumes contain no contribution from the Earth's core

NASA Astrophysics Data System (ADS)

Scherstén, Anders; Elliott, Tim; Hawkesworth, Chris; Norman, Marc

2004-01-01

Osmium isotope ratios provide important constraints on the sources of ocean-island basalts, but two very different models have been put forward to explain such data. One model interprets 187Os-enrichments in terms of a component of recycled oceanic crust within the source material. The other model infers that interaction of the mantle with the Earth's outer core produces the isotope anomalies and, as a result of coupled 186Os-187Os anomalies, put time constraints on inner-core formation. Like osmium, tungsten is a siderophile (`iron-loving') element that preferentially partitioned into the Earth's core during core formation but is also `incompatible' during mantle melting (it preferentially enters the melt phase), which makes it further depleted in the mantle. Tungsten should therefore be a sensitive tracer of core contributions in the source of mantle melts. Here we present high-precision tungsten isotope data from the same set of Hawaiian rocks used to establish the previously interpreted 186Os-187Os anomalies and on selected South African rocks, which have also been proposed to contain a core contribution. None of the samples that we have analysed have a negative tungsten isotope value, as predicted from the core-contribution model. This rules out a simple core-mantle mixing scenario and suggests that the radiogenic osmium in ocean-island basalts can better be explained by the source of such basalts containing a component of recycled crust.

Internal Grains Within KFC Graphites: Implications for Their Stellar Source

NASA Astrophysics Data System (ADS)

Croat, T. K.; Stadermann, F. J.; Bernatowicz, T. J.

2005-03-01

TEM and NanoSIMS investigations find high s-process element enrichments in internal carbides, suggesting an AGB origin for most Murchison KFC presolar graphites. Other rare phases (iron phases and metallic osmium) are consistent with a SN origin.

Anomalous stress response of ultrahard WB n compounds

DOE PAGES

Li, Quan; Zhou, Dan; Zheng, Weitao; ...

2015-10-29

Boron-rich tungsten borides are premier prototypes of a new class of ultrahard compounds. Here, we show by first-principles calculations that their stress-strain relations display surprisingly diverse and anomalous behavior under a variety of loading conditions. Most remarkable is the dramatically changing bonding configurations and deformation modes with rising boron concentration in WB n (n=2, 3, 4), resulting in significantly different stress responses and unexpected indentation strength variations. This novel phenomenon stems from the peculiar structural arrangements in tungsten borides driven by boron’s ability to form unusually versatile bonding states. Our results elucidate the intriguing deformation mechanisms that define a distinctmore » type of ultrahard material. Here, these new insights underscore the need to explore unconventional structure-property relations in a broad range of transition-metal light-element compounds.« less

NASA research on refractory compounds.

NASA Technical Reports Server (NTRS)

Gangler, J. J.

1971-01-01

The behavior and properties of the refractory carbides, nitrides, and borides are being investigated by NASA as part of its research aimed at developing superior heat resistant materials for aerospace applications. Studies of the zirconium-carbon-oxygen system show that zirconium oxycarbides of different compositions and lattice parameters can be formed between 1500 C and 1900 C and are stable below 1500 C. More applied studies show that hot working generally improves the microstructure and therefore the strength of TiC and NbC. Sintering studies on UN indicate that very high densities can be achieved. Hot pressing of cermets of HfN and HfC produces good mechanical properties for high temperature bearing applications. Attempts to improve the impact resistance of boride composites by the addition of a nickel or carbon yarn were not overly successful.

Re-Os systematics of early proterozoic ferropicrites, Pechenga Complex, northwestern Russia: Evidence for ancient 187Os-enriched plumes

NASA Astrophysics Data System (ADS)

Walker, Richard J.; Morgan, John W.; Hanski, Eero J.; Smolkin, Valery F.

1997-08-01

The Re-Os isotopic systematics of various ferropicritic flows and sills of the Pechenga Complex, Russia, have been examined. During crystallization about 1.98 Ga ago, many of these bodies became highly differentiated. In addition, some of the larger igneous units are associated with major NiCu ore deposits. The melts that produced these rocks have been termed ferropicritic because of their high FeO and MgO contents. They are also enriched in light rare earth elements (LREEs), TiO 2, Zr, and many other incompatible trace elements. Previous studies have concluded that the ferropicrites were most likely derived from an Fe-rich mantle plume that had a complex history of long-term LREE depletion (initial ɛNd = + 1.4), but that also experienced a LREE enrichment event within 200 Ma of the generation of the rocks. Whole rock samples believed to be most representative of primary melt compositions indicate that initial melt concentrations of rhenium and osmium were approximately 1.1 ppb and 0.5 ppb, respectively. The high primary melt concentrations presumably made the osmium contained in the melts relatively immune to the effects of crustal contamination. Nonetheless, all ore-bearing intrusions examined show osmium isotopic evidence for crustal contamination. For example, the initial γOs for some primary magmatic sulfides from the Pilgujärvi intrusion average +46. Other ore-bearing intrusions, such as the Kammikivi sill, appear to have been similarly contaminated by crustal osmium during the injection of magma, with initial yo, values as high as +251. The seemingly high levels of crustal osmium may be attributed to the rapidly diminishing concentrations of osmium in the melts as the larger bodies differentiated, combined with localized in situ assimilation of the metasedimentary rocks that comprise the country rocks. The Re-Os systematics of some whole rock samples of both mineralized and sulfide-poor intrusions were affected by post-magmatic events, especially the

Computer Modeling of Ceramic Boride Composites

DTIC Science & Technology

2014-11-01

the reinforcer deform elastically, for the theoretical strength of the composite it can be written [46] BBBAAABBAAK EE δεδεσδσδσ +=+= (51) where...coefficients of thermal expansion. Approximately linear expansion coefficient of the composite is determined by the relation [52] EEE BBBAAAk...1 δαδαα ⋅+⋅= , (58) where AE and BE are Young moduli of components, and E – average modulus for composition BBAA EEE δδ

Catalytic asymmetric dihydroxylation of olefins using a recoverable and reusable OsO(4)2- in ionic liquid [bmim][PF6].

PubMed

Branco, Luís C; Afonso, Carlos A M

2002-12-21

The use of the solvent systems water/ionic liquid or water/ionic liquid/tert-butanol provides a recoverable, reusable, robust and simple system for the asymmetric dihydroxylation of olefins, based on the immobilization of the osmium-ligand catalyst in the ionic liquid phase.

10 CFR Appendix L to Part 110 - Illustrative List of Byproduct Materials Under NRC Export/Import Licensing Authority a

Code of Federal Regulations, 2010 CFR

2010-01-01

... 149 (Nd 149) Neptunium 235 (Np 235) Neptunium 237 (Np 237) Nickel 59 (Ni 59) Nickel 63 (Ni 63) Nickel 65 (Ni 65) Niobium 93m (Nb 93m) Niobium 94 (Nb 94) Niobium 95 (Nb 95) Niobium 97 (Nb 97) Osmium 185...

40 CFR 421.261 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... apply to this subpart. (b) The term precious metals shall mean gold, platinum, palladium, rhodium, iridium, osmium, and ruthenium. (c) The term Combined Metals, shall mean the total of gold, platinum and... AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY Secondary Precious Metals...

Specific features of thermal and magnetic properties of Yb B50 at low temperatures

NASA Astrophysics Data System (ADS)

Novikov, V. V.; Zhemoedov, N. A.; Matovnikov, A. V.; Mitroshenkov, N. V.; Popova, E. A.; Tolstosheev, A. K.; Malkin, B. Z.; Bud'ko, S. L.

2018-05-01

Heat capacity, thermal expansion, and magnetization of ytterbium boride Yb B50 were studied at temperatures 0.6-300 K, 5-300 K, and 2-300 K, respectively. We revealed two smooth peaks at about 4.0 and 60 K in the temperature dependence of the heat capacity. A comparison with the heat capacity of the diamagnetic isostructural boride Lu B50 shows that these anomalies can be attributed to excitations in the ytterbium sublattice (Schottky anomalies). A scheme for splitting of the ground F 7 /2 2 multiplet of Y b3 + ions in the crystal field is proposed. Reliability of the proposed crystal-field energies of the Y b3 + ions is confirmed by the analysis of temperature dependencies of magnetic susceptibility and magnetization in applied magnetic fields up to 55 kOe. A clear anisotropy of the thermal expansion and a negative expansion within a wide temperature range (40-185 K) were observed. Assuming that this anomaly of the thermal expansion in higher borides is caused by the specific thermal evolution of a crystal lattice observed earlier, in particular, in Lu B50 , and the interaction of rare-earth ions with lattice strains, we have determined phenomenological Grüneisen parameters which characterize effects due to thermal transitions of Y b3 + ions between the ground and excited states. A phase transition of Yb B50 to any magnetically ordered state was not observed down to the lowest temperatures of experiments.

Fusion welding of a modern borated stainless steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robino, C.V.; Cieslak, M.J.

1997-01-01

Experiments designed to assess the fabrication and service weldability of 304B4A borated stainless steel were conducted. Welding procedures and parameters for manual gas tungsten arc (GTA) welding, autogenous electron beam (EB) welding and filler-added EB welding were developed and found to be similar to those for austenitic stainless steels. Following the procedure development, four test welds were produced and evaluated by microstructural analysis and Charpy impact testing. Further samples were used for determination of the postweld heat treatment (PWHT) response of the welds. The fusion zone structure of welds in this alloy consists of primary austenite dendrites with an interdendriticmore » eutectic-like austenite/boride constituent. Welds also show an appreciable partially molten zone that consists of the austenite/boride eutectic surrounding unmelted austenite islands. The microstructure of the EB welds was substantially finer than that of the GTA welds, and boride coarsening was not observed in the solid state heat-affected zone (HAZ) of either weld type. The impact toughness of as-welded samples was found to be relatively poor, averaging less than 10 J for both GTA and EB welds. For fusion zone notched GTA and EB samples and centerline notched EB samples, fracture generally occurred along the boundary between the partially molten and solid-state regions of the HAZ. The results of the PWHT study were very encouraging, with typical values of the impact energy for HAZ notched samples approaching 40 J, or twice the minimum code-acceptable value.« less

Mineral resource of the month: platinum-group metals

USGS Publications Warehouse

Hilliard, Henry

2003-01-01

The precious metals commonly referred to as platinum-group metals (PGM) include iridium, osmium, palladium, platinum, rhodium and ruthenium. PGM are among the rarest of elements, and their market values — particularly for palladium, platinum and rhodium — are the highest of all precious metals.

40 CFR 266.70 - Applicability and requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) STANDARDS FOR THE MANAGEMENT OF SPECIFIC HAZARDOUS WASTES AND SPECIFIC TYPES OF HAZARDOUS WASTE... requirements. (a) The regulations of this subpart apply to recyclable materials that are reclaimed to recover economically significant amounts of gold, silver, platinum, palladium, iridium, osmium, rhodium, ruthenium, or...

Electrocatalyst compositions

DOEpatents

Mallouk, Thomas E.; Chan, Benny C.; Reddington, Erik; Sapienza, Anthony; Chen, Guoying; Smotkin, Eugene; Gurau, Bogdan; Viswanathan, Rameshkrishnan; Liu, Renxuan

2001-09-04

Compositions for use as catalysts in electrochemical reactions are described. The compositions are alloys prepared from two or more elemental metals selected from platinum, molybdenum, osmium, ruthenium, rhodium, and iridium. Also described are electrode compositions including such alloys and electrochemical reaction devices including such catalysts.

Photovoltaic cell

DOEpatents

Gordon, Roy G.; Kurtz, Sarah

1984-11-27

In a photovoltaic cell structure containing a visibly transparent, electrically conductive first layer of metal oxide, and a light-absorbing semiconductive photovoltaic second layer, the improvement comprising a thin layer of transition metal nitride, carbide or boride interposed between said first and second layers.

Preparation and characterization of some alkanethiolatoosmium compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schobert, Harold Harris

1970-11-01

Results of magnetic susceptibility and infrared spectroscopy studies are presented and briefly discussed. The reaction of osmium tetrachloride with simple alkanethiols was found to proceed readily at room temperature, yielding in a few days a product of black amorphous solid soluble in most common organic solvents.

Ultrastructure of sea urchin calcified tissues after high-pressure freezing and freeze substitution.

PubMed

Ameye, L; Hermann, R; Dubois, P

2000-08-01

The improvements brought by high-pressure freezing/freeze substitution fixation methods to the ultrastructural preservation of echinoderm mineralized tissues are investigated in developing pedicellariae and teeth of the echinoid Paracentrotus lividus. Three freeze substitution (FS) protocols were tested: one in the presence of osmium tetroxide, one in the presence of uranyl acetate, and the last in the presence of gallic acid. FS in the presence of osmium tetroxide significantly improved cell ultrastructure preservation and should especially be used for ultrastructural studies involving vesicles and the Golgi apparatus. With all protocols, multivesicular bodies, suggested to contain Ca(2+), were evident for the first time in skeleton-forming cells. FS in the presence of gallic acid allowed us to confirm the structured and insoluble character of a part of the organic matrix of mineralization in the calcification sites of the tooth, an observation which modifies the current understanding of biomineralization control in echinoderms. Copyright 2000 Academic Press.

Ultra High Temperature Ceramics' Processing Routes and Microstructures Compared

NASA Technical Reports Server (NTRS)

Gusman, Michael; Stackpoole, Mairead; Johnson, Sylvia; Gasch, Matt; Lau, Kai-Hung; Sanjurjo, Angel

2009-01-01

Ultra High Temperature Ceramics (UHTCs), such as HfB2 and ZrB2 composites containing SiC, are known to have good thermal shock resistance and high thermal conductivity at elevated temperatures. These UHTCs have been proposed for a number of structural applications in hypersonic vehicles, nozzles, and sharp leading edges. NASA Ames is working on controlling UHTC properties (especially, mechanical properties, thermal conductivity, and oxidation resistance) through processing, composition, and microstructure. In addition to using traditional methods of combining additives to boride powders, we are preparing UHTCs using coat ing powders to produce both borides and additives. These coatings and additions to the powders are used to manipulate and control grain-boundary composition and second- and third-phase variations within the UHTCs. Controlling the composition of high temperature oxidation by-products is also an important consideration. The powders are consolidated by hot-pressing or field-assisted sintering (FAS). Comparisons of microstructures and hardness data will be presented.

The physical and mechanical metallurgy of advanced O+BCC titanium alloys

NASA Astrophysics Data System (ADS)

Cowen, Christopher John

This thesis comprises a systematic study of the microstructural evolution, phase transformation behavior, elevated-temperature creep behavior, room-temperature and elevated-temperature tensile behavior, and room-temperature fatigue behavior of advanced titanium-aluminum-niobium (Ti-Al-Nb) alloys with and without boron additions. The specific alloys studied were: Ti-5A1-45Nb (at%), Ti-15Al-33Nb (at%), Ti-15Al-33Nb-0.5B (at%), Ti-15Al-33Nb-5B (at%), Ti-21Al-29Nb (at%), Ti-22Al-26Nb (at%), and Ti-22Al-26Nb-5B (at%). The only alloy composition that had been previously studied before this thesis work began was Ti-22Al-26Nb (at%). Publication in peer-reviewed material science journals of the work performed in this thesis has made data available in the scientific literature that was previously non-existent. The knowledge gap for Ti-Al-Nb phase equilibria over the compositional range of Ti-23Al-27Nb (at%) to Ti-12Al-38Nb (at%) that existed before this work began was successfully filled. The addition of 5 at% boron to the Ti-15Al-33Nb alloy produced 5-9 volume percent boride phase needles within the microstructure. The chemical composition of the boride phase measured by electron microprobe was determined to be approximately B 2TiNb. The lattice parameters of the boride phase were simulated through density functional theory calculations by collaborators at the Air Force Research Laboratory based on the measured composition. Using the simulated lattice parameters, electron backscatter diffraction kikuchi patterns and selected area electron diffraction patterns obtained from the boride phase were successfully indexed according to the space group and site occupancies of the B27 orthorhombic crystal structure. This suggests that half the Ti (c) Wyckoff positions are occupied by Ti atoms and the other half are occupied by Nb atoms in the boride phase lattice. Creep deformation behavior is the main focus of this thesis and in particular understanding the dominant creep

(Pt1-xCux)3Cu2B and Pt9Cu3B5, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

NASA Astrophysics Data System (ADS)

Salamakha, Leonid P.; Sologub, Oksana; Stöger, Berthold; Michor, Herwig; Bauer, Ernst; Rogl, Peter F.

2015-09-01

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt1-xCux)3Cu2B (x=0.33) forms a B-filled β-Mn-type structure (space group P4132; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt9Cu3B5 (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt9Zn3B5-δ-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt6] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt6] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt6] and [Pt6] trigonal prisms, rotated perpendicularly to the central one. There is no B-B contact as well as Cu-B contact in the structure. The relationships of Pt9Cu3B5 structure with the structure of Ti1+xOs2-xRuB2 as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt1-xCux)3Cu2B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ0HC2(0)WHH of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt9Cu3B5 (Pt9Zn3B5-δ-type structure) from electrical resistivity measurements.

Thermal emission property of solid solution Gd{sub 1-x}Nd{sub x}B{sub 6} (x=0, 0.6, 0.8)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xing Zhang, Jiu; Hong Bao, Li; Lin Zhou, Shen, E-mail: zjiuxing@bjut.edu.cn, E-mail: Baolihong_10@yahoo.com.cn, E-mail: zhoushenlin@emails.bjut.edu.cn

2011-07-01

In this paper, to further explore the excellent emission properties of rare earth boride cathode, herein we present the synthesis, characterization and properties of polycrystalline Nd{sub 1-x}Gd{sub x}B{sub 6} (x = 0, 0.6, 0.8) bulk via arc plasma and reactive SPS. (author)

Effect of Discharge Time on Plasma Electrolytic Borocarbonitriding of Pure Iron

NASA Astrophysics Data System (ADS)

Jin, Xiaoyue; Wu, Jie; Wang, Bin; Yang, Xuan; Chen, Lin; Qu, Yao; Xue, Wenbin

The plasma electrolytic borocarbonitriding (PEB/C/N) process on pure iron was carried out in 25% borax solution with glycerine and carbamide additives under different discharge time at 360V. The morphology and structure of PEB/C/N hardened layers were analyzed by SEM and XRD. The hardness profiles of hardened layers were measured by microhardness test. Corrosion behavior of PEB/C/N layers was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Their wear performance was carried out using a pin-disc friction and wear tester under dry sliding test. The PEB/C/N samples mainly consisted of α-Fe, Fe2B, Fe3C, FeN, FeB, Fe2O3 and Fe4N phases, and the Fe2B phase was the dominant phase in the boride layer. It was found that the thickness of boride layer increased with the discharge time and reached 14μm after 60min treatment. The microhardness of the boride layer was up to 2100HV, which was much higher than that of the bare pure iron (about 150HV). After PEB/C/N treatment, the corrosion resistance of pure iron was slightly improved. The friction coefficient of PEB/C/N treated pure iron decreased to 0.129 from 0.556 of pure iron substrate. The wear rate of the PEB/C/N layer after 60min under dry sliding against ZrO2 ball was only 1/10 of that of the bare pure iron. The PEB/C/N treatment is an effective way to improve the wear behavior of pure iron.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-09-23

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4more » and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Ultracapacitor current collector

DOEpatents

Jerabek, Elihu Calfin; Mikkor, Mati

2001-10-16

An ultracapacitor having two solid, nonporous current collectors, two porous electrodes separating the collectors, a porous separator between the electrodes and an electrolyte occupying the pores in the electrodes and separator. At least one of the current collectors comprises a conductive metal substrate coated with a metal nitride, carbide or boride coating.

Process research into metallic pipe wear of hot chamber die casting machines and methods ofincreasing wear resistance

NASA Astrophysics Data System (ADS)

Mukhametzyanova, G. F.; Kolesnikov, MS; Mukhametzyanov, I. R.; Astatshenko, V. I.

2017-09-01

The kinetics and reasons for metallic pipe wear of hot chamberzinc alloy die casting machines are established.Increasing metallic pipe wear components wear resistance is being achieved by means of die steelДИ - 22 with electroslag remelting modification and electron-beamremelting modification and after the processes of nitriding and boriding besides.

Temporal record of osmium concentrations and 187Os/188Os in organic-rich mudrocks: Implications for the osmium geochemical cycle and the use of osmium as a paleoceanographic tracer

NASA Astrophysics Data System (ADS)

Lu, Xinze; Kendall, Brian; Stein, Holly J.; Hannah, Judith L.

2017-11-01

We present a compilation of 192Os concentrations (representing non-radiogenic Os) and initial 187Os/188Os isotope ratios from organic-rich mudrocks (ORM) to explore the evolution of the Os geochemical cycle during the past three billion years. The initial 187Os/188Os isotope ratio of a Re-Os isochron regression for ORM constrains the local paleo-seawater 187Os/188Os, which is governed by the relative magnitudes of radiogenic Os (old continental crust) and unradiogenic Os (mantle, extraterrestrial, and juvenile/mafic/ultramafic crust) fluxes to seawater. A first-order increase in seawater 187Os/188Os ratios occurs from the Archean to the Phanerozoic, and may reflect a combination of increasing atmosphere-ocean oxygenation and weathering of progressively more radiogenic continental crust due to in-growth of 187Os from radioactive decay of 187Re. Superimposed on this long-term trend are shorter-term fluctuations in seawater 187Os/188Os ratios as a result of climate change, emplacement of large igneous provinces, bolide impacts, tectonic events, changes in seafloor spreading rates, and lithological changes in crustal terranes proximal to sites of ORM deposition. Ediacaran-Phanerozoic ORM have mildly higher 192Os concentrations overall compared with pre-Ediacaran Proterozoic ORM based on the mean and 95% confidence interval of 10,000 median values derived using a bootstrap analysis for each time bin (insufficient Archean data exist for robust statistical comparisons). However, there are two groups with anomalously high 192Os concentrations that are distinguished by their initial 187Os/188Os isotope ratios. Ediacaran-Cambrian ORM from South China have radiogenic initial 187Os/188Os, suggesting their high 192Os concentrations reflect proximal Os-rich crustal source(s), ultraslow sedimentation rates, and/or other unusual depositional conditions. In contrast, the unradiogenic initial 187Os/188Os and high 192Os concentrations of some Mesozoic ORM can be tied to emplacement of large igneous provinces. Excluding these two anomalous groups and repeating the bootstrap analysis, we find that, overall, the 192Os concentrations for the Ediacaran-Phanerozoic and pre-Ediacaran Proterozoic time bins are not significantly different. An improved understanding of Os geochemical behavior in modern environments is required before our compilation can be fully used to constrain the temporal evolution of the seawater Os reservoir.

Combustion synthesis of boride and other composites

DOEpatents

Halverson, Danny C.; Lum, Beverly Y.; Munir, Zuhair A.

1989-01-01

A self-sustaining combustion synthesis process for producing hard, tough, lightweight B.sub.4 C/TiB.sub.2 composites is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B.sub.4 C and TiB.sub.2 reactants. For lightweight products the composition must be relatively rich in the B.sub.4 C component. B.sub.4 C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component.

Combustion synthesis of boride and other composites

DOEpatents

Halverson, D.C.; Lum, B.Y.; Munir, Z.A.

1988-07-28

A self-sustaining combustion synthesis process for producing hard, tough, lightweight B/sub 4/C/TiB/sub 2/ composites is described. It is based on the thermodynamic dependence of adiabatic temperature and product composition on the stoichiometry of the B/sub 4/C and TiB/sub 2/ reactants. For lightweight products the composition must be relatively rich in the B/sub 4/C component. B/sub 4/C-rich composites are obtained by varying the initial temperature of the reactants. The product is hard, porous material whose toughness can be enhanced by filling the pores with aluminum or other metal phases using a liquid metal infiltration process. The process can be extended to the formation of other composites having a low exothermic component. 9 figs., 4 tabs.

Applications of the 190Pt-186Os isotope system to geochemistry and cosmochemistry

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Beary, E.S.; Smoliar, M.I.; Czamanske, G.K.; Horan, M.F.

1997-01-01

Platinum is fractionated from osmium primarily as a consequence of processes involving sulfide and metal crystallization. Consequently, the 190Pt-186Os isotope system (190Pt ??? 186Os + ??) shows promise for dating some types of magmatic sulfide ores and evolved iron meteorites. The first 190Pt-186Os isochrons are presented here for ores from the ca. 251 Ma Noril'sk, Siberia plume, and for group IIAB magmatic iron meteorites. Given the known age of the Noril'sk system, a decay constant for 190Pt is determined to be 1.542 ?? 10-12a-1, with ??1% uncertainty. The isochron generated for the IIAB irons is consistent with this decay constant and the known age of the group. The 186Os/188Os ratios of presumably young, mantle-derived osmiridiums and also the carbonaceous chondrite Allende were measured to high-precision to constrain the composition of the modern upper mantle. These compositions overlap, indicating that the upper mantle is chondritic within the level of resolution now available. Our best estimate for this 186Os/188Os ratio is 0.119834 ?? 2 (2??M). The 190Pt/186Os ratios determined for six enstatite chondrites average 0.001659 ?? 75, which is very similar to published values for carbonaceous chondrites. Using this ratio and the presumed composition of the modern upper mantle and chondrites, a solar system initial 186Os/188Os ratio of 0.119820 is calculated. In comparison to the modern upper mantle composition, the 186Os/188Os ratio of the Noril'sk plume was approximately 0.012% enriched in 186Os. Possible reasons for this heterogeneity include the recycling of Pt-rich crust into the mantle source of the plume and derivation of the osmium from the outer core. Derivation of the osmium from the outer core is our favored model. Copyright ?? 1997 Elsevier Science Ltd.

Fabrication of crystals from single metal atoms

PubMed Central

Barry, Nicolas P. E.; Pitto-Barry, Anaïs; Sanchez, Ana M.; Dove, Andrew P.; Procter, Richard J.; Soldevila-Barreda, Joan J.; Kirby, Nigel; Hands-Portman, Ian; Smith, Corinne J.; O’Reilly, Rachel K.; Beanland, Richard; Sadler, Peter J.

2014-01-01

Metal nanocrystals offer new concepts for the design of nanodevices with a range of potential applications. Currently the formation of metal nanocrystals cannot be controlled at the level of individual atoms. Here we describe a new general method for the fabrication of multi-heteroatom-doped graphitic matrices decorated with very small, ångström-sized, three-dimensional (3D)-metal crystals of defined size. We irradiate boron-rich precious-metal-encapsulated self-spreading polymer micelles with electrons and produce, in real time, a doped graphitic support on which individual osmium atoms hop and migrate to form 3D-nanocrystals, as small as 15 Å in diameter, within 1 h. Crystal growth can be observed, quantified and controlled in real time. We also synthesize the first examples of mixed ruthenium–osmium 3D-nanocrystals. This technology not only allows the production of ångström-sized homo- and hetero-crystals, but also provides new experimental insight into the dynamics of nanocrystals and pathways for their assembly from single atoms. PMID:24861089

DFT investigations of hydrogen storage materials

NASA Astrophysics Data System (ADS)

Wang, Gang

Hydrogen serves as a promising new energy source having no pollution and abundant on earth. However the most difficult problem of applying hydrogen is to store it effectively and safely, which is smartly resolved by attempting to keep hydrogen in some metal hydrides to reach a high hydrogen density in a safe way. There are several promising metal hydrides, the thermodynamic and chemical properties of which are to be investigated in this dissertation. Sodium alanate (NaAlH4) is one of the promising metal hydrides with high hydrogen storage capacity around 7.4 wt. % and relatively low decomposition temperature of around 100 °C with proper catalyst. Sodium hydride is a product of the decomposition of NaAlH4 that may affect the dynamics of NaAlH4. The two materials with oxygen contamination such as OH- may influence the kinetics of the dehydriding/rehydriding processes. Thus the solid solubility of OH - groups (NaOH) in NaAlH4 and NaH is studied theoretically by DFT calculations. Magnesium boride [Mg(BH4)2] is has higher hydrogen capacity about 14.9 wt. % and the decomposition temparture of around 250 °C. However one flaw restraining its application is that some polyboron compounds like MgB12H12 preventing from further release of hydrogen. Adding some transition metals that form magnesium transition metal ternary borohydride [MgaTMb(BH4)c] may simply the decomposition process to release hydrogen with ternary borides (MgaTMbBc). The search for the probable ternary borides and the corresponding pseudo phase diagrams as well as the decomposition thermodynamics are performed using DFT calculations and GCLP method to present some possible candidates.

Grain Refinement and Texture Mitigation in Low Boron Containing TiAl-Alloys

NASA Astrophysics Data System (ADS)

Hecht, Ulrike; Witusiewicz, Victor T.

2017-12-01

Controlling the grain size and texture of lamellar TiAl-alloys is essential for well-balanced creep and fatigue properties. Excellent refinement and texture mitigation are achieved in aluminum lean alloys by low boron additions of 0.2 at.%. This amount is sufficient to promote in situ formation of ultrafine borides during the last stages of body centered cubic (BCC) solidification. The borides subsequently serve as nucleation sites for hexagonal close packed (HCP) during the BCC-HCP phase transformation. Bridgman solidification experiments with alloy Ti-43Al-8Nb-0.2C-0.2B were performed under a different growth velocity, i.e., cooling rate, to evaluate the HCP grain size distribution and texture. For slow-to-moderate cooling rates, about 65% of HCP grains are randomly oriented, despite the pronounced texture of the parent BCC phase resulting from directional solidification. For high cooling rates, obtained by quenching, texture mitigation is less pronounced. Only 28% of the HCP grains are randomly oriented, the majority being crystallographic variants of the Burgers orientation relationship.

PREFACE: Anisotropic and multiband pairing: from borides to multicomponent superconductivity Anisotropic and multiband pairing: from borides to multicomponent superconductivity

NASA Astrophysics Data System (ADS)

Annett, James; Kusmartsev, Feodor; Bianconi, Antonio

2009-01-01

In 2001, the discovery of superconductivity in MgB2 rapidly led to the understanding that its complex multi-sheeted Fermi surface had two distinct values of the gap parameter Δ, each with its own characteristic temperature dependence. While the theory of multigap superconductivity had been developed long ago, this was the first well studied example where multigap behaviour was observed clearly, and indeed is essential to understand the full superconducting properties of the material. Following this discovery, evidence for multigap behaviour has appeared in a number of materials, including cuprates, ruthenates, and most recently the iron pnictides. As well as multigap pairing on different Fermi-surface sheets, strong gap anisotropy in k-space and strong modulations of the gap in real space (e.g. stripes and phase separation models) are also important in cuprates. The aim of this special section is to present a selection of high-quality papers from experts in these diverse systems, showing the links and common physical issues arising from the existence of multi-component Cooper pairing. The papers collected together for the special section provide a snapshot of the current state of the understanding of multi-component superconductivity in a wide range of materials. In a model motivated by MgB2, Tanaka and Eschrig describe Abrikosov vortex lattice in a two-gap superconductor, examining how the vortex structure is modified by three-dimensionality or quasi two-dimensionality of the Fermi surface. The multi-sheeted Fermi surfaces of the nickel borocarbides are probed using angle-resolved positron annihilation spectroscopy, described by Dugdale et al, leading to a full three-dimensional picture of the complex Fermi surface in this superconducting material. Possible evidence for multigap superconductivity in the iron pnictides, obtained using Andreev point contact spectroscopy, is described by Samuely et al. The iron pnictides are also the subject of the article by Caivano et al, in which it is proposed that the Feschbach resonance mechanism operating near to a quantum critical point may lead to stripe-like fluctuations in these materials. A number of papers describe multigap-related effects in high-Tc superconductors. In particular, Atkinson shows how the existence of CuO chain states at the Fermi surface leads to a set of resonances in the induced gap in the chain layer, which have a pronounced effect on the vortex core shape. Kristoffel et al discuss the existence of the two coherence lengths in two-gap superconductors, and describe how this leads to spatially periodic fluctuations, with possible application to high-temperature superconductivity. Kugel et al describe a scenario for phase separation due to long-range Coulomb forces leading to microstrain and nanoscale inhomogeneities in high-Tc cuprates. Kusmartsev and Saarela also argue that charge over-screening may lead to 'Coulomb bubbles' in high-Tc superconductors. Finally, Wysokiński et al describe multigap effects in strontium ruthenate, in particular the effects on the NMR relaxation rate spectra, which are obtained for NMR on different nuclear species.

A simple method for maintaining relative positions of separate tissue elements during processing for electron microscopy.

PubMed

Stirling, C A

1978-09-01

Molten (328 K) 20% gelatin is used as a 'glue' to hold together separate tissue elements or tissue elements that may be separated when cutting small blocks of tissue for plastic embedding. Standard aldehyde and osmium fixation, dehydration and epoxy embedding are compatible with this as is semi-thin sectioning for light microscopy or thin sectioning for electron microscopy.

CONTROL ROD ALLOY CONTAINING NOBLE METAL ADDITIONS

DOEpatents

Anderson, W.K.; Ray, W.E.

1960-05-01

Silver-base alloys suitable for use in the fabrication of control rods for neutronic reactors are given. The alloy consists of from 0.5 wt.% to about 1.5 wt.% of a noble metal of platinum, ruthenium, rhodium, osmium, or palladium, up to 10 wt.% of cadmium, from 2 to 20 wt.% indium, the balance being silver.

N-doping of organic semiconductors by bis-metallosandwich compounds

DOEpatents

Barlow, Stephen; Qi, Yabing; Kahn, Antoine; Marder, Seth; Kim, Sang Bok; Mohapatra, Swagat K.; Guo, Song

2016-01-05

The various inventions disclosed, described, and/or claimed herein relate to the field of methods for n-doping organic semiconductors with certain bis-metallosandwich compounds, the doped compositions produced, and the uses of the doped compositions in organic electronic devices. Metals can be manganese, rhenium, iron, ruthenium, osmium, rhodium, or iridium. Stable and efficient doping can be achieved.

Vapor pressure and evaporation rate of certain heat-resistant compounds in a vacuum at high temperatures

NASA Technical Reports Server (NTRS)

Bolgar, A. S.; Verkhoglyadova, T. S.; Samsonov, G. V.

1985-01-01

The vapor pressure and evaporation rate of borides of titanium, zirconium, and chrome; and of strontium and carbides of titanium, zirconium, and chrome, molybdenum silicide; and nitrides of titanium, niobium, and tantalum in a vacuum were studied. It is concluded that all subject compounds evaporate by molecular structures except AlB sub 12' which dissociates, losing the aluminum.

Mid-Cenomanian Event I (MCE I, 96 Ma): elemental and osmium isotope evidence for sea level, climate, and palaeocirculation changes in the NW European epicontinental sea

NASA Astrophysics Data System (ADS)

Jarvis, Ian; Roest-Ellis, Sascha; Selby, David

2017-04-01

Cenomanian times (100.5-93.9 Ma) represent perhaps the best documented episode of eustatic rise in sea level in Earth history and the beginning of the Late Mesozoic thermal maximum, driving global expansion of epicontinental seas and the onset of widespread pelagic and hemipelagic carbonate (chalk) deposition. Significant changes occurred in global stable-isotope records, including two prominent perturbations of the carbon cycle -Mid-Cenomanian Event I (MCEI; 96.5-96.2 Ma) and Oceanic Anoxic Event 2 (OAE2; 94.5-93.8 Ma). OAE2 was marked by the widespread deposition of black shales in the deep ocean and epicontinental seas, and a global positive carbon stable-isotope excursion of 2.0 - 2.5‰ δ13C in marine carbonates. Osmium isotopes and other geochemical data indicate that OAE2 was associated with a major pulse of LIP-associated volcanism, with coincident changes in eustatic sea level, rising atmospheric pCO2 and warming climate, but including a transient phase of global cooling - the Plenus Cold Event. MCEI, by contrast, shows a <1‰ δ13Ccarb excursion, and has no associated black shales in most areas, yet it also displays evidence of two episodes of cooling, comparable to the Plenus Cold Event. MCEI marks a major breakpoint on long-term carbon-isotope profiles, from relatively constant to very slowly rising δ13C values through the Lower Cenomanian, to a trend of generally increasing δ13C values through the Middle and Upper Cenomanian. This represents a significant long-term change in the global carbon cycle starting with MCEI. Here, we present new high-resolution major- (Si, Ti, Al, Fe, Mn, Mg, Ca, Na, K, P) and trace-element (Ba, Cr, Re, Os, Sr, Zr) data and 187Os/188Os isotope results for MCEI from an English Chalk reference section at Folkestone. Our results are compared to published δ13Ccarb, δ18Ocarb, δ13Corg stable isotope and neodymium isotope ɛNd(t) data from the same section. Elemental proxies (Mn, Ti/Al, Zr/Al, Si/Al) define key sequence

Ultrasonic Characterization of Superhard Material: Osmium Diboride

NASA Astrophysics Data System (ADS)

Yadawa, P. K.

2012-12-01

Higher order elastic constants have been calculated in hexagonal structured superhard material OsB2 at room temperature following the interaction potential model. The temperature variation of the ultrasonic velocities is evaluated along different angles with unique axis of the crystal using the second order elastic constants. The ultrasonic velocity decreases with the temperature along particular orientation with the unique axis. Temperature variation of the thermal relaxation time and Debye average velocities are also calculated along the same orientation. The temperature dependency of the ultrasonic properties is discussed in correlation with elastic, thermal and electrical properties. It has been found that the thermal conductivity is the main contributor to the behaviour of ultrasonic attenuation as a function of temperature and the responsible cause of attenuation is phonon-phonon interaction. The mechanical properties of OsB2 at low temperature are better than at high temperature, because at low temperature it has low ultrasonic velocity and ultrasonic attenuation. Superhard material OsB2 has many industrial applications, such as abrasives, cutting tools and hard coatings.

Catalytic Cyclization of o-Alkynyl Phenethylamines via Osmacyclopropene Intermediates: Direct Access to Dopaminergic 3-Benzazepines.

PubMed

Álvarez-Pérez, Andrea; González-Rodríguez, Carlos; García-Yebra, Cristina; Varela, Jesús A; Oñate, Enrique; Esteruelas, Miguel A; Saá, Carlos

2015-11-02

A novel osmium-catalyzed cyclization of o-alkynyl phenethylamines to give 3-benzazepines is reported. The procedure allows the straightforward preparation of a broad range of dopaminergic 3-benzazepine derivatives. Mechanistic investigations revealed that the process takes place via osmacyclopropene intermediates, which were isolated and characterized by X-ray crystallography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of the Nuclear Structure of Rhenium-186 Using Neutron-Induced Reactions

DTIC Science & Technology

2015-03-26

5 1.5 Methods ... radioisotope power source for use on the battlefield. 1 Re-Os Cosmochronometer. The isotope 187Re has a half-life in its ground state of 4.35⇥ 1010 years [2...187Os in meteorites permits one to date the nucleosynthesis of rhenium and osmium by high neutron flux events such as supernovae. The Re-Os radioactive

Domestic Production Issues in Chromium and Platinum-Group Metals

DTIC Science & Technology

1988-09-01

iridium, and minor amounts of osmium. 12 Uses. Platinum-group metals (PGM) are critical as catalysts in fossil fuel processing and electronic...metals (PGM) were then described as critical in fossil fuel production, and in electronic and electrical components. The international market is...this research process . ii Table of Contents Page Preface.. .............. ii List of Figures ................ vi List of Tables ................ vi

Proceedings of the Conference on Toxicology Held in Dayton, Ohio on 28- 30 October 1986

DTIC Science & Technology

1987-12-01

paints (3). TBT is released from the painted surfaces by hydrolysis , forming species such as TBT hydroxide and TBT chloride. Several organotin-based...postfixation, and followed by dehydration through an increasing series of ethanol concentrations, lacked the electron-dense intramembranous...observed in osmium-fixed preparations. Presumably, the ethanol dehydration extracted any tin aggregates from the membranes because of the solubility

Selective degradation of thymidine and thymine deoxynucleotides

PubMed Central

Burton, K.; Riley, W. T.

1966-01-01

1. Osmium tetroxide in dilute ammonia oxidizes various pyrimidine nucleosides at different rates. Thymidine is oxidized about 45 times as fast as deoxycytidine. The phosphate groups may be eliminated from oxidized thymine nucleotides by successive treatments with alkali and then with diphenylamine in aqueous formic acid. The reactions can be applied to the selective degradation of thymidine in oligodeoxynucleotides. PMID:5938667

Nb2OsB2, with a new twofold superstructure of the U3Si2 type: Synthesis, crystal chemistry and chemical bonding

NASA Astrophysics Data System (ADS)

Mbarki, Mohammed; Touzani, Rachid St.; Fokwa, Boniface P. T.

2013-07-01

The new ternary metal-rich boride, Nb2OsB2, was synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The compound was characterized from single-crystal X-ray data and EDX measurements. It crystallizes as a new superstructure (space group P4/mnc, no. 128) of the tetragonal U3Si2-structure type with lattice parameters a=5.922(1) Å and c=6.879(2) Å. All of the B atoms are involved in B2 dumbbells with B-B distances of 1.89(4) Å. Structure relaxation using VASP (Vienna ab intio Simulation Package) has confirmed the space group and the lattice parameters. According to electronic structure calculations (TB-LMTO-ASA), the homoatomic B-B interactions are optimized and very strong, but relatively strong heteroatomic Os-B, Nb-B and Nb-Os bonds are also found: These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of this new phase. The density of state at the Fermi level predicts metallic behavior, as expected, from this metal-rich boride.

Boronization and Carburization of Superplastic Stainless Steel and Titanium-Based Alloys

PubMed Central

Matsushita, Masafumi

2011-01-01

Bronization and carburization of fine-grain superplastic stainless steel is reviewed, and new experimental results for fine grain Ti88.5Al4.5V3Fe2Mo2 are reported. In superplastic duplex stainless steel, the diffusion of carbon and boron is faster than in non-superplastic duplex stainless steel. Further, diffusion is activated by uniaxial compressive stress. Moreover, non-superplastic duplex stainless steel shows typical grain boundary diffusion; however, inner grain diffusion is confirmed in superplastic stainless steel. The presence of Fe and Cr carbides or borides is confirmed by X-ray diffraction, which indicates that the diffused carbon and boron react with the Fe and Cr in superplastic stainless steel. The Vickers hardness of the carburized and boronized layers is similar to that achieved with other surface treatments such as electro-deposition. Diffusion of boron into the superplastic Ti88.5Al4.5V3Fe2Mo2 alloy was investigated. The hardness of the surface exposed to boron powder can be increased by annealing above the superplastic temperature. However, the Vickers hardness is lower than that of Ti boride. PMID:28824144

Charge Transfer in Multiple Site Chemical Systems.

DTIC Science & Technology

1985-05-30

oxidation either chemically (using excess Ce+(IV)) or electrochemically (using a reticulated vitreous carbon electrode potentiostated at +1.20 V vs.. SCE...The resulting polymers form fairly stable, electrochemically active films on the cxidizing electrode, which can be Pt, SnO2 or vitreous carbon ...surface, including platinum and glassy carbon electrodes. The redox couples incorporated include polypyrydyl omplexes of iron, ruthenium and osmium

Investigation of the fracture mechanics of boride composites

NASA Technical Reports Server (NTRS)

Clougherty, E. V.; Pober, R. L.; Kaufman, L.

1972-01-01

Significant results were obtained in fabrication studies of the role of metallic additives of Zr, Ti, Ni, Fe and Cr on the densification of ZrB2. All elemental additions lower the processing temperatures required to effect full densification of ZrB2. Each addition effects enhanced densification by a clearly distinguishable and different mechanism and the resulting fabricated materials are different. A significant improvement in strength and fracture toughness was obtained for the ZrB2/Ti composition. Mechanical characterization studies for the ZrB2/SiC/C composites and the new ZrB2/Metal materials produced data relevant to the effect of impacting load on measured impact energies, a specimen configuration for which controlled fracture could occur in a suitably hard testing apparatus, and fracture strength data. Controlled fracture--indicative of measurable fracture toughness--was obtained for the ZrB2-SiC-C composite, and a ZrB2/Ti composite fabricated from ZrB2 with an addition of 30 weight per cent Ti. The increased strength and toughness of the ZrB2/Ti composite is consistent with the presence of a significantly large amount of a fine grained acicular phase formed by reaction of Ti with ZrB2 during processing.

Fundamental Thermal and Mechanical Properties of Boride Ceramics

DTIC Science & Technology

2014-02-28

Zr ,Y)B2 ( Zr ,Hf)B2 ( Zr ,Ti)B2 ZrB2 El ec tri ca l R es is tiv ity (µ Ω -c m ) Temperature (°C) Figure 17. Electrical resistivity as a function...family as Zr , namely Ti and Hf, had minimal effect on thermal conductivity, while others such as Nb , Ta, and W had an increasing impact based on their...diffusivity (α), heat capacity (Cp) from the NIST-JANAF tables, and bulk density (ρ) using Equation 6. (5) (6) Electrical resistivity

LINER FOR EXTRUSION BILLET CONTAINERS

DTIC Science & Technology

Shrink-fit assembly device for buildup of ceramic-coated liner and sleeve assemblies was tested and modified to develop desired temperatures and...preliminary evaluation of suitability for extrusion liner use. Procedures were developed for welding short, hollow ceramic cylinders of high-strength metal...carbides and borides to form a ceramic extrusion liner of suitable length. Disassembly tooling for rapid separation of shrink-fitted sleeves from a worn

Investigation of the thermophysical properties of high-melting materials with the aid of a complex of instruments

NASA Technical Reports Server (NTRS)

Bolgar, A. S.; Gordiyenko, S. P.; Guseva, Y. A.; Turchanin, A. G.; Fenochka, B. V.; Fesenko, V. V.

1984-01-01

The evaporation rate, vapor pressure, heats of evaporation reaction (sublimation, dissociation), enthalpy, electrical resistance, heat capacity, emissivity, and heat conductivity of various carbides, borides, sulfides, nitrides, selenides, and phosphides were investigated. A set of high temperature high vacuum devices, calorimeters (designed for operation at 400 to 1300 K and from 1200 K), and mass spectrometers, most of which were specially developed for these studies, is described.

Correlation between thermodynamical stabilities of metal borohydrides and cation electronegativites: First-principles calculations and experiments

NASA Astrophysics Data System (ADS)

Nakamori, Yuko; Miwa, Kazutoshi; Ninomiya, Akihito; Li, Haiwen; Ohba, Nobuko; Towata, Shin-Ichi; Züttel, Andreas; Orimo, Shin-Ichi

2006-07-01

The thermodynamical stabilities for the series of metal borohydrides M(BH4)n ( M=Li , Na, K, Cu, Mg, Zn, Sc, Zr, and Hf; n=1-4 ) have been systematically investigated by first-principles calculations. The results indicated that an ionic bonding between Mn+ cations and [BH4]- anions exists in M(BH4)n , and the charge transfer from Mn+ cations to [BH4]- anions is a key feature for the stability of M(BH4)n . A good correlation between the heat of formation ΔHboro of M(BH4)n and the Pauling electronegativity of the cation χP can be found, which is represented by the linear relation, ΔHboro=248.7χP-390.8 in the unit of kJ/mol BH4 . In order to confirm the predicted correlation experimentally, the hydrogen desorption reactions were studied for M(BH4)n ( M=Li , Na, K, Mg, Zn, Sc, Zr, and Hf), where the samples of the later five borohydrides were mechanochemically synthesized. The thermal desorption analyses indicate that LiBH4 , NaBH4 , and KBH4 desorb hydrogen to hydride phases. Mg(BH4)2 , Sc(BH4)3 , and Zr(BH4)4 show multistep desorption reactions through the intermediate phases of hydrides and/or borides. On the other hand, Zn(BH4)2 desorbs hydrogen and borane to elemental Zn due to instabilities of Zn hydride and boride. A correlation between the desorption temperature Td and the Pauling electronegativity χP is observed experimentally and so χP is an indicator to approximately estimate the stability of M(BH4)n . The enthalpy change for the desorption reaction, ΔHdes , is estimated using the predicted ΔHboro and the reported data for decomposed product, ΔHhyd/boride . The estimated ΔHdes show a good correlation with the observed Td , indicating that the predicted stability of borohydride is experimentally supported. These results are useful for exploring M(BH4)n with appropriate stability as hydrogen storage materials.

Muon spin relaxation and rotation studies of the filled skutterudite alloys praseodymium osmium ruthenium antimonide and praseodymium lanthanum osmium antimonide

NASA Astrophysics Data System (ADS)

Shu, Lei

Some filled skutterudite compounds have recently been found to exhibit very interesting properties. The first Pr-based heavy-fermion superconductor, PrOs4Sb12, is an intriguing material due to the unusual properties of both its normal and superconducting states. Comprehensive muon spin rotation and relaxation studies and magnetic susceptibility measurements, described in this dissertation, have been performed to investigate the microscopic properties of PrOs4Sb12 and its Ru and La doped alloys. The temperature dependence of penetration depth measured in the vortex state of PrOs4Sb12 using transverse-field muon spin rotation (TF-muSR) is weaker than those measured by radiofrequency measurements. A scenario based on two-band superconductivity in PrOs4Sb 12, is proposed to resolve this difference. TF-muSR experiments also suggest the suppression of superfluid density with Ru doping, probably due to impurity scattering. In addition, magnetic susceptibility data as well as analysis of the muSR data in PrOs4Sb12 reveal a nearly linear relation of mu+ Knight shift vs. magnetic susceptibility. This suggests that the muon charge does not affect the crystalline electric field splitting of Pr3+ near neighbors. Additional evidence comes from the fact that the superconducting transition temperature Tc measured from muSR is consistent with the bulk superconducting values. Zero-field muon spin relaxation (ZF-muSR) experiments have been carried out in the Pr(Os1-xRux) 4Sb12 and Pr1-yLayOs 4Sb12 alloy systems to investigate the time-reversal symmetry (TRS) breaking found in an earlier ZF-muSR study of the end compound PrOs 4Sb12. The results from measurements at KEK, Japan, suggest that Ru doping is considerably more efficient than La doping in suppressing TRS breaking superconducting in PrOs4Sb12. However, we think that the spontaneous local field that indicates TRS breaking detected by ZF-muSR may depend on sample quality if those fields are from inhomogeneity in the superconducting order parameter, since our ZF-muSR experiment detects nonzero spontaneous fields for Pr(Os0.9Ru0.1)4 Sb12 from measurement at ISIS, United Kingdom in different samples. Longitudinal-field muon spin relaxation experiments also have been carried out to elucidate the anomalous dynamic muon spin relaxation detected by ZF-muSR in those alloys. The dynamic muon relaxation found in the alloys appears to be due to 141Pr nuclear spin fluctuations, where the 141Pr moments are enhanced by hyperfine coupling to the Pr 3+ Van Vleck susceptibility.

Phase-contrast tomography of sciatic nerves: image quality and experimental parameters

NASA Astrophysics Data System (ADS)

Töpperwien, M.; Krenkel, M.; Ruhwedel, T.; Möbius, W.; Pacureanu, A.; Cloetens, P.; Salditt, T.

2017-06-01

We present propagation-based phase-contrast tomography of mouse sciatic nerves stained with osmium, leading to an enhanced contrast in the myelin sheath around the axons, in order to visualize the threedimensional (3D) structure of the nerve. We compare different experimental parameters and show that contrast and resolution are high enough to identify single axons in the nerve, including characteristic functional structures such as Schmidt-Lanterman incisures.

Mineral resource of the month: platinum group metals

USGS Publications Warehouse

Loferski, Patricia J.

2010-01-01

The article focuses on platinum group metals (PGMs) and their properties. According to the author, PGMs, which include iridium, osmium, palladium, platinum, rhodium, and ruthenium, are among the rarest mineral commodities in the Earth's crust. PGMs are primarily used as catalytic converters that clean harmful exhaust from vehicle engines. They are also used in the chemical industry as catalysts in the production of nitric acid and in the petroleum refining industry.

High-Temperature Ceramic Matrix Composite with High Corrosion Resistance

DTIC Science & Technology

2010-06-02

ceramics with silicide additives may be explained in the following ways: 1) metal oxide, for example Ta2O5, formed at oxidation of TaSi2, in the...practically monophase ones, possibly, the additives of corresponding metals in silicide powders were present in insignificant amounts. For...boride with zirconium silicide we prepared the mixtures with 20 vol. % of silicide , the latter being hot pressed in the temperature range of 1600

Osmium Isotope Compositions of Komatiite Sources Through Time

NASA Astrophysics Data System (ADS)

Walker, R. J.

2001-12-01

Extending Os isotopic measurements to ancient plume sources may help to constrain how and when the well-documented isotopic heterogeneities in modern systems were created. Komatiites and picrites associated with plume-related volcanism are valuable tracers of the Os isotopic composition of plumes because of their typically high Os concentrations and relatively low Re/Os. Re-Os data are now available for a variety of Phanerozoic, Proterozoic and Archean komatiites and picrites. As with modern plumes, the sources of Archean and Proterozoic komatiites exhibit a large range of initial 187Os/188Os ratios. Most komatiites are dominated by sources with chondritic Os isotopic compositions (e.g. Song La; Norseman-Wiluna; Pyke Hill; Alexo), though some (e.g. Gorgona) derive from heterogeneous sources. Of note, however, two ca. 2.7 Ga systems, Kostomuksha (Russia) and Belingwe (Zimbabwe), have initial ratios enriched by 2-3% relative to the contemporary convecting upper mantle. These results suggest that if the 187Os enrichment was due to the incorporation of minor amounts of recycled crust into the mantle source of the rocks, the crust formed very early in Earth history. Thus, the Os results could reflect derivation of melt from hybrid mantle whose composition was modified by the addition of mafic crustal material that would most likely have formed between 4.2 and 4.5 Ga. Alternately, the mantle sources of these komatiites may have derived a portion of their Os from the putative 187Os - and 186Os -enriched outer core. For this hypothesis to be applicable to Archean rocks, an inner core of sufficient mass would have to have crystallized sufficiently early in Earth history to generate an outer core with 187Os enriched by at least 3% relative to the chondritic average. Using the Pt-Re-Os partition coefficients espoused by our earlier work, and assuming linear growth of the inner core started at 4.5 Ga and continued to present, would yield an outer core at 2.7 Ga with a gamma Os value of only +1.2 and a 186Os/188Os enrichment relative to the contemporary upper mantle of only +13 ppm. Greater isotopic enrichments could have been achieved by 2.7 Ga if either the inner core comprised >2.8% of the mass of the core by 2.7 Ga, or if Re and Os solid metal-liquid metal D's for core crystallization were greater that those applied in the initial calculation.

Osmium isotopic homogeneity in the CK carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Goderis, Steven; Brandon, Alan D.; Mayer, Bernhard; Humayun, Munir

2017-11-01

Variable proportions of isotopically diverse presolar components are known to account for nucleosynthetic isotopic anomalies for a variety of elements (e.g., Ca, Ti, Cr, Ni, Sr, Zr, Mo, Ru, Pd, Ba, Nd, and Sm) in both bulk chondrites and achondrites. However, although large Os isotopic anomalies have been measured in acid leachates and residues of unequilibrated chondrites, bulk chondrites of various groups, iron meteorites, and pallasites exhibit Os isotopic compositions that are indistinguishable from terrestrial or bulk solar isotopic abundances. Since the magnitude of nucleosynthetic anomalies is typically largest in the carbonaceous chondrites, this study reports high-precision Os isotopic compositions and highly siderophile element (HSE) concentrations for ten CK chondrites. The isotope dilution concentration data for HSE and high-precision Os isotope ratios were determined on the same digestion aliquots, to precisely correct for radiogenic contributions to 186Os and 187Os. While acid leached bulk unequilibrated carbonaceous chondrites show deficits of s-process Os components to the same extent as revealed by unequilibrated enstatite, ordinary, and Rumuruti chondrites, equilibrated bulk CK chondrites exhibit no resolvable Os isotopic anomalies. These observations support the idea that acid-resistant, carbon-rich presolar grains, such as silicon carbide (SiC) or graphite, are major carriers for nucleosynthetic isotopic anomalies of Os. The destruction of these presolar grains, which are omnipresent in unequilibrated meteorites, must have occurred during aqueous alteration and thermal metamorphism, early in the CK chondrite parent body history. The dispersal of CK chondrites along the IIIAB iron meteorite isochron on a 187Os/188Os versus 187Re/188Os diagram, with Re/Os ratios from 0.032 to 0.083, in combination with the observed redistribution of other HSE (e.g., Pt, Pd), highlights the influence of parent body processes, overprinted by effects of recent terrestrial alteration. Under the oxidizing conditions prevalent on the CK parent body, evident from high abundances of magnetite and limited Fe-Ni metal in CK chondrites, these parent body processes made all isotopically anomalous Os, originally hosted in reduced presolar grains, accessible. The absence of Os isotopic anomalies in ordinary, enstatite, and now also carbonaceous chondrites, implies that the carriers of s- and r-process Os must have been effectively homogenized across the region of chondrite formation, and possibly even the entire solar protoplanetary nebula, as suggested by the Os isotopic compositions of iron meteorites and non-anomalous ureilites. Except for a limited number of ureilites, the relative proportions of presolar s- and r-process carriers of Os (and other elements such as W) in chondrites, and most other planetary bodies, must have remained constant during all subsequent nebular and planetary processes, which appears not to have been the case for other siderophile elements, including Mo, Ru, and Pd. The existence of Mo, Ru, Pd and other siderophile element isotopic anomalies thus appears to be in part controlled by the chemical properties of these elements (e.g., volatility), their host phase(s) (e.g., SiC, graphite, metal, sulfides), and the nature of the nebular or planetary processes experienced in the early solar system.

Relativistic effects in iron-, ruthenium-, and osmium porphyrins

NASA Astrophysics Data System (ADS)

Liao, Meng-Sheng; Scheiner, Steve

2002-12-01

Nonrelativistic and relativistic DFT calculations are performed on four-coordinate metal porphyrins MP and their six-coordinate adducts MP(py) 2 and MP(py)(CO) (py=pyridine) with M=Fe, Ru, and Os. The electronic structures of the MPs are investigated by considering all possible low-lying states with different configurations of nd-electrons. FeP and OsP have a 3A2 g ground state, while this state is nearly degenerate with 3Eg for RuP. Without relativistic corrections, the ground states of both RuP and OsP would be 3Eg. For the six-coordinate adducts with py and CO, the strong-field axial ligands raise the energy of the M d z2-orbital, thereby making the M II ion diamagnetic. The calculated redox properties of MP(py) 2 and MP(py)(CO) are in agreement with experiment. The difference between RuP(py)(CO) and OsP(py)(CO), in terms of site of oxidation, is due to relativistic effects.

Global warming and ocean acidification through halted weathering feedback during the Middle Eocene Climatic Optimum

NASA Astrophysics Data System (ADS)

van der Ploeg, R.; Selby, D. S.; Cramwinckel, M.; Bohaty, S. M.; Sluijs, A.; Middelburg, J. J.

2016-12-01

The Middle Eocene Climatic Optimum (MECO) represents a 500 kyr period of global warming 40 million years ago associated with a rise in atmospheric CO2 concentrations, but its cause remains enigmatic. Moreover, on the timescale of the MECO, an increase in silicate weathering rates on the continents is expected to balance carbon input and restore the alkalinity of the oceans, but this is in sharp disagreement with observations of extensive carbonate dissolution. Here we show, based on osmium isotope ratios of marine sediments from three different sites, that CO2 rise and warming did not lead to enhanced continental weathering during the MECO, in contrast to expectations from carbon cycle theory. Remarkably, a minor shift to lower, more unradiogenic osmium isotope ratios rather indicates an episode of increased volcanism or reduced continental weathering. This disproves silicate weathering as a geologically constant feedback to CO2 variations. Rather, we suggest that global Early and Middle Eocene warmth diminished the weatherability of continental rocks, ultimately leading to CO2 accumulation during the MECO, and show the plausibility of this scenario using carbon cycle modeling simulations. We surmise a dynamic weathering feedback might explain multiple enigmatic phases of coupled climate and carbon cycle change in the Cretaceous and Cenozoic.

The use of surface layer with boron in friction pairs lubricated by engine oils

NASA Astrophysics Data System (ADS)

Szczypiński-Sala, W.; Lubas, J.

2016-09-01

The aim of the present work is to determine the influence of surface layers with boron and engine oil on the processes of friction and wear in friction pairs. The ring samples with borided surface layer cooperated under test conditions with counterparts made with CuPb30 and AlSn20 bearing alloys. During the tests, the friction pairs were lubricated with 15W/40 Lotos mineral oil and 5W/40 Lotos synthetic oil. The lubrication of friction area with Lotos mineral oil causes the reduction of the friction force, the temperature in the friction area and the wear of the bearing alloys under study, whereas the lubrication with Lotos synthetic oil reduces the changes in the geometrical structure of the cooperating friction pair elements. Lubrication of the friction area in the start-up phase of the friction pair by mineral oil causes faster stabilization of the friction conditions in the contact area than in the cause of lubrication of the friction pair by synthetic oil. The intensity of wear of the AlSn20 bearing alloy cooperating with the borided surface layer is three times smaller than the intensity of use of the CuPb30 alloy bearing.

Mechanical, Electronic and Optical Properties of Two Phases of NbB4: First-Principles Calculations

NASA Astrophysics Data System (ADS)

Yang, Ruike; Ma, Shaowei; Wei, Qun; Zhang, Dongyun

2018-05-01

As transition metal borides have been successfully synthesised, the study of the combination of transition metal and boron is another effective way to investigate the properties of boride. We have predicted the novel phase Amm2-NbB4. Using the Cambridge Serial Total Energy Package (CASTEP) code, we further researched on the mechanical, electronic and optical properties of C2/c- and Amm2-NbB4. It is found that both the phases of NbB4 are dynamically and mechanically stable at 0 and 100 GPa. Their Vickers hardness values are both 34 GPa, which indicate that they are hard materials. The band gap of C2/c-NbB4 is 0.145 eV, which indicates that it is a semiconductor (or metalloid) at 0 GPa. For the Amm2-NbB4, the band structure without band gap indicates it is a metal at 0 GPa. The optical properties of these two structures are similar. At 0 eV, the real part of dielectric function is 28.8 for C2/c-NbB4, and the real part value for Amm2-NbB4 is 43. We hope our work will provide some help to the experimental work about the technology of the material.

A study of the microstructure of a rapidly solidified nickel-base superalloy modified with boron. M.S. Thesis. Final Contractor Report

NASA Technical Reports Server (NTRS)

Speck, J. S.

1986-01-01

The microstructures of melt-spun superalloy ribbons with variable boron levels have been studied by transmission electron microscopy. The base alloy was of approximate composition Ni-11% Cr-5%Mo-5%Al-4%Ti with boron levels of 0.06, 0.12, and 0.60 percent (all by weight). Thirty micron thick ribbons display an equiaxed chill zone near the wheel contact side which develops into primary dendrite arms in the ribbon center. Secondary dendrite arms are observed near the ribbon free surface. In the higher boron bearing alloys, boride precipitates are observed along grain boundaries. A concerted effort has been made to elucidate true grain shapes by the use of bright field/dark field microscopy. In the low boron alloy, grain shapes are often convex, and grain faces are flat. Boundary faces frequently have large curvature, and grain shapes form concave polygons in the higher boron level alloys. It is proposed that just after solidification, in all of the alloys studied, grain shapes were initially concave and boundaries were wavy. Boundary straightening is presumed to occur on cooling in the low boron alloy. Boundary migration is precluded in the higher boron alloys by fast precipitation of borides at internal interfaces.

Nations Hospitable to Organized Crime and Terrorism

DTIC Science & Technology

2003-10-01

illegal migrants from Somalia, Ethiopia, China, India, and Sri Lanka pass through the airport’s weak customs barriers en route to Western Europe and...osmium-187, possibly en route to terrorist organizations or Iraq. In December 2001, Moscow authorities arrested a group of Chechens from Kazakhstan...utilizes the city as a transit point en route to Sri Lanka.492 The LTTE continues to procure arms from arsenals abandoned after Cambodia’s civil war

Method to produce catalytically active nanocomposite coatings

DOEpatents

Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa; Kazmanli, Kursat

2016-02-09

A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erdemir, Ali; Eryilmaz, Osman Levent; Urgen, Mustafa

A nanocomposite coating and method of making and using the coating. The nanocomposite coating is disposed on a base material, such as a metal or ceramic; and the nanocomposite consists essentially of a matrix of an alloy selected from the group of Cu, Ni, Pd, Pt and Re which are catalytically active for cracking of carbon bonds in oils and greases and a grain structure selected from the group of borides, carbides and nitrides.

METHOD OF PROTECTING TANTALUM CRUCIBLES AGAINST REACTION WITH MOLTEN URANIUM

DOEpatents

Feder, H.M.; Chellew, N.R.

1960-08-16

Tantalum crucibles against reaction with molten uranium by contacting the surfaces to be protected with metallic boron (as powder, vapor, or suspension in a liquid-volatilenonreacting medium, such as acetone and petroleum oil) at about 1800 deg C in vacuum, discontinuing contact with the boron, and heating the crucibles to a temperature of between 1800 aad 2000 deg C, whereby the tantalum boride formed in the first heating step is converted to tantalum monoboride.

Exercise Decreases Marrow Adipose Tissue Through ß-Oxidation in Obese Running Mice

PubMed Central

Styner, Maya; Pagnotti, Gabriel M; McGrath, Cody; Wu, Xin; Sen, Buer; Uzer, Gunes; Xie, Zhihui; Zong, Xiaopeng; Styner, Martin A; Rubin, Clinton T; Rubin, Janet

2017-01-01

The relationship between marrow adipose tissue (MAT) and bone health is poorly understood. We used running exercise to ask whether obesity-associated MAT can be attenuated via exercise and whether this correlates with gains in bone quantity and quality. C57BL/6 mice were divided into diet-induced obesity (DIO, n = 14) versus low-fat diet (LFD, n = 14). After 3 months, 16-week-old mice were allocated to an exercise intervention (LFD-E, DIO-E) or a control group (LFD, DIO) for 6 weeks (4 groups, n = 7/group). Marrow adipocyte area was 44% higher with obesity (p<0.0001) and after exercise 33% lower in LFD (p<0.0001) and 39% lower in DIO (p<0.0001). In LFD, exercise did not affect adipocyte number; however, in DIO, the adipocyte number was 56% lower (p<0.0001). MAT was 44% higher in DIO measured by osmium-µCT, whereas exercise associated with reduced MAT (–23% in LFD, –48% in DIO, p<0.05). MAT was additionally quantified by 9.4TMRI, and correlated with osmium-µCT (r = 0.645; p<0.01). Consistent with higher lipid beta oxidation, perilipin 3 (PLIN3) rose with exercise in tibial mRNA (+92% in LFD,+60% in DIO, p<0.05). Tibial µCT-derived trabecular bone volume (BV/TV) was not influenced by DIO but responded to exercise with an increase of 19% (p<0.001). DIO was associated with higher cortical periosteal and endosteal volumes of 15% (p = 0.012) and 35% (p<0.01), respectively, but Ct. Ar/Tt.Ar was lower by 2.4% (p<0.05). There was a trend for higher stiffness (N/m) in DIO, and exercise augmented this further. In conclusion, obesity associated with increases in marrow lipid—measured by osmium-µCT and MRI—and partially due to an increase in adipocyte size, suggesting increased lipid uptake into preexisting adipocytes. Exercise associated with smaller adipocytes and less bone lipid, likely invoking increased ß-oxidation and basal lipolysis as evidenced by higher levels of PLIN3. PMID:28436105

Molecular Modeling of High-Temperature Oxidation of Refractory Borides

DTIC Science & Technology

2008-02-01

generate the classical potential, we adopt the van Beest , Kramer and van Santen (BKS) parameterization for Si-O interactions, but fit B-O and Si-B...seminar at Department of Aerospace and Mechanical Engineering, University of Notre Dame, March 20, 2007. 6 Los Alamos National Lab Physics & Theoretical

Feasibility study of the welding of SiC

NASA Technical Reports Server (NTRS)

Moore, T. J.

1985-01-01

In a brief study of the feasibility of welding sintered alpha-SiC, solid-state welding and brazing were investigated. Joint quality was determined solely by microstructural examination. Hot-pressure welding was shown to be feasible at 1950 C. Diffusion welding and brazing were also successful under hot isostatic pressure at 1950 C when boride, carbide, and silicide interlayers were used. Furnace brazing was accomplished at 1750 C when a TiSi2 interlayer was introduced.

Development of a method for fabricating metallic matrix composite shapes by a continuous mechanical process

NASA Technical Reports Server (NTRS)

Divecha, A. P.

1974-01-01

Attempts made to develop processes capable of producing metal composites in structural shapes and sizes suitable for space applications are described. The processes must be continuous and promise to lower fabrication costs. Special attention was given to the aluminum boride (Al/b) composite system. Results show that despite adequate temperature control, the consolidation characteristics did not improve as expected. Inadequate binder removal was identified as the cause responsible. An Al/c (aluminum-graphite) composite was also examined.

Identification of thermodynamically stable ceramic reinforcement materials for iron aluminide matrices

NASA Technical Reports Server (NTRS)

Misra, Ajay K.

1990-01-01

Aluminide-base intermetallic matrix composites are currently being considered as potential high-temperature materials. One of the key factors in the selection of a reinforcement material is its chemical stability in the matrix. In this study, chemical interactions between iron aluminides and several potential reinforcement materials, which include carbides, oxides, borides, and nitrides, are analyzed from thermodynamic considerations. Several chemically compatible reinforcement materials are identified for the iron aluminides with Al concentrations ranging from 40 to 50 at. pct.

ULTRASTRUCTURAL ORGANIZATION OF CILIA AND BASAL BODIES OF THE EPITHELIUM OF THE CHOROID PLEXUS IN THE CHICK EMBRYO

PubMed Central

Doolin, Paul F.; Birge, Wesley J.

1966-01-01

Ultrastructural studies were performed on normal and abnormal cilia and basal bodies associated with the choroidal epithelium of the chick embryo. Tissues were prepared in each of several fixatives including: 1% osmium tetroxide, in both phosphate and veronal acetate buffers; 2% glutaraldehyde, followed by postfixation in osmium tetroxide; 1% potassium permanganate in veronal acetate buffer. Normal cilia display the typical pattern of 9 peripheral doublets and 2 central fibers, as well as a system of 9 secondary fibers. The latter show distinct interconnections between peripheral and central fibers. Supernumerary fibers were found to occur in certain abnormal cilia. The basal body is complex, bearing 9 transitional fibers at the distal end and numerous cross-striated rootlets at the proximal end. The distal end of the basal body is delimited by a basal plate of moderate density. The tubular cylinder consists of 9 triple fibers. The C subfibers end at the basal plate, whereas subfibers A and B continue into the shaft of the cilium. The 9 transitional fibers radiate out from the distal end of the basal body, ending in bulblike terminal enlargements which are closely associated with the cell membrane in the area of the basal cup. One or 2 prominent basal feet project laterally from the basal body. These structures characteristically show several dense cross-bands and, on occasion, are found associated with microtubules. PMID:5335827

CALCIUM BINDING TO INTESTINAL MEMBRANES

PubMed Central

Oschman, James L.; Wall, Betty J.

1972-01-01

Flame photometry reveals that glutaraldehyde and buffer solutions in routine use for electron microscopy contain varying amounts of calcium. The presence of electron-opaque deposits adjacent to membranes in a variety of tissues can be correlated with the presence of calcium in the fixative. In insect intestine (midgut), deposits occur adjacent to apical and lateral plasma membranes. The deposits are particularly evident in tissues fixed in glutaraldehyde without postosmication. They are also observed in osmicated tissue if calcium is added to wash and osmium solutions. Deposits are absent when calcium-free fixatives are used, but are present when traces of CaCl2 (as low as 5 x 10-5 M) are added. The deposits occur at regular intervals along junctional membranes, providing images strikingly similar to those obtained by other workers who have used pyroantimonate in an effort to localize sodium. Other divalent cations (Mg++, Sr++, Ba++, Mn++, Fe++) appear to substitute for calcium, while sodium, potassium, lanthanum, and mercury do not. After postfixing with osmium with calcium added, the deposits can be resolved as patches along the inner leaflet of apical and lateral plasma membranes. The dense regions may thus localize membrane constituents that bind calcium. The results are discussed in relation to the role of calcium in control of cell-to-cell communication, intestinal calcium uptake, and the pyroantimonate technique for ion localization. PMID:4569411

Evidence for a Meteoritic Component in Impact Melt Rock from the Chicxulub Structure

NASA Technical Reports Server (NTRS)

Koeberl, Christian; Sharpton, Virgil L.; Schuraytz, Benjamin C.; Shirey, Steven B.; Blum, Joel D.; Marin, Luis E.

1994-01-01

The Chicxulub structure in Yucatan, Mexico, has recently been recognized as a greater then 200-km-diameter multi-ring impact crater of K-T boundary age. Crystalline impact melt rocks and breccias from within the crater, which have compositions similar to those of normal continental crustal rocks and which show shock metamorphic effects, have been studied for trace element and Re-Os isotope compositions. Re-Os isotope systematics allow the sensitive and selective determination of an extraterrestrial component in impact-derived rocks. A melt rock sample shows elevated iridium concentrations, an osmium concentration of 25 ppb, and a low Os-187/Os-188 ratio of 0.113, which are incompatible with derivation from the continental crust. Even though the Os-187/Os-188 ratio is slightly lower than the range so far measured in meteorites, a mantle origin seems unlikely for mass balance reasons and because the cratering event is unlikely to have excavated mantle material. The data support the hypothesis of a heterogeneously distributed meteoritic component in the Chicxulub melt rock. A sample of impact glass from the Haitian K-T boundary at Beloc yielded about 0.1 ppb osmium and an Os-187/0s-188 ratio of 0.251, indicating the presence of a small meteoritic component in the impact ejecta as well.

Accelerator-based production of the (99m)Tc-(186)Re diagnostic-therapeutic pair using metal disulfide targets (MoS2, WS2, OsS2).

PubMed

Gott, Matthew D; Hayes, Connor R; Wycoff, Donald E; Balkin, Ethan R; Smith, Bennett E; Pauzauskie, Peter J; Fassbender, Michael E; Cutler, Cathy S; Ketring, Alan R; Wilbur, D Scott; Jurisson, Silvia S

2016-08-01

Novel, natural abundance metal disulfide targets were irradiated for 1h with a 10µA proton beam in a small, medical cyclotron. Osmium disulfide was synthesized by simple distillation and precipitation methods while MoS2 and WS2 were commercially available. The targets dissolved under mild conditions and were analyzed by γ-spectroscopy. Production rates and potential applications are discussed, including target recovery and recycling schemes for OsS2 and WS2. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evaluation and prediction of long-term environmental effects on non metallic materials

NASA Technical Reports Server (NTRS)

Papazian, H.

1985-01-01

Predictive modeling of environmental conditions on nonmetallic materials was studied. The in-flight data of the atomic oxygen reaction with carbon and osmium, the laboratory and in-flight data of the atomic oxygen reaction with polymeric films and the effect of electron irradiation on the rates of oxidation are discussed. No information is found that can be used to model such effects on composites. The effects of the space environment on thermal control coatings and its effect on the space station are examined.

Ceramic Coating Method

DTIC Science & Technology

2002-07-02

cobalt , zirconia, boron carbide, BN, SiC, Si3 N4, zirconium carbide, chromium , gold, silver, platinum, osmium, and the like. The TiB2 (melting point 29000...possible with the new diamond doping Periodic Table such as N, P, As, Sb, Bi, V, Cb, Ta, Pa; method. elements in the Sixth Group (0, S, Se, Te, Po, Cr ...also the surface of many reactive others are done at low temperatures to avoid unwanted metals such as aluminum, magnesium, chromium , silicon, thermal

Hardness behavior of binary and ternary niobium alloys at 77 and 300 K

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1974-01-01

The effects of alloy additions of zirconium, hafnium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, and iridium on the hardness of niobium was determined. Both binary and ternary alloys were investigated by means of hardness tests at 77 K and 300 K. Results showed that atomic size misfit plays a dominant role in controlling hardness of binary niobium alloys. Alloy softening, which occurred at dilute solute additions, is most likely due to an extrinsic mechanism involving interaction between solute elements and interstitial impurities.

Titanium Diboride Electrodeposited Coatings

DTIC Science & Technology

1977-06-01

4 Ti02. This material was deposited in the form of a porous mass or loose particles which must be leached in water and acid to remove adherent...poudres metallique par electrolyse ignee. Revue de Metallurgie, v. 45, 1948, p. 49-59. 7. POWELL, C. F. Borides in High Temperature Materials and... water solution of thallium formate-thallium malonate 50-50 mole percent mixture with a density ranging from about 5 g/cm^ at the bottom to about 2 g/cm

Alumina-based ceramic composite

DOEpatents

Alexander, Kathleen B.; Tiegs, Terry N.; Becher, Paul F.; Waters, Shirley B.

1996-01-01

An improved ceramic composite comprising oxide ceramic particulates, nonoxide ceramic particulates selected from the group consisting of carbides, borides, nitrides of silicon and transition metals and mixtures thereof, and a ductile binder selected from the group consisting of metallic, intermetallic alloys and mixtures thereof is described. The ceramic composite is made by blending powders of the ceramic particulates and the ductile to form a mixture and consolidating the mixture of under conditions of temperature and pressure sufficient to produce a densified ceramic composite.

Anti-scratch AlMgB14 Gorilla® Glass coating

NASA Astrophysics Data System (ADS)

Putrolaynen, V. V.; Grishin, A. M.; Rigoev, I. V.

2017-10-01

Hard aluminum-magnesium boride (BAM) films were fabricated onto Corning® Gorilla® Glass by radio-frequency magnetron sputtering of a single stoichiometric AlMgB14 target. BAM films exhibit a Vickers hardness from 10 to 30 GPa and a Young's modulus from 80 to 160 GPa depending on applied loading forces. Deposited hard coating increases the critical load at which glass substrate cracks. The adhesion energy of BAM films on Gorilla® Glass is 6.4 J/m2.

Ultra-hard AlMgB14 coatings fabricated by RF magnetron sputtering from a stoichiometric target

NASA Astrophysics Data System (ADS)

Grishin, A. M.; Khartsev, S. I.; Böhlmark, J.; Ahlgren, M.

2015-01-01

For the first time hard aluminum magnesium boride films were fabricated by RF magnetron sputtering from a single stoichiometric ceramic AlMgB14 target. Optimized processing conditions (substrate temperature, target sputtering power and target-to-substrate distance) enable fabrication of stoichiometric in-depth compositionally homogeneous films with the peak values of nanohardness 88 GPa and Young's modulus 517 GPa at the penetration depth of 26 nm and, respectively, 35 and 275 GPa at 200 nm depth in 2 μm thick film.

Synthesis and properties of nickel cobalt boron nanoparticles

NASA Astrophysics Data System (ADS)

Patel, J.; Pankhurst, Q. A.; Parkin, I. P.

2005-01-01

Amorphous cobalt nickel boride nanoparticles were synthesised by chemical reduction synthesis in aqueous solution. Careful control of synthesis conditions and post reaction oxidation enabled the nanoparticles to be converted into a core-shell structure comprising of an amorphous Co-Ni-B core and an outer metal oxide sheet. These particles had interesting magnetic properties including saturation magnetisations and coercivities of the order of 80 emu/g and 170 Oe respectively, making them suitable for a potential use as an exchange-pinned magnetic material.

Sweetening ruthenium and osmium: organometallic arene complexes containing aspartame.

PubMed

Gray, Jennifer C; Habtemariam, Abraha; Winnig, Marcel; Meyerhof, Wolfgang; Sadler, Peter J

2008-09-01

The novel organometallic sandwich complexes [(eta(6)-p-cymene)Ru(eta(6)-aspartame)](OTf)(2) (1) (OTf = trifluoromethanesulfonate) and [(eta(6)-p-cymene)Os(eta(6)-aspartame)](OTf)(2) (2) incorporating the artificial sweetener aspartame have been synthesised and characterised. A number of properties of aspartame were found to be altered on binding to either metal. The pK(a) values of both the carboxyl and the amino groups of aspartame are lowered by between 0.35 and 0.57 pH units, causing partial deprotonation of the amino group at pH 7.4 (physiological pH). The rate of degradation of aspartame to 3,6-dioxo-5-phenylmethylpiperazine acetic acid (diketopiperazine) increased over threefold from 0.12 to 0.36 h(-1) for 1, and to 0.43 h(-1) for 2. Furthermore, the reduction potential of the ligand shifted from -1.133 to -0.619 V for 2. For the ruthenium complex 1 the process occurred in two steps, the first (at -0.38 V) within a biologically accessible range. This facilitates reactions with biological reductants such as ascorbate. Binding to and activation of the sweet taste receptor was not observed for these metal complexes up to concentrations of 1 mM. The factors which affect the ability of metal-bound aspartame to interact with the receptor site are discussed.

OsB 2 and RuB 2, ultra-incompressible, hard materials: First-principles electronic structure calculations

NASA Astrophysics Data System (ADS)

Chiodo, S.; Gotsis, H. J.; Russo, N.; Sicilia, E.

2006-07-01

Recently it has been reported that osmium diboride has an unusually large bulk modulus combined with high hardness, and consequently is a most interesting candidate as an ultra-incompressible and hard material. The electronic and structural properties of the transition metal diborides OsB 2 and RuB 2 have been calculated within the local density approximation (LDA). It is shown that the high hardness is the result of covalent bonding between transition metal d states and boron p states in the orthorhombic structure.

High-pressure crystal growth and electromagnetic properties of 5d double-perovskite Ca3OsO6

NASA Astrophysics Data System (ADS)

Feng, Hai Luke; Shi, Youguo; Guo, Yanfeng; Li, Jun; Sato, Akira; Sun, Ying; Wang, Xia; Yu, Shan; Sathish, Clastin I.; Yamaura, Kazunari

2013-05-01

Single crystals of the osmium-containing compound Ca3OsO6 have been successfully grown under high-pressure conditions, for the first time. The crystal structure of Ca3OsO6 were characterized as an ordered double-perovskite structure of space group P21/n with the Ca and Os atoms being fully ordered at the perovskite B-site. The electromagnetic analysis shows that the crystal exhibits a semiconductor-like behavior below 300 K and undergoes an antiferromagnetic transition at 50 K.

Method of making a light weight battery plaque

NASA Technical Reports Server (NTRS)

Reid, M. A.; Post, R. E.; Soltis, D. G. (Inventor)

1984-01-01

A nickel plaque which may be coated with a suitable metal or compound to make an electrode for a fuel cell or battery is fabricated by directing nickel sensitizer, catalyst and plating solutions through a porous plastic substrate in the order named and at prescribed temperatures and flow rates. A boride compound dissolved in the plating solution decreases the electrical resistance of the plaque. Certain substrates may require treatment in an alkali solution to dissolve filler materials thereby increasing porosity to a required 65%.

Alumina-based ceramic composite

DOEpatents

Alexander, K.B.; Tiegs, T.N.; Becher, P.F.; Waters, S.B.

1996-07-23

An improved ceramic composite comprising oxide ceramic particulates, nonoxide ceramic particulates selected from the group consisting of carbides, borides, nitrides of silicon and transition metals and mixtures thereof, and a ductile binder selected from the group consisting of metallic, intermetallic alloys and mixtures thereof is described. The ceramic composite is made by blending powders of the ceramic particulates and the ductile to form a mixture and consolidating the mixture of under conditions of temperature and pressure sufficient to produce a densified ceramic composite. 5 figs.

Thermodynamic analysis of chemical compatibility of several reinforcement materials with niobium aluminides

NASA Technical Reports Server (NTRS)

Misra, Ajay K.

1989-01-01

Chemical compatibility of several reinforcement materials with three niobium aluminides, Nb3Al, Nb2Al, and NbAl3, were examined from thermodynamic considerations. The reinforcement materials considered in this study include carbides, borides, nitrides, oxides, silicides, and Engel-Brewer compounds. Thermodynamics of the Nb-Al system were reviewed and activities of Nb and Al were derived at desired calculation temperatures. Criteria for chemical compatibility between the reinforcement material and Nb-Al compounds have been defined and several chemically compatible reinforcement materials have been identified.

Role of atomic bonding for compound and glass formation in Ni-Si, Pd-Si, and Ni-B systems

NASA Astrophysics Data System (ADS)

Tanaka, K.; Saito, T.; Suzuki, K.; Hasegawa, R.

1985-11-01

Valence electronic structures of crystalline compounds and glassy alloys of Ni silicides, Pd silicides, and Ni borides are studied by soft-x-ray spectroscopy over wide ranges of Si and B concentrations. The samples prepared include bulk compounds, glassy ribbons, and amorphous sputtered films. Silicon Kβ emissions of Ni and Pd silicides generally consist of a prominent peak fixed at ~=4.5 and ~=5.8 eV below the Fermi level EF, respectively, with a shoulder near EF which grows and shifts toward lower energy with increasing Si concentration. The former is identified as due to Si p-like states forming Si 3p-Ni 3d or Si 3p-Pd 4d bonding states while the latter as due to the corresponding antibonding states. Ni L3 and Pd L3 emissions of these silicides indicate that Ni 3d and Pd 4d states lie between the above two states. These local electronic configurations are consistent with partial-density-of-states (PDOS) calculations performed by Bisi and Calandra. Similar electronic configurations are suggested for Ni borides from B Kα and Ni L3 emissions. Differences of emission spectra between compounds and glasses of similar compositions are rather small, but some enhancement of the contribution of antibonding states to the PDOS near EF is suggested for certain glasses over that of the corresponding compounds. These features are discussed in connection with the compound stability and glass formability.

Manganese mono-boride, an inexpensive room temperature ferromagnetic hard material

PubMed Central

Ma, Shuailing; Bao, Kuo; Tao, Qiang; Zhu, Pinwen; Ma, Teng; Liu, Bo; Liu, Yazhou; Cui, Tian

2017-01-01

We synthesized orthorhombic FeB-type MnB (space group: Pnma) with high pressure and high temperature method. MnB is a promising soft magnetic material, which is ferromagnetic with Curie temperature as high as 546.3 K, and high magnetization value up to 155.5 emu/g, and comparatively low coercive field. The strong room temperature ferromagnetic properties stem from the positive exchange-correlation between manganese atoms and the large number of unpaired Mn 3d electrons. The asymptotic Vickers hardness (AVH) is 15.7 GPa which is far higher than that of traditional ferromagnetic materials. The high hardness is ascribed to the zigzag boron chains running through manganese lattice, as unraveled by X-ray photoelectron spectroscopy result and first principle calculations. This exploration opens a new class of materials with the integration of superior mechanical properties, lower cost, electrical conductivity, and fantastic soft magnetic properties which will be significant for scientific research and industrial application as advanced structural and functional materials. PMID:28262805

Femtosecond pulsed laser deposition of amorphous, ultrahard boride thin films

NASA Astrophysics Data System (ADS)

Stock, Michael; Molian, Pal

2004-05-01

Amorphous thin films (300-500 nm) of ultrahard AlMgB10 with oxygen and carbon impurities were grown on Si (100) substrates at 300 K using a solid target of AlMgB14 containing a spinel phase (MgAl2O4) and using a 120 fs pulsed, 800 nm wavelength Ti:sapphire laser. The films were subsequently annealed in argon gas up to 1373 K for 2 h. Scanning electron microscopy (SEM) was used to examine the particulate formation, atomic force microscopy was employed to characterize the film surface topography, x-ray diffraction and transmission electron microscopy were used to determine the microstructure, x-ray photoelectron spectroscopy was performed to examine the film composition, and nanoindentation was employed to study the hardness of thin films. The as-deposited and postannealed films (up to 1273 K) had a stochiometry of AlMgB10 with a significant amount of oxygen and carbon impurities and exhibited amorphous structures for a maximum hardness of 40+/-3 GPa. However, postannealing at higher temperatures led to crystallization and transformation of the film to SiB6 with a substantial loss in hardness. Results are also compared with our previous study on 23 ns, 248 nm wavelength (KrF excimer) pulsed laser deposition of AlMgB14 reported in this journal [Y. Tian, A. Constant, C. C. H. Lo, J. W. Anderegg, A. M. Russell, J. E. Snyder, and P. A. Molian, J. Vac. Sci. Technol. A 21, 1055 (2003)]. .

Redox polymer electrodes for advanced batteries

DOEpatents

Gregg, Brian A.; Taylor, A. Michael

1998-01-01

Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene.

Role of electron concentration in softening and hardening of ternary molybdenum alloys

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1975-01-01

Effects of various combinations of hafnium, tantalum, rhenium, osmium, iridium, and platinum in ternary molybdenum alloys on alloy softening and hardening were determined. Hardness tests were conducted at four test temperatures over the temperature range 77 to 411 K. Results showed that hardness data for ternary molybdenum alloys could be correlated with anticipated results from binary data based upon expressions involving the number of s and d electrons contributed by the solute elements. The correlation indicated that electron concentration plays a dominant role in controlling the hardness of ternary molybdenum alloys.

Method For Synthesizing Extremely High-Temperature Melting Materials

DOEpatents

Saboungi, Marie-Louise; Glorieux, Benoit

2005-11-22

The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as borides, carbides and transition-metal, lanthanide and actinide oxides, using an Aerodynamic Levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

Corrosion of Ceramic Materials

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.; Jacobson, Nathan S.

1999-01-01

Non-oxide ceramics are promising materials for a range of high temperature applications. Selected current and future applications are listed. In all such applications, the ceramics are exposed to high temperature gases. Therefore it is critical to understand the response of these materials to their environment. The variables to be considered here include both the type of ceramic and the environment to which it is exposed. Non-oxide ceramics include borides, nitrides, and carbides. Most high temperature corrosion environments contain oxygen and hence the emphasis of this chapter will be on oxidation processes.

Reactive multilayer synthesis of hard ceramic foils and films

DOEpatents

Makowiecki, Daniel M.; Holt, Joseph B.

1996-01-01

A method for synthesizing hard ceramic materials such as carbides, borides nd aluminides, particularly in the form of coatings provided on another material so as to improve the wear and abrasion performance of machine tools, for example. The method involves the sputter deposition of alternating layers of reactive metals with layers of carbon, boron, or aluminum and the subsequent reaction of the multilayered structure to produce a dense crystalline ceramic. The material can be coated on a substrate or formed as a foil which can be coild as a tape for later use.

Reactive multilayer synthesis of hard ceramic foils and films

DOEpatents

Makowiecki, D.M.; Holt, J.B.

1996-02-13

A method is disclosed for synthesizing hard ceramic materials such as carbides, borides and aluminides, particularly in the form of coatings provided on another material so as to improve the wear and abrasion performance of machine tools, for example. The method involves the sputter deposition of alternating layers of reactive metals with layers of carbon, boron, or aluminum and the subsequent reaction of the multilayered structure to produce a dense crystalline ceramic. The material can be coated on a substrate or formed as a foil which can be coiled as a tape for later use.

Thermodynamic analysis of chemical compatibility of several compounds with Fe-Cr-Al alloys

NASA Technical Reports Server (NTRS)

Misra, Ajay K.

1993-01-01

Chemical compatibility between Fe-19.8Cr-4.8Al (weight percent), which is the base composition for the commercial superalloy MA956, and several carbides, borides, nitrides, oxides, and silicides was analyzed from thermodynamic considerations. The effect of addition of minor alloying elements, such as Ti, Y, and Y2O3, to the Fe-Cr-Al alloy on chemical compatibility between the alloy and various compounds was also analyzed. Several chemically compatible compounds that can be potential reinforcement materials and/or interface coating materials for Fe-Cr-Al based composites were identified.

High temperature solar energy absorbing surfaces

DOEpatents

Schreyer, J.M.; Schmitt, C.R.; Abbatiello, L.A.

A solar collector having an improved coating is provided. The coating is a plasma-sprayed coating comprising a material having a melting point above 500/sup 0/C at which it is stable and selected from the group of boron carbide, boron nitride, metals and metal oxides, nitrides, carbides, borides, and silicates. The coatings preferably have a porosity of about 15 to 25% and a thickness of less than 200 micrometers. The coatings can be provided by plasma-spraying particles having a mean diameter of about 10 to 200 micrometers.

Method for Synthesizing Extremeley High Temperature Melting Materials

DOEpatents

Saboungi, Marie-Louise and Glorieux, Benoit

2005-11-22

The invention relates to a method of synthesizing high-temperature melting materials. More specifically the invention relates to a containerless method of synthesizing very high temperature melting materials such as borides, carbides and transition-metal, lanthanide and actinide oxides, using an Aerodynamic Levitator and a laser. The object of the invention is to provide a method for synthesizing extremely high-temperature melting materials that are otherwise difficult to produce, without the use of containers, allowing the manipulation of the phase (amorphous/crystalline/metastable) and permitting changes of the environment such as different gaseous compositions.

Infrared resonance Raman, and excitation profile studies of Os/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/Cl/sub 2/ and Os/sub 2/(O/sub 2/CCD/sub 3/)/sub 4/Cl/sub 2/. The assignment of the osmium-osmium stretching vibration for a complex involving an osmium-osmium multiple bond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, R.J.H.; Hempleman, A.J.; Tocher, D.A.

1988-08-31

Extensive Raman studies (1525-40 cm/sup /minus/1/) of Os/sub 2/(O/sub 2/CCH/sub 3/)/sub 4/Cl/sub 2/ have led to the identification of the three strong bands, /nu//sub 1/, /nu//sub 2/, and /nu//sub 3/, at 229, 393, and 292 cm/sup /minus/1/ to the key skeletal stretching modes, /nu/(OsOs), /nu/(OsO), and /nu/(OsCl), respectively. Raman spectra of the complex at resonance with the intense electronic band at /lambda//sub max/ = 383 nm lead to the development of a six-membered overtone progression in /nu//sub 1/ as well as combination band progressions in /nu//sub 1/ based upon one quantum of either /nu//sub 2/ or /nu//sub 3/. This indicatesmore » that the principal structural change attendant upon excitation to the resonant state is along the OsOs coordinate. Fourier transform infrared spectra (3500-40 cm/sup /minus/1/) have also been obtained. Acetate deuteriation provides conclusive evidence for many of the infrared and Raman band assignments. The study provides the first firm identification of /nu/(OsOs) for a multiply bonded species.« less

Search for Extraterrestrial Osmium at the Allerod - Younger Dryas Boundary

NASA Astrophysics Data System (ADS)

Beets, C.; Sharma, M.; Kasse, K.; Bohncke, S.

2008-12-01

Ir and Os are excellent markers of extraterrestrial impact events, due to their high abundance in ET objects (Alvarez et al., 1980 Science; Turekian, 1982 Geol. Bull. Am. Spec. Pap.). Os has the advantage over Ir, in that the 187Os/188Os ratio also greatly differs between meteorites and upper continental crust (UCC). The combination of [Os] and 187Os/188Os analyses would be superior in detecting any ET contribution. Firestone et al (2007 PNAS) attributed a widespread 12.9 ka Ir containing black carbon layer to a potential extraterrestrial impact at the Allerød-Younger Dryas (A-YD) boundary. In order to test this inference, we measured [Os] and 187Os/188Os on a radiocarbon dated A-YD record (13.210 to 12.788 cal years BP) from the Netherlands. This location is close to Lommel, a Belgian site studied by Firestone et al.(2007). The organic-rich sequence was sampled continuously over a 12 cm interval at 2 cm resolution (~70 years). About 10 g samples were freeze-dried, ground and homogenized in a zirconia ball-mill. The samples mixed with 190Os tracer solutions were dissolved in carius tubes and Os extracted in liquid bromine. Os was further purified using micro-distillation. Os isotopes were measured using N-TIMS on Dartmouth Triton. The procedural blank was 7 fg/g Os with an isotopic composition of 0.41±0.01 The Allerød samples have an order of magnitude higher abundance than UCC (200 vs. 30 pg/g), but similar 187Os/188Os ratios, >1.1. The sample at the base of the YD (12.893±75 cal years BP) contains a similar amount of Os, but has a distinctly lower isotopic signature, 0.53±0.002. The high [Os] in the A-YD section possibly reflects enrichment by preferential partitioning into organic matter. The Os isotope composition of 0.53, sandwiched between values >1.1, implies contribution of a significant amount of non-radiogenic Os. Since the pollen spectra show no reworking, the non-radiogenic Os could only have been delivered as a discrete pulse at 12.893 cal yr BP. The observation of the non-radiogenic Os isotope composition would therefore be consistent with a meteorite impact. However, it is intriguing to note there was a small volcanic eruption of Laacher See tephra (LST) at this time (surface immediately below LST = 12.979±147 cal years BP, Bittmann, 2007 Veget Hist Archeobot) approximately 150 km away. The timing of this eruption has been traditionally placed in upper Allerød, about 200 years before the onset of YD. More work is needed to resolve the issue of ET Os at the YD boundary.

Negative thermal ion mass spectrometry of osmium, rhenium, and iridium

NASA Technical Reports Server (NTRS)

Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

1991-01-01

This paper describes a technique for obtaining, in a conventional surface ionization mass spectrometer, intense ion beams of negatively charged oxides of Os, Re, and Ir by thermal ionization. It is shown that the principal ion species of these ions are OsO3(-), ReO4(-), and IrO2(-), respectively. For Re-187/Os-187 studies, this technique offers the advantage of isotopic analyses without prior chemical separation of Re from Os.

Rhenium-osmium isotope systematics of ordinary chondrites and iron meteorites

NASA Technical Reports Server (NTRS)

Walker, R. J.; Morgan, J. W.; Horan, M. F.; Grossman, J. N.

1993-01-01

Using negative thermal ionization mass spectrometry, Re and Os abundances were determined by isotope dilution and Os-187/Os-186 measured in 11 ordinary chondrites, and also in 1 IIB and 3 IIIB irons. In addition, Os-186/Os-188 and Os-189/Os-188 ratios were precisely determined for 3 unspiked ordinary chondrites as a means of constraining the intensity of any neutron irradiation these meteorites may have experienced.

Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(mu-C triple bondCC triple bond C)].

PubMed

Bruce, Michael I; Costuas, Karine; Davin, Thomas; Halet, Jean-François; Kramarczuk, Kathy A; Low, Paul J; Nicholson, Brian K; Perkins, Gary J; Roberts, Rachel L; Skelton, Brian W; Smith, Mark E; White, Allan H

2007-12-14

The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os([=C=CH2)(dppe)Cp*]PF6 ([11]PF6), [Os(C triple bond CH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{mu-(=C=CH-CH=C=)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}(2)(mu-C triple bond CC triple bond C)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(mu-C triple bond CC triple bond C)] (M = Fe, Ru, Os). The molecular structures of []PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(C triple bond CPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe approximately Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(mu-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.

Complex anthropogenic sources of platinum group elements in aerosols on Cape Cod, USA.

PubMed

Sen, Indra S; Peucker-Ehrenbrink, Bernhard; Geboy, Nicholas

2013-09-17

Platinum group elements (PGE) of anthropogenic origin have been reported in rainwater, snow, roadside soil and vegetation, industrial waste, and urban airborne particles around the world. As recent studies have shown that PGE are bioavailable in the environment and pose health risks at chronic levels, the extent of PGE pollution is of global concern. In this study, we report PGE concentrations and osmium isotope ((187)Os/(188)Os) ratios of airborne particles (particulate matter, PM10) collected in Woods Hole, a small coastal village on Cape Cod, Massachusetts, U.S.A. The sampling site is more than 100 km away from the nearest urban centers (Boston, Providence) and has no large industrial emission center within a 30 km radius. The study reveals that, although PGE concentrations in rural airborne particulate matter are orders of magnitude lower than in urban aerosols, 69% of the total osmium is of anthropogenic origin. Anthropogenic PGE signatures in airborne particles are thus not restricted to large cities with high traffic flows and substantial industries; they can also be found in rural environments. We further conclude that the combination of Pt/Rh concentration ratios and (187)Os/(188)Os composition can be used to trace PGE sources. The Pt/Rh and (187)Os/(188)Os composition of Woods Hole aerosols indicate that the anthropogenic PGE fraction is primarily sourced from ore smelting processes, with possible minor contributions from fossil fuel burning and automobile catalyst-derived materials. Our results further substantiate the use of (187)Os/(188)Os in source apportionment studies on continental scales.

Features of surface phase formation during case-hardening of iron- and titanium-based alloys

NASA Astrophysics Data System (ADS)

Vintaikin, B. E.; Kamynin, A. V.; Kraposhin, V. S.; Smirnov, A. E.; Terezanova, K. V.; Cherenkova, S. A.; Sheykina, V. I.

2017-11-01

The article provides a detailed analysis of formation features for surface phases in technical iron and Cr20-Ni80 alloy samples that undergo case-hardening at a temperature of 850°C for 2, 4 and 6 hours of saturation in two different environments: acetylene, and molten salt consisting of sodium tetraborate and amorphous boron. We carried out an X-ray phase analysis to determine the phase structure of surface material layers that formed as a result of the case-hardening process. We discovered that after carburising it was possible to detect Fe3C and Fe-α phases on the surface of technical iron samples, and after boriding we found FeB, Fe2B and Fe3B phases; we noted a lack of characteristic Fe-α and Fe-γ peaks on the X-ray diffraction pattern. We detected many different phases in the Cr20-Ni80 alloy after the same type of case-hardening. Titanium oxides appeared after case-hardening of titanium in air at 800°C. We provide data on surface structure of samples subjected to vacuum carburising: over a 2 to 6 hour interval, the layer thickness is a parabolic function of time. When carrying out electrolysis-free liquid boriding, increasing exposure time from 2 to 6 hours alters the thickness of the strengthened layer only slightly, so, when carrying out case-hardening, it is less efficient to increase saturation time in molten salt containing sodium tetraborate and amorphous boron.

Boron oxynitride nanoclusters on tungsten trioxide as a metal-free cocatalyst for photocatalytic oxygen evolution from water splitting

NASA Astrophysics Data System (ADS)

Xie, Ying Peng; Liu, Gang; Lu, Gao Qing (Max); Cheng, Hui-Ming

2012-02-01

Here we show that B2O3-xNx nanoclusters can be formed on the surface of WO3 particles by a combination of thermal oxidation of tungsten boride (WB) in air and the subsequent nitriding process in gaseous ammonia. The resultant nanoclusters are found to play an apparent role in improving the photocatalytic oxygen evolution of WO3 by promoting the surface separation of photoexcited charge-carriers.Here we show that B2O3-xNx nanoclusters can be formed on the surface of WO3 particles by a combination of thermal oxidation of tungsten boride (WB) in air and the subsequent nitriding process in gaseous ammonia. The resultant nanoclusters are found to play an apparent role in improving the photocatalytic oxygen evolution of WO3 by promoting the surface separation of photoexcited charge-carriers. Electronic supplementary information (ESI) available: (1) Experimental section. (2) XRD patterns, FT-IR and Raman spectra of B2O3@WO3 and B2O3-xNx@WO3. (3) Time course of O2 evolution from water splitting using B2O3@WO3 and B2O3-xNx@WO3. (4) XRD pattern and SEM image of pure WO3, UV-visible absorption spectra of pure WO3 and N-WO3. (5) UV-visible absorption spectra of bulk B2O3 and schematic of band edges of WO3, bulk B2O3, and B2O3-xNx nanocluster. See DOI: 10.1039/c2nr11846g

Use of a tissue sectioner to expose internal structures of biological samples for scanning electron microscopy.

PubMed

Brown, M F; Brotzman, H G; Kinden, D A

1976-09-01

A procedure yielding sections of unembedded biological samples for observation by scanning electron microscopy is described. Sections of samples, fixed and hardened in OsO4, were obtained in quantity with a tissue sectioner. Subsequent treatments to osmium-coat cut surfaces were employed prior to critical point drying. The procedure yields cleanly cut surfaces through cells and cytoplasmic organelles which are retained in their normal position. Sections of apple leaf and mouse kidney are illustrated. Sections can be readily cut in a desired plane with less structural damage than is typically encountered by other sectioning or dissection techniques.

Redox polymer electrodes for advanced batteries

DOEpatents

Gregg, B.A.; Taylor, A.M.

1998-11-24

Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene. 2 figs.

An Ordinary Chondrite Impactor Composition for the Bosumtwi Impact Structure, Ghana, West Africa: Discussion of Siderophile Element Contents and Os and Cr Isotope Data

NASA Technical Reports Server (NTRS)

Koeberl, Christian; Shukolyukov, Alex; Lugmair, Guenter

2004-01-01

Osmium isotope data had shown that Ivory Coast tektites contain an extraterrestrial component, but do not allow distinction between chondritic and iron meteorite contamination. PGE abundances of Ivory Coast tektites and impactites and target rocks from the Bosumtwi crater, the source crater of the Ivory Coast tektites, were all relatively high and did not allow to resolve the presence, or identify the nature, of the meteoritic component. However, Cr isotope analyses of an Ivory Coast tektite yielded a distinct 53Cr excess of 0.30+/-0.06, which indicates that the Bosumtwi impactor was an ordinary chondrite.

Effects on optical systems from interactions with oxygen atoms in low earth orbits

NASA Technical Reports Server (NTRS)

Peters, P. N.; Swann, J. T.; Gregory, J. C.

1986-01-01

Modifications of material surface properties due to interactions with ambient atomic oxygen have been observed on surfaces facing the orbital direction in low earth orbits. Some effects are very damaging to surface optical properties while some are more subtle and even beneficial. Most combustible materials are heavily etched, and some coatings, such as silver and osmium, are seriously degraded or removed as volatile oxides. The growth of oxide films on metals and semiconductors considered stable in dry air was measured. Material removal, surface roughness, reflectance, and optical densities are reported. Effects of temperature, contamination, and overcoatings are noted.

Effects on optical systems from interactions with oxygen atoms in low earth orbits

NASA Astrophysics Data System (ADS)

Peters, P. N.; Swann, J. T.; Gregory, J. C.

1986-04-01

Modifications of material surface properties due to interactions with ambient atomic oxygen have been observed on surfaces facing the orbital direction in low earth orbits. Some effects are very damaging to surface optical properties while some are more subtle and even beneficial. Most combustible materials are heavily etched, and some coatings, such as silver and osmium, are seriously degraded or removed as volatile oxides. The growth of oxide films on metals and semiconductors considered stable in dry air was measured. Material removal, surface roughness, reflectance, and optical densities are reported. Effects of temperature, contamination, and overcoatings are noted.

Alloy hardening and softening in binary molybdenum alloys as related to electron concentration

NASA Technical Reports Server (NTRS)

Stephens, J. R.; Witzke, W. R.

1972-01-01

An investigation was conducted to determine the effects of alloy additions of hafnium, tantalum, tungsten, rhenium, osmium, iridium, and platinum on hardness of molybdenum. Special emphasis was placed on alloy softening in these binary molybdenum alloys. Results showed that alloy softening was produced by those elements having an excess of s+d electrons compared to molybdenum, while those elements having an equal number or fewer s+d electrons that molybdenum failed to produce alloy softening. Alloy softening and alloy hardening can be correlated with the difference in number of s+d electrons of the solute element and molybdenum.

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

PubMed

Pandey, Krishna K

2012-03-21

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of

How to estimate hardness of crystals on a pocket calculator

NASA Astrophysics Data System (ADS)

Šimůnek, Antonín

2007-05-01

A generalization of the semiempirical microscopic model of hardness is presented and applied to currently studied borides, carbides, and nitrides of heavy transition metals. The hardness of OsB, OsC, OsN, PtN, RuC, RuB2 , ReB2 , OsB2 , IrN2 , PtN2 , and OsN2 crystals in various structural phases is predicted. It is found that none of the transition metal crystals is superhard, i.e., with hardness greater than 40GPa . The presented method provides materials researchers with a practical tool in the search for new hard materials.

First-principles modeling of hardness in transition-metal diborides

NASA Astrophysics Data System (ADS)

Lazar, Petr; Chen, Xing-Qiu; Podloucky, Raimund

2009-07-01

Based on recent experiments, the diborides OsB2 and ReB2 were proposed to be ultraincompressible and superhard materials. By application of an ab initio density-functional theory approach we investigate the elastic and cleavage fracture properties of the borides MB2 ( M=Hf , Ta, W, Re, Os, and Ir). We derive a direct correlation between the lowest calculated critical cleavage stress and the experimental (micro)hardness. By calculating the critical shear stress and estimating the possibility of dislocation emission we can justify the prediction that ReB2 is indeed a superhard material.

Thermodynamic Analysis of Compatibility of Several Reinforcement Materials with Beta Phase NiAl Alloys

NASA Technical Reports Server (NTRS)

Misra, Ajay K.

1988-01-01

Chemical compatibility of several reinforcement materials with beta phase NiAl alloys within the concentration range 40 to 50 at. percent Al have been analyzed from thermodynamic considerations at 1373 and 1573 K. The reinforcement materials considered in this study include carbides, borides, oxides, nitrides, beryllides, and silicides. Thermodynamic data for NiAl alloys have been reviewed and activity of Ni and Al in the beta phase have been derived at 1373 and 1573 K. Criteria for chemical compatibility between the reinforcement material and the matrix have been defined and several chemically compatible reinforcement materials have been defined.

Material comprising two different non-metallic parrticles having different particle sizes for use in solar reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klausner, James F.; Momen, Ayyoub Mehdizadeh; Al-Raqom, Fotouh A.

Disclosed herein is a composite particle comprising a first non-metallic particle in which is dispersed a second non-metallic particle, where the first non-metallic particle and the second non-metallic particle are inorganic; and where a chemical composition of the first non-metallic particle is different from a chemical composition of the second non-metallic particle; and where the first non-metallic particle and the second non-metallic particle are metal oxides, metal carbides, metal nitrides, metal borides, metal silicides, metal oxycarbides, metal oxynitrides, metal boronitrides, metal carbonitrides, metal borocarbides, or a combination thereof.

Lightweight porous plastic plaque. [nickel cadmium batteries

NASA Technical Reports Server (NTRS)

Reid, M.

1978-01-01

The porosity and platability of various materials were investigated to determine a suitable substrate for nickel-plated electrodes. Immersion, ultrasonics, and flow-through plating techniques were tried using nonproprietary formulations, and proprietary phosphide and boride baths. Modifications to the selected material include variations in formulation and treatment, carbon loading to increase conductivity, and the incorporation of a grid. Problems to be solved relate to determining conductivities and porosities as a function of amount of nickel plated on the plastics; loading; charge and discharge curves of electrodes at different current densities; cell performance; and long-term degradation of electrodes.

Identification of novel sulfur-containing steroids in sediments and petroleum: probable incorporation of sulfur into δ 5,7-sterols during early diagenesis

NASA Astrophysics Data System (ADS)

Sinninghe Damsté, Jaap S.; Schouten, Stefan; de Leeuw, Jan W.; van Duin, Adri C. T.; Geenevasen, Jan A. J.

1999-01-01

A novel sulfur-containing sterane, 4α,7α-epithio-5β-cholestane, has been identified in a sediment extract from the Miocene Northern Apennines marl (Italy) after its isolation by column chromatography and high pressure liquid chromatography. The compound has been characterised by GC-MS and mild Nickel boride desulfurisation and one and two-dimensional 1H NMR techniques. C 27-C 29 homologs have been detected in sediment extracts of three different formations and in one petroleum sample. These sulfur-containing steroids are probably formed by an intramolecular reaction of inorganic sulfides with early diagenetic products of Δ 5,7-sterols.

In-situ Formation of Reinforcement Phases in Ultra High Temperature Ceramic Composites

NASA Technical Reports Server (NTRS)

Stackpoole, Margaret M (Inventor); Gasch, Matthew J (Inventor); Olson, Michael W (Inventor); Hamby, Ian W. (Inventor); Johnson, Sylvia M (Inventor)

2013-01-01

A tough ultra-high temperature ceramic (UHTC) composite comprises grains of UHTC matrix material, such as HfB.sub.2, ZrB.sub.2 or other metal boride, carbide, nitride, etc., surrounded by a uniform distribution of acicular high aspect ratio reinforcement ceramic rods or whiskers, such as of SiC, is formed from uniformly mixing a powder of the UHTC material and a pre-ceramic polymer selected to form the desired reinforcement species, then thermally consolidating the mixture by hot pressing. The acicular reinforcement rods may make up from 5 to 30 vol % of the resulting microstructure.

Modeling the mechanical behavior of ceramic and heterophase structures manufactured using selective laser sintering and spark plasma sintering

NASA Astrophysics Data System (ADS)

Skripnyak, Vladimir A.; Skripnyak, Evgeniya G.; Skripnyak, Vladimir V.; Vaganova, Irina K.

A model for predicting mechanical properties of ultra-high temperature ceramics and composites manufactured by selective laser sintering (SLS) and spark plasma sintering (SPS) under shock loading is presented. The model takes into account the porous structure, the specific volume and average sizes of phases, and the temperature of sintering. Residual stresses in ceramic composites reinforced with particles of refractory borides, carbides and nitrides after SLS or SPS were calculated. It is shown that the spall strength of diboride-zirconium matrix composites can be increased by the decreasing of porosity and the introduction of inclusions of specially selected refractory strengthening phases.

Foreword

NASA Astrophysics Data System (ADS)

Manghnani, Murli H.

2015-09-01

The 18th International Symposium on Boron, Borides and Related Materials was held in Hawaii Prince Hotel Waikiki, Honolulu, Hawaii, USA on August 31 to September 5, 2014 (ISBB 2014). A booklet of the Program and Abstracts prepared for the Symposium served as an important record of the scientific papers presented as oral paper (68) and as posters (53). The wide range of contributions in various areas of inter-disciplinary research in boron-related materials, and the discussions during the sessions, demonstrated impressive advancements and offer many future opportunities for individual as well as collaborative endeavors globally.

Chemical precursors to non-oxide ceramics: Macro to nanoscale materials

NASA Astrophysics Data System (ADS)

Forsthoefel, Kersten M.

Non-oxide ceramics exhibit a number of important properties that make them ideal for technologically important applications (thermal and chemical stability, high strength and hardness, wear-resistance, light weight, and a range of electronic and optical properties). Unfortunately, traditional methodologies to these types of materials are limited to fairly simple shapes and complex processed forms cannot be attained through these methods. The establishment of the polymeric precursor approach has allowed for the generation of advanced materials, such as refractory non-oxide ceramics, with controlled compositions, under moderate conditions, and in processed forms. The goal of the work described in this dissertation was both to develop new processible precursors to technologically important ceramics and to achieve the formation of advanced materials in processed forms. One aspect of this research exploited previously developed preceramic precursors to boron carbide, boron nitride and silicon carbide for the generation of a wide variety of advanced materials: (1) ultra-high temperature ceramic (UHTC) structural materials composed of hafnium boride and related composite materials, (2) the quaternary borocarbide superconductors, and (3) on the nanoscale, non-oxide ceramic nanotubules. The generation of the UHTC and the quaternary borocarbide materials was achieved through a method that employs a processible polymer/metal(s) dispersion followed by subsequent pyrolyses. In the case of the UHTC, hafnium oxide, hafnium, or hafnium boride powders were dispersed in a suitable precursor to afford hafnium borides or related composite materials (HfB2/HfC, HfB2/HfN, HfB2/SiC) in high yields and purities. The quaternary borocarbide superconducting materials were produced from pyrolyses of dispersions containing appropriate stoichiometric amounts of transition metal, lanthanide metal, and the polyhexenyldecaborane polymer. Both chemical vapor deposition (CVD) based routes employing a

The Physics and Chemistry of carbides, Nitrides and Borides. Volume 185

DTIC Science & Technology

1990-01-01

and C-B-C chains [15,17]. Clearly, the use of boron-rich solids as electronic materials will place new demands on the quality of materials. In this...first heated in a pyrolytic boron nitride (PBN) crucible ( Union Carbide Corp.) under high vacuum (< 50 mTorr) to 1900°C. This removed surface...contamination of the sample. The powders were loaded into a graphite die with a high-purity BN die liner ( Union Carbide Grade HBC) with inner diameter of 3/8

Basal deposits and drusen in eyes with age-related maculopathy: evidence for solid lipid particles.

PubMed

Curcio, Christine A; Presley, J Brett; Millican, C Leigh; Medeiros, Nancy E

2005-06-01

Neutral lipid, including esterified cholesterol, and apolipoproteins B and E are abundant in basal deposits and drusen of aged and age-related maculopathy (ARM) eyes. The principal component of basal linear deposit (BlinD), a specific ARM lesion, is membranous debris, which if actually derived from membranes cannot account for extracellular neutral lipid. We therefore used a lipid-preserving ultrastructural method to obtain improved images of membranous debris. Maculas from 44 human donors (71-96 yr) were preserved <7.5 hr after death. Blocks were post-fixed in 2% osmium or osmium-tannic acid-paraphenylenediamine (OTAP) to preserve neutral lipid for thin-section transmission electron microscopic (TEM) examination. Solid particles identified by OTAP were considered closest to the in vivo state of extracellular lipids. Micrographs were examined for intermediate forms, with greatest weight given to comparable images from different preparations of same or fellow eyes. Twenty eyes of older adults (12 with ARM including fellows treated with photodynamic and radiation therapies) had adequately preserved extracellular lipid. The exterior surface of membranous debris was thicker and more electron-dense than basal infoldings of retinal pigment epithelium (RPE) cells. By OTAP, individual membranous debris profiles were solid (diameters, 80-200 nm) and formed tracks across or aggregations within basal laminar deposits. Solid particles and/or pools of neutral lipid were visible in BlinD and drusen. When processed to preserve lipid, membranous debris resembles neither membranes of surrounding cells nor vesicles possessing aqueous interiors but rather solid particles. These results are consistent with recent evidence implicating lipoprotein particles of intra-ocular origin as a potential source of neutral lipids, including esterified cholesterol, in the specific lesions of ARM.

Design for low-cost gas metal arc weld-based aluminum 3-D printing

NASA Astrophysics Data System (ADS)

Haselhuhn, Amberlee S.

Additive manufacturing, commonly known as 3-D printing, has the potential to change the state of manufacturing across the globe. Parts are made, or printed, layer by layer using only the materials required to form the part, resulting in much less waste than traditional manufacturing methods. Additive manufacturing has been implemented in a wide variety of industries including aerospace, medical, consumer products, and fashion, using metals, ceramics, polymers, composites, and even organic tissues. However, traditional 3-D printing technologies, particularly those used to print metals, can be prohibitively expensive for small enterprises and the average consumer. A low-cost open-source metal 3-D printer has been developed based upon gas metal arc weld (GMAW) technology. Using this technology, substrate release mechanisms have been developed, allowing the user to remove a printed metal part from a metal substrate by hand. The mechanical and microstructural properties of commercially available weld alloys were characterized and used to guide alloy development in 4000 series aluminum-silicon alloys. Wedge casting experiments were performed to screen magnesium, strontium, and titanium boride alloying additions in hypoeutectic aluminum-silicon alloys for their properties and the ease with which they could be printed. Finally, the top performing alloys, which were approximately 11.6% Si modified with strontium and titanium boride were cast, extruded, and drawn into wire. These wires were printed and the mechanical and microstructural properties were compared with those of commercially available alloys. This work resulted in an easier-to-print aluminum-silicon-strontium alloy that exhibited lower porosity, equivalent yield and tensile strengths, yet nearly twice the ductility compared to commercial alloys.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hossain, M. Anwar; Center for Crystal Science and Technology, University of Yamanashi, Miyamae 7-32, Kofu, Yamanashi 400-8511; Tanaka, Isao

We studied thermoelectric properties of YB{sub 41}Si{sub 1.3} single crystals grown by the floating zone method. The composition of the grown crystal was confirmed by electron probe micro-analysis. We have determined the growth direction for the first time for these borosilicides, and discovered relatively large anisotropy in electrical properties. We measured the electrical resistivity and Seebeck coefficient along [510] (the growth direction) and [052] directions and we found that this crystal exhibits strong electrical anisotropy with a maximum of more than 8 times. An interesting layered structural feature is revealed along [510] with dense boron cluster layers and yttrium layers,more » with conductivity enhanced along this direction. We obtained 3.6 times higher power factor along [510] compared to that along [052]. Although the ZT of the present system is low, anisotropy in the thermoelectric properties of a boride was reported for the first time, and can be a clue in developing other boride systems also. - Graphical abstract: The growth direction ([510]) was determined for the first time in YB{sub 41}Si{sub 1.3} single crystals and revealed an interesting layered feature of boron clusters and metal atoms, along which the electrical conductivity and thermoelectric power factor was strongly enhanced. - Highlights: • We have grown YB{sub 41}Si{sub 1.3} single crystals by the floating zone method. • Growth direction of [510] determined for first time in REB{sub 41}Si{sub 1.2}. • Electrical resistivity was strongly anisotropic with possible enhancement along metal layers. • The obtained power factor along [510] is 3.6 times higher than that along [052].« less

Three-dimensional nanometer scale analyses of precipitate structures and local compositions in titanium aluminide engineering alloys

NASA Astrophysics Data System (ADS)

Gerstl, Stephan S. A.

Titanium aluminide (TiAl) alloys are among the fastest developing class of materials for use in high temperature structural applications. Their low density and high strength make them excellent candidates for both engine and airframe applications. Creep properties of TiAl alloys, however, have been a limiting factor in applying the material to a larger commercial market. In this research, nanometer scale compositional and structural analyses of several TiAl alloys, ranging from model Ti-Al-C ternary alloys to putative commercial alloys with 10 components are investigated utilizing three dimensional atom probe (3DAP) and transmission electron microscopies. Nanometer sized borides, silicides, and carbide precipitates are involved in strengthening TiAl alloys, however, chemical partitioning measurements reveal oxygen concentrations up to 14 at. % within the precipitate phases, resulting in the realization of oxycarbide formation contributing to the precipitation strengthening of TiAl alloys. The local compositions of lamellar microstructures and a variety of precipitates in the TiAl system, including boride, silicide, binary carbides, and intermetallic carbides are investigated. Chemical partitioning of the microalloying elements between the alpha2/gamma lamellar phases, and the precipitate/gamma-matrix phases are determined. Both W and Hf have been shown to exhibit a near interfacial excess of 0.26 and 0.35 atoms nm-2 respectively within ca. 7 nm of lamellar interfaces in a complex TiAl alloy. In the case of needle-shaped perovskite Ti3AlC carbide precipitates, periodic domain boundaries are observed 5.3+/-0.8 nm apart along their growth axis parallel to the TiAl[001] crystallographic direction with concomitant composition variations after 24 hrs. at 800°C.

Method and system for ethanol production

DOEpatents

Feder, H.M.; Chen, M.J.

1980-05-21

A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. The only other significant by-product is methane. Selected transition metal carbonyls include those of iron, ruthenium and possibly manganese and osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 24-diazabicyclooctane, dimethyneopentylamine and 2-pryidinol.

Method and system for ethanol production

DOEpatents

Feder, Harold M.; Chen, Michael J.

1981-01-01

A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. The only other significant by product is methane. Selected transition metal carbonyls include those of iron, ruthenium and possibly manganese and osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 24-diazabicyclooctane, dimethyneopentylamine and 2-pryidinol.

Method and system for ethanol production

DOEpatents

Feder, Harold M.; Chen, Michael J.

1983-01-01

A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.

Method and system for ethanol production

DOEpatents

Feder, H.M.; Chen, M.J.

1981-09-24

A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium, ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.

Structure of transition-metal cluster compounds: Use of an additional orbital resulting from the f, g character of spd bond orbitals*

PubMed Central

Pauling, Linus

1977-01-01

A general theory of the structure of complexes of the transition metals is developed on the basis of the enneacovalence of the metals and the requirements of the electroneutrality principle. An extra orbital may be provided through the small but not negligible amount of f and g character of spd bond orbitals, and an extra electron or electron pair may be accepted in this orbital for a single metal or a cluster to neutralize the positive electric charge resulting from the partial ionic character of the bonds with ligands, such as the carbonyl group. Examples of cluster compounds of cobalt, ruthenium, rhodium, osmium, and gold are discussed. PMID:16592470

Structure of transition-metal cluster compounds: Use of an additional orbital resulting from the f, g character of spd bond orbitals.

PubMed

Pauling, L

1977-12-01

A general theory of the structure of complexes of the transition metals is developed on the basis of the enneacovalence of the metals and the requirements of the electroneutrality principle. An extra orbital may be provided through the small but not negligible amount of f and g character of spd bond orbitals, and an extra electron or electron pair may be accepted in this orbital for a single metal or a cluster to neutralize the positive electric charge resulting from the partial ionic character of the bonds with ligands, such as the carbonyl group. Examples of cluster compounds of cobalt, ruthenium, rhodium, osmium, and gold are discussed.

Mineral resource of the month: Chromium

USGS Publications Warehouse

Schulte, Ruth

2018-01-01

Although chromium is a metal, it does not occur naturally in metallic form. Chromium can be found in many minerals, but the only economically significant chromium-bearing mineral is chromite. Chromite has been mined from four different deposit types: stratiform chromite, podiform chromite, placer chromite, and laterite deposits. Most of the world's resources, however, are located in stratiform chromite deposits, such as the Bushveld Complex in South Africa. The economic potential of chromite resources depends on the thickness and continuity of the deposit and on the grade of the ore. Many of the major stratiform chromite deposits also contain economic levels of platinum, paladium, rhodium, osmium, iridium, and ruthenium.

[Calcium in the developing skeletal muscles of the chick embryo].

PubMed

Samosudova, N V; Enenko, S O; Larin, Iu S; Shungskaia, V E

1982-07-01

The osmium-pyroantimonate technique was used for the ultrastructural study of Ca2+-localization in two types of chick embryo skeletal muscles: m. pectoralis and m. soleus. In 8- and 12-day old embryos the pyroantimonate precipitate was found on plasmalemma, condensed chromatine and ribosomes and in N-lines of I-band. During myogenesis (15-, 21-day old embryos) the calcium precipitate is redistributed from the above mentioned sites to terminal cisternae and N-line of I-band. It is proposed that calcium of N-lines may be involved in the glycogenolysis, its association with the muscle contraction occurring particularly at early developmental stages.

A whiff of oxygen before the great oxidation event?

PubMed

Anbar, Ariel D; Duan, Yun; Lyons, Timothy W; Arnold, Gail L; Kendall, Brian; Creaser, Robert A; Kaufman, Alan J; Gordon, Gwyneth W; Scott, Clinton; Garvin, Jessica; Buick, Roger

2007-09-28

High-resolution chemostratigraphy reveals an episode of enrichment of the redox-sensitive transition metals molybdenum and rhenium in the late Archean Mount McRae Shale in Western Australia. Correlations with organic carbon indicate that these metals were derived from contemporaneous seawater. Rhenium/osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 +/- 8 million years ago (Ma). Molybdenum and rhenium were probably supplied to Archean oceans by oxidative weathering of crustal sulfide minerals. These findings point to the presence of small amounts of O2 in the environment more than 50 million years before the start of the Great Oxidation Event.

Concentrations of platinum group elements in 122 U.S. coal samples

USGS Publications Warehouse

Oman, C.L.; Finkelman, R.B.; Tewalt, S.J.

1997-01-01

Analysis of more than 13,000 coal samples by semi-quantitative optical emission spectroscopy (OES) indicates that concentrations of the platinum group elements (iridium, palladium, platinum, osmium, rhodium, and ruthenium) are less than 1 ppm in the ash, the limit of detection for this method of analysis. In order to accurately determine the concentration of the platinum group elements (PGE) in coal, additional data were obtained by inductively coupled plasma mass spectroscopy, an analytical method having part-per-billion (ppb) detection limits for these elements. These data indicate that the PGE in coal occur in concentrations on the order of 1 ppb or less.

INTERACTION OF INTERSTITIAL CLUSTERS WITH RHENIUM, OSMIUM, AND TANTALUM IN TUNGSTEN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Setyawan, Wahyu; Nandipati, Giridhar; Kurtz, Richard J.

2016-09-01

In the previous semi annual report, we explored the stability of interstitial clusters in W up to size seven. In this report, we study the binding of those clusters to Re, Os, and Ta atoms. For each cluster size, the three most stable configurations are considered to average the binding property. The average binding energy to a Re decreases from 0.79 eV for a size-1 cluster (a [111] dumbbell) to 0.65 eV for a size-7 cluster. For Os, the binding decreases from 1.61 eV for a [111] dumbbell to 1.34 eV for a size-7 cluster. Tantalum is repulsive to interstitialmore » clusters with binding energy ranges from -0.61 eV for a [111] dumbbell to -0.5 eV for a size-7 cluster.« less

Osmium Isotope Evidence for an S-Process Carrier in Primitive Chondrites

NASA Technical Reports Server (NTRS)

Brandon, A. D.; Puchtel, I. S.; Humayun, M.; Zolensky, M.

2005-01-01

The degree of isotopic mixing in the solar nebula and the nature of pre-solar components that have contributed to our solar system remain subjects of vigorous debate. Isotopic anomalies have been identified in Ca-Al inclusions in chondrites [1-4]. This indicates that refractory pre-solar components were not completely homogenized or processed away at the high temperatures experienced by CAIs. Pre-solar grains (SiC, C, etc.) are prevalent in primitive chondrites, and preserve isotopic heterogeneity resulting from the nucleosynthetic processes occurring in the stars from which these grains formed [2,4]. Several recent studies employing precise techniques for measuring Ru, Mo and Zr isotopes in bulk meteorites, have come up with varying conclusions on the degree of effectiveness of nebular mixing on the scale of bulk meteorite material. Some of these studies have reported isotopic anomalies in Mo and Ru [3,5-7], while others have not observed anomalies in Mo, Ru, or Zr [8-10]. Debate over the quality of the data, the normalization techniques employed, the absence or presence of isobaric interferences during the measurements on different types of instruments (e.g. TIMS versus ICP-MS), and other factors, has ensued [11,12].

Osmium Isotopic Evolution of the Mantle Sources of Precambrian Ultramafic Rocks

NASA Astrophysics Data System (ADS)

Gangopadhyay, A.; Walker, R. J.

2006-12-01

The Os isotopic composition of the modern mantle, as recorded collectively by ocean island basalts, mid- oceanic ridge basalts (MORB) and abyssal peridotites, is evidently highly heterogeneous (γ Os(I) ranging from <-10 to >+25). One important question, therefore, is how and when the Earth's mantle developed such large-scale Os isotopic heterogeneities. Previous Os isotopic studies of ancient ultramafic systems, including komatiites and picrites, have shown that the Os isotopic heterogeneity of the terrestrial mantle can be traced as far back as the late-Archean (~ 2.7-2.8 Ga). This observation is based on the initial Os isotopic ratios obtained for the mantle sources of some of the ancient ultramafic rocks determined through analyses of numerous Os-rich whole-rock and/or mineral samples. In some cases, the closed-system behavior of these ancient ultramafic rocks was demonstrated via the generation of isochrons of precise ages, consistent with those obtained from other radiogenic isotopic systems. Thus, a compilation of the published initial ^{187}Os/^{188}Os ratios reported for the mantle sources of komatiitic and picritic rocks is now possible that covers a large range of geologic time spanning from the Mesozoic (ca. 89 Ma Gorgona komatiites) to the Mid-Archean (e.g., ca. 3.3 Ga Commondale komatiites), which provides a comprehensive picture of the Os isotopic evolution of their mantle sources through geologic time. Several Precambrian komatiite/picrite systems are characterized by suprachondritic initial ^{187}Os/^{188}Os ratios (e.g., Belingwe, Kostomuksha, Pechenga). Such long-term enrichments in ^{187}Os of the mantle sources for these rocks may be explained via recycling of old mafic oceanic crust or incorporation of putative suprachondritic outer core materials entrained into their mantle sources. The relative importance of the two processes for some modern mantle-derived systems (e.g., Hawaiian picrites) is an issue of substantial debate. Importantly, however, the high-precision initial Os isotopic compositions of the majority of ultramafic systems show strikingly uniform initial ^{187}Os/^{188}Os ratios, consistent with their derivation from sources that had Os isotopic evolution trajectory very similar to that of carbonaceous chondrites. In addition, the Os isotopic evolution trajectories of the mantle sources for most komatiites show resolvably lower average Re/Os than that estimated for the Primitive Upper Mantle (PUM), yet significantly higher than that obtained in some estimates for the modern convecting upper mantle, as determined via analyses of abyssal peridotites. One possibility is that most of the komatiites sample mantle sources that are unique relative to the sources of abyssal peridotites and MORB. Previous arguments that komatiites originate via large extents of partial melting of relatively deep upper mantle, or even lower mantle materials could, therefore, implicate a source that is different from the convecting upper mantle. If so, this source is remarkably uniform in its long-term Re/Os, and it shows moderate depletion in Re relative to the PUM. Alternatively, if the komatiites are generated within the convective upper mantle through relatively large extents of partial melting, they may provide a better estimate of the Os isotopic composition of the convective upper mantle than that obtained via analyses of MORB, abyssal peridotites and ophiolites.

Osmium isotopes demonstrate distal transport of contaminated sediments in Chesapeake Bay

USGS Publications Warehouse

Helz, G.R.; Adelson, J.M.; Miller, C.V.; Cornwell, J.C.; Hill, J.M.; Horan, M.; Walker, R.J.

2000-01-01

Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post- Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.Because the isotopic composition of anthropogenic Os is normally distinctive in comparison to continental crust and is precisely measurable, this platinum-group element is attractive as a tracer of transport pathways for contaminated sediments in estuaries. Evidence herein and elsewhere suggest that biomedical research institutions are the chief source of anthropogenic Os. In the Chesapeake Bay region, uncontaminated sediments bear a crustal 187Os/188Os signature of 0.73 ?? 0.10. Slightly higher 187Os/188Os ratios occur in Re-rich Coastal Plain deposits due to post-Miocene 187Re decay. The upper Susquehanna Basin yields sediments also with higher 187Os/188Os. Beginning in the late 1970s, this signal was overprinted by a low 187Os/188Os (anthropogenic) source in the lower Susquehanna Basin. In the vicinity of Baltimore, which is a major center of heavy industry as well as biomedical research, anthropogenic Os has been found only in sediments impacted by the principal wastewater treatment plant. Surprisingly, a mid-Bay site distant from anthropogenic sources contains the strongest anthropogenic Os signal in the data set, having received anthropogenic Os sporadically since the mid-20th Century. Transport of particles to this site overrode the northward flowing bottom currents. Finding anthropogenic Os at this site cautions that other particle-borne substances, including hazardous ones, could be dispersed broadly in this estuary.

Rhenium-osmium systematics of calcium-aluminium-rich inclusions in carbonaceous chondrites

USGS Publications Warehouse

Becker, H.; Morgan, J.W.; Walker, R.J.; MacPherson, G.J.; Grossman, J.N.

2001-01-01

The Re-Os isotopic systematics of calcium-aluminium-rich inclusions (CAIs) in chondrites were investigated in order to shed light on the behavior of the Re-Os system in bulk chondrites, and to constrain the timing of chemical fractionation in primitive chondrites. CAIs with relatively unfractionated rare earth element (REE) patterns (groups I, III, V, VI) define a narrow range of 187Re/188Os (0.3764-0.4443) and 187Os/188Os (0.12599-0.12717), and high but variable Re and Os abundances (3209-41,820 ppb Os). In contrast, CAIs that show depletions in highly refractory elements and strongly fractionated REE patterns (group II) also show a much larger range in 187Re/188Os (0.409-0.535) and 187Os/188Os (0.12695-0.13770), and greater than an order of magnitude lower Re and Os abundances than other groups (e.g., 75.7-680.2 ppb Os). Sixteen bulk CAIs and CAI splits plot within analytical uncertainty of a 4558 Ga reference isochron, as is expected for materials of this antiquity. Eight samples, however, plot off the isochron. Several possible reasons for these deviations are discussed. Data for multiple splits of one CAI indicate that the nonisochronous behavior for at least this CAI is the result of Re-Os reequilibration at approximately 1.6 Ga. Thus, the most likely explanation for the deviations of most of the nonisochronous CAIs is late-stage open-system behavior of Re and Os in the asteroidal environment. The 187Os/188Os-Os systematics of CAIs are consistent with previous models that indicate group II CAIs are mixtures of components that lost the bulk of their highly refractory elements in a previous condensation event and a minor second component that provided refractory elements at chondritic relative proportions. The high Re/Os of group II CAIs relative to other CAIs and chondrite bulk rocks may have been caused by variable mobilization of Re and Os during medium- to low-temperature parent body alteration ??4.5 Ga ago. This model is favored over nebular models, which pose several difficulties. The narrow range of 187Os/188Os in group I, III, V, and VI bulk CAIs, and the agreement with 187Os/188Os of whole rock carbonaceous chondrites suggest that on a bulk inclusion scale, secondary alteration only modestly fractionated Re/Os in these CAIs. The average of 187Os/188Os for group I, III, V, and VI CAIs is indistinguishable from average CI chondrites, indicating a modern solar system value for 187Os/188Os of 0.12650, corresponding to a 187Re/188Os of 0.3964. Copyright ?? 2001 Elsevier Science Ltd.

Rhenium-osmium and samarium-neodymium isotopic systematics of the Stillwater complex

NASA Technical Reports Server (NTRS)

Lambert, David D.; Shirey, Steven B.; Carlson, Richard W.; Morgan, John W.; Walker, Richard J.

1989-01-01

The role of magma mixing in the formation of strategic platinum-group element ore deposits is examined using isotopic data from the Stillwater Complex, Montana. Nd and Os isotopic data show that the intrusion formed from at least two distinct magmas: ultramafic (U-type) affinity magmas and anorthositic (A-type) affinity magmas. The U-type magmas formed from a lithospheric mantle source containing recycled crustal materials and the A-type magmas originated either by crustal contamination of basaltic magmas or by partial melting of basalt in the lower crust. The results also suggest that the platinum-group element ore deposits were derived from A-type magmas which were injected into the U-type magma chamber at several stages during the development of the ultramafic series.

Numerical and experimental study of electron-beam coatings with modifying particles FeB and FeTi

NASA Astrophysics Data System (ADS)

Kryukova, Olga; Kolesnikova, Kseniya; Gal'chenko, Nina

2016-07-01

An experimental study of wear-resistant composite coatings based on titanium borides synthesized in the process of electron-beam welding of components thermo-reacting powders are composed of boron-containing mixture. A model of the process of electron beam coating with modifying particles of boron and titanium based on physical-chemical transformations is supposed. The dissolution process is described on the basis of formal kinetic approach. The result of numerical solution is the phase and chemical composition of the coating under nonequilibrium conditions, which is one of the important characteristics of the coating forming during electron beam processing. Qualitative agreement numerical calculations with experimental data was shown.

Plasma-induced damage of tungsten coatings on graphite limiters

NASA Astrophysics Data System (ADS)

Fortuna, E.; Rubel, M. J.; Psoda, M.; Andrzejczuk, M.; Kurzydowski, K. J.; Miskiewicz, M.; Philipps, V.; Pospieszczyk, A.; Sergienko, G.; Spychalski, M.; Zielinski, W.

2007-03-01

Vaccum plasma sprayed tungsten coatings with an evaporated sandwich Re-W interlayer on graphite limiter blocks were studied after the experimental campaign in the TEXTOR tokamak. The coating morphology was modified by high-heat loads and co-deposition of species from the plasma. Co-deposits contained fuel species, carbon, boron and silicon. X-ray diffractometer phase analysis indicated the coexistence of metallic tungsten and its carbides (WC and W2C) and boride (W2B). In the Re-W layer the presence of carbon was detected in a several micrometres thick zone. In the overheated part of the limiter, the Re-W layer was transformed into a sigma phase.

Passivating overcoat bilayer for multilayer reflective coatings for extreme ultraviolet lithography

DOEpatents

Montcalm, Claude; Stearns, Daniel G.; Vernon, Stephen P.

1999-01-01

A passivating overcoat bilayer is used for multilayer reflective coatings for extreme ultraviolet (EUV) or soft x-ray applications to prevent oxidation and corrosion of the multilayer coating, thereby improving the EUV optical performance. The overcoat bilayer comprises a layer of silicon or beryllium underneath at least one top layer of an elemental or a compound material that resists oxidation and corrosion. Materials for the top layer include carbon, palladium, carbides, borides, nitrides, and oxides. The thicknesses of the two layers that make up the overcoat bilayer are optimized to produce the highest reflectance at the wavelength range of operation. Protective overcoat systems comprising three or more layers are also possible.

First principle study of UHTC ternary diboride, Cr2AlB2

NASA Astrophysics Data System (ADS)

Rastogi, Anugya; Rajpoot, Priyanka; Verma, U. P.

2018-04-01

In this paper ab-initio study of the structural, electronic and optical properties of ternary metal boride Cr2AlB2 using full potential linear augmented plane wave (FP-LAPW) method based on the density functional theory (DFT). The study of structural properties shows that Cr2AlB2 is metallic in nature and have orthorhombic crystal structure. The optical properties show that it possess anisotropic behavior, which have wide applications in electricity production through concentration of solar power (CSP) technology. To the best of our knowledge, theoretical study of the optical properties of Cr2AlB2 is reported for the first time.

High-Temperature Deformation and Strengthening Mechanisms of Titanium Boride/nickel Aluminide Composites

NASA Astrophysics Data System (ADS)

Wang, Liqin

Intermetallic matrix composites, with ceramic particle reinforcements, are among the most important candidates for high-temperature structural applications. These composites, however, are not always stronger than their matrix materials at elevated temperatures. Some of the composites have much better high-temperature strength than their matrix materials, such as NiAl and FeAl, while others are just the opposite, e.g. TiAl, Ti_3Al, and Ni_3Al. The reasons for either the strengthening or the weakening observed in the discontinuous aluminide matrix composites are not obvious. The purpose of this research is to understand the mechanisms which caused the increase of the strength achieved by adding TiB_2 particulates to NiAl, and to recognize the fundamental principles of the deformation process in TiB_2/NiAl composites. In order to accomplish this objective, the mechanical properties and thermal activation parameters of the deformation process in TiB_2/NiAl composites have been systematically evaluated. The microstructures, dislocation structures and the interface structures of TiB _2/NiAl composites have been also thoroughly characterized before and after the deformation. Emphasis is placed on the relationship between the microstructures and mechanical properties of TiB_2/NiAl composites.

Ground State Structures of Boron-Rich Rhodium Boride: An Ab Initio Study

NASA Astrophysics Data System (ADS)

Chu, Bin-Hua; Zhao, Yuan; Yan, Jin-Liang; Li, Da

2018-01-01

Not Available Supported by the Natural Science Foundation of Shandong Province under Grant Nos ZR2016AP02, ZR2016FM38 and ZR2016EMP01, the Innovation Project of Ludong University under Grant No LB2016013, the Open Project of State Key Laboratory of Superhard Materials of Jilin University under Grant No 201605, and the National Natural Science Foundation of China under Grant Nos 11704170 and 61705097.

Assessment of different sample preparation routes for mass spectrometric monitoring and imaging of lipids in bone cells via ToF-SIMS

PubMed Central

Schaepe, Kaija; Kokesch-Himmelreich, Julia; Rohnke, Marcus; Wagner, Alena-Svenja; Schaaf, Thimo; Wenisch, Sabine; Janek, Jürgen

2015-01-01

In ToF-SIMS analysis, the experimental outcome from cell experiments is to a great extent influenced by the sample preparation routine. In order to better judge this critical influence in the case of lipid analysis, a detailed comparison of different sample preparation routines is performed—aiming at an optimized preparation routine for systematic lipid imaging of cell cultures. For this purpose, human mesenchymal stem cells were analyzed: (a) as chemically fixed, (b) freeze-dried, and (c) frozen-hydrated. For chemical fixation, different fixatives, i.e., glutaraldehyde, paraformaldehyde, and a mixture of both, were tested with different postfixative handling procedures like storage in phosphate buffered saline, water or critical point drying. Furthermore, secondary lipid fixation via osmium tetroxide was taken into account and the effect of an ascending alcohol series with and without this secondary lipid fixation was evaluated. Concerning freeze-drying, three different postprocessing possibilities were examined. One can be considered as a pure cryofixation technique while the other two routes were based on chemical fixation. Cryofixation methods known from literature, i.e., freeze-fracturing and simple frozen-hydrated preparation, were also evaluated to complete the comparison of sample preparation techniques. Subsequent data evaluation of SIMS spectra in both, positive and negative, ion mode was performed via principal component analysis by use of peak sets representative for lipids. For freeze-fracturing, these experiments revealed poor reproducibility making this preparation route unsuitable for systematic investigations and statistic data evaluation. Freeze-drying after cryofixation showed improved reproducibility and well preserved lipid contents while the other freeze-drying procedures showed drawbacks in one of these criteria. In comparison, chemical fixation techniques via glutar- and/or paraformaldehyde proved most suitable in terms of reproducibility

Assessment of different sample preparation routes for mass spectrometric monitoring and imaging of lipids in bone cells via ToF-SIMS.

PubMed

Schaepe, Kaija; Kokesch-Himmelreich, Julia; Rohnke, Marcus; Wagner, Alena-Svenja; Schaaf, Thimo; Wenisch, Sabine; Janek, Jürgen

2015-03-19

In ToF-SIMS analysis, the experimental outcome from cell experiments is to a great extent influenced by the sample preparation routine. In order to better judge this critical influence in the case of lipid analysis, a detailed comparison of different sample preparation routines is performed-aiming at an optimized preparation routine for systematic lipid imaging of cell cultures. For this purpose, human mesenchymal stem cells were analyzed: (a) as chemically fixed, (b) freeze-dried, and (c) frozen-hydrated. For chemical fixation, different fixatives, i.e., glutaraldehyde, paraformaldehyde, and a mixture of both, were tested with different postfixative handling procedures like storage in phosphate buffered saline, water or critical point drying. Furthermore, secondary lipid fixation via osmium tetroxide was taken into account and the effect of an ascending alcohol series with and without this secondary lipid fixation was evaluated. Concerning freeze-drying, three different postprocessing possibilities were examined. One can be considered as a pure cryofixation technique while the other two routes were based on chemical fixation. Cryofixation methods known from literature, i.e., freeze-fracturing and simple frozen-hydrated preparation, were also evaluated to complete the comparison of sample preparation techniques. Subsequent data evaluation of SIMS spectra in both, positive and negative, ion mode was performed via principal component analysis by use of peak sets representative for lipids. For freeze-fracturing, these experiments revealed poor reproducibility making this preparation route unsuitable for systematic investigations and statistic data evaluation. Freeze-drying after cryofixation showed improved reproducibility and well preserved lipid contents while the other freeze-drying procedures showed drawbacks in one of these criteria. In comparison, chemical fixation techniques via glutar- and/or paraformaldehyde proved most suitable in terms of reproducibility

RESEARCH ON PHYSICAL AND CHEMICAL PRINCIPLES AFFECTING HIGH TEMPERATURE MATERIALS FOR ROCKET NOZZLES. Quarterly Progress Report, April 1, 1963-June 30, 1963

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lowrie, R.

1963-10-31

The development and properties of refractory materials are described. Corrosion of zirconium carbide, niobium carbide, and niobium carbide-zirconium carbide systems by carbon dioxide and hydrochloric acid at 2250 deg C is reported. Corrosion of silver-tungsten alloys by carbon dioxide and oxygen at 2150 to 2440 deg K is summarized. Measurements of pyrolytic and ZTA graphite corrosion by carbon dioxide and oxygen at 2100 to 2800 deg K are shown. At 2300 deg C the rate of formation of methane from graphite and hydrogen is greatly reduced by the addition of helium, at constant hydrogen pressure. Up to 2000 deg Cmore » the effect of helium is small. The pyrolysis of methane on graphite at 2000 deg C is tabulated. Oxidation of tungsten to form WO/sub 2/ and WO/sub 3/ is reported. Vaporization of hafnium borides at 2297 to 2538 deg K is analyzed. The lattice parameters of ZrB/sub 2/ at of TiN/sub 0.6/ and TiN/sub 0.75/ are discussed. Powder metallurgical techniques are used to prepare TiB/sub 2/, ZrB/sub 2/, HfB/ sub 2/, NbB/sub 2/, a nd TaB/sub 2/ for detailed x-ray characterization. The electric conductivity of NbC-ZrC systems is reported. General descriptions are given of analytical techniques for free carbon in carbides and spectrographic methods for metallic impurities in carbides and borides. Preliminary roomtemperature measurements are reported of the elastic properties of polycrystalline ZrB/sub 2/. Titanium carbide is brazed to tungsten with a platinum-boron system. A largegrained polycrystalline specimen of ZrC is plastically deformed in creep at 2134 deg C. Metallographic and x-ray examinations of polycrystalline TiC specimens deformed in creep reveal an increasing development with deformation of subgrains having preferred orientation. (N.W.R.)« less

Vittorio Marchi, MD (1851-1908): an unsung pioneer of neuroscience.

PubMed

Talamonti, Giuseppe; D'Aliberti, Giuseppe; Debernardi, Alberto; Innocenti, Gloria

2013-11-01

Vittorio Marchi was an Italian neuroscientist who lived during the second half of the 19th century. He is generally remembered for developing a novel staining method to trace the degeneration of nervous fibers in lesions of the central nervous system. This osmium-based method was used worldwide for approximately a century and continues to be cited in modern textbooks. Despite several important original scientific contributions, Marchi was never awarded a university chair. Discouraged, he left to practice neurology in a rural area but continued to write outstanding articles, and in 1897, he became a pioneer of meningioma surgery. Today, he is remembered only in specialized contexts. We hope this article can provide the recognition that Marchi deserves.

Nanocrystalline diamond micro-anvil grown on single crystal diamond as a generator of ultra-high pressures

DOE PAGES

Samudrala, Gopi K.; Moore, Samuel L.; Velisavljevic, Nenad; ...

2016-09-29

By combining mask-less lithography and chemical vapor deposition (CVD) techniques, a novel two-stage diamond anvil has been fabricated. A nanocrystalline diamond (NCD) micro-anvil 30 μm in diameter was grown at the center of a [100]-oriented, diamond anvil by utilizing microwave plasma CVD method. The NCD micro-anvil has a diamond grain size of 115 nm and micro-focused Raman and X-ray Photoelectron spectroscopy analysis indicate sp3-bonded diamond content of 72%. Lastly, these CVD grown NCD micro-anvils were tested in an opposed anvil configuration and the transition metals osmium and tungsten were compressed to high pressures of 264 GPa in a diamond anvilmore » cell.« less

[Ultrastructure of the digestive system in Dermatophagoides farinae (Acariformes:Pyroglyphidae)].

PubMed

Wang, Yue-Ming; Liu, Xiao-Yu; Jiang, Cong-Li; Huang, Li-Nian; Sun, Xin; Liu, Zhi-Gang

2013-12-01

Fifty living mites (Dermatophagoides farinae) were fixed in 2.5% glutaraldehyde, postfixed in 1% osmium tetroxide, dehydrated in a graded ethanol series, embedded in embedding medium. The ultrastructure of the digestive tract in D. farinae was observed by serial ultrathin sections with a transmission electron microscope. The alimentary canal of D. farinae consists of the cuticle-lined foregut and hindgut separated by a microvilli-lined midgut (anterior midgut, posterior midgut). There are different types of epithelial cells in the anterior midgut The microvilli of epithelial cells in posterior midgut are longer than that of the anterior midgut In posterior midgut, the food bolus is surrounded by the peritrophic membrane. The midgut is the main site of digestion and absorption.

Geochemical constraints on sustainable development: Can an advanced global economy achieve long-term stability?

NASA Astrophysics Data System (ADS)

Pickard, William F.

2008-04-01

The eighty-one stable chemical elements are examined individually with respect to (i) recent annual demand and (ii) worst case long-term availability in a distant future in which they must be extracted from the background sources of air, seawater, and ordinary rock. It is shown that, if a conventional use scenario is envisioned, the supplies of ruthenium, rhodium, palladium, tellurium, rhenium, osmium, iridium, platinum, gold, and especially phosphorus will be questionable while the supplies of copper, zinc, molybdenum, silver, cadmium, tin, antimony, tungsten, mercury, lead, and bismuth will be inadequate. It is therefore concluded that, in the long run, only the promotion of massive recycling and substitution technologies will suffice to maintain the global industrial society now developing.

The friction and wear properties of sputtered hard refractory compounds

NASA Technical Reports Server (NTRS)

Brainard, W. A.

1978-01-01

Several refractory silicide, boride, and carbide coatings were examined. The coatings were applied to type 440C steel surfaces by radio-frequency sputtering. The friction and wear properties of the coatings were found to be related to stoichiometry and impurity content of the bulk coating as well as the degree of interfacial adherence between coating and substrate. Bulk coating stoichiometry could to a large extent be controlled by the application of a negative bias voltage during deposition. Adherence was promoted by the formation of an oxidized layer at the interface. Deliberate preoxidizing of the 440C produced enhanced adherence for many compounds which are related to the formation of a mixed oxide transition region.

The effect of anti-phase domain size on the ductility of a rapidly solidified Ni3Al-Cr alloy

NASA Technical Reports Server (NTRS)

Carro, G.; Bertero, G. A.; Wittig, J. E.; Flanagan, W. F.

1989-01-01

Tensile tests on splat-quenched Ni3Al-Cr alloys showed a sharp decrease in ductility with long-time annealing. The growth of the initially very-fine-size anti-phase domains showed a tenuous correlation with ductility up to a critical size, where ductility was lost. The grain size was relatively unaffected by these annealing treatments, but the grain-boundary curvature decreased, implying less toughness. An important observation was that, for the longest annealing time, a chromium-rich precipitate formed, which the data indicate could be a boride. Miniaturized tensile tests were performed on samples which were all obtained from the same splat-quenched foil, and the various domain sizes were controlled by subsequent annealing treatments.

Assessment of the State of the Art of Ultra High Temperature Ceramics

NASA Technical Reports Server (NTRS)

Johnson, Sylvia; Gasch, Matt; Stackpoole, Mairead

2009-01-01

Ultra High Temperature Ceramics (UHTCs) are a family of materials that includes the borides, carbides and nitrides of hafnium-, zirconium- and titanium-based systems. UHTCs are famous for possessing some of the highest melting points of known materials. In addition, they are very hard, have good wear resistance, mechanical strength, and relatively high thermal conductivities (compared to other ceramic materials). Because of these attributes, UHTCs are ideal for thermal protection systems, especially those that require chemical and structural stability at extremely high operating temperatures. UHTCs have the potential to revolutionize the aerospace industry by enabling the development of sharp hypersonic vehicles or atmospheric entry probes capable of the most extreme entry conditions.

Materials for high-temperature thermoelectric conversion

NASA Technical Reports Server (NTRS)

Feigelson, R. S.; Elwell, D.

1983-01-01

High boron materials of high efficiency for thermoelectric power generation and capable of prolonged operation at temperatures over 1200 C are discussed. Background theoretical studies indicated that the low carrier mobility of materials with beta boron and related structures is probably associated with the high density of traps. Experimental work was mainly concerned with silicon borides in view of promising data from European laboratories. A systematic study using structure determination and lattice constant measurements failed to confirm the existence of an SiBn phase. Only SiB6 and a solid solution of silicon in beta boron with a maximum solid solubility of 5.5-6 at % at 1650 C were found.

Rhenium-osmium isotope and highly-siderophile-element abundance systematics of angrite meteorites

NASA Astrophysics Data System (ADS)

Riches, Amy J. V.; Day, James M. D.; Walker, Richard J.; Simonetti, Antonio; Liu, Yang; Neal, Clive R.; Taylor, Lawrence A.

2012-11-01

Coupled 187Os/188Os compositions and highly-siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, and Re) abundance data are reported for eight angrite achondrite meteorites that include quenched- and slowly-cooled textural types. These data are combined with new major- and trace-element concentrations determined for bulk-rock powder fractions and constituent mineral phases, to assess angrite petrogenesis. Angrite meteorites span a wide-range of HSE abundances from <0.005 ppb Os (e.g., Northwest Africa [NWA] 1296; Angra dos Reis) to >100 ppb Os (NWA 4931). Chondritic to supra-chondritic 187Os/188Os (0.1201-0.2127) measured for Angra dos Reis and quenched-angrites correspond to inter- and intra-sample heterogeneities in Re/Os and HSE abundances. Quenched-angrites have chondritic-relative rare-earth-element (REE) abundances at 10-15×CI-chondrite, and their Os-isotope and HSE abundance variations represent mixtures of pristine uncontaminated crustal materials that experienced addition (<0.8%) of exogenous chondritic materials during or after crystallization. Slowly-cooled angrites (NWA 4590 and NWA 4801) have fractionated REE-patterns, chondritic to sub-chondritic 187Os/188Os (0.1056-0.1195), as well as low-Re/Os (0.03-0.13), Pd/Os (0.071-0.946), and relatively low-Pt/Os (0.792-2.640). Sub-chondritic 187Os/188Os compositions in NWA 4590 and NWA 4801 are unusual amongst planetary basalts, and their HSE and REE characteristics may be linked to melting of mantle sources that witnessed prior basaltic melt depletion. Angrite HSE-Yb systematics suggest that the HSE behaved moderately-incompatibly during angrite magma crystallization, implying the presence of metal in the crystallizing assemblage. The new HSE abundance and 187Os/188Os compositions indicate that the silicate mantle of the angrite parent body(ies) (APB) had HSE abundances in chondritic-relative proportions but at variable abundances at the time of angrite crystallization. The HSE systematics of angrites are consistent with protracted post-core formation accretion of materials with chondritic-relative abundances of HSE to the APB, and these accreted materials were rapidly, yet inefficiently, mixed into angrite magma source regions early in Solar System history.

Osmium(VI) complexes as a new class of potential anti-cancer agents.

PubMed

Ni, Wen-Xiu; Man, Wai-Lun; Cheung, Myra Ting-Wai; Sun, Raymond Wai-Yin; Shu, Yuan-Lan; Lam, Yun-Wah; Che, Chi-Ming; Lau, Tai-Chu

2011-02-21

A nitridoosmium(VI) complex [Os(VI)(N)(sap)(OH(2))Cl] (H(2)sap = N-salicylidene-2-aminophenol) displays prominent in vitro and in vivo anti-cancer properties, induces S- and G2/M-phase arrest and forms a stable adduct with dianionic 5'-guanosine monophosphate.

Osmium isotopes suggest fast and efficient mixing in the oceanic upper mantle.

NASA Astrophysics Data System (ADS)

Bizimis, Michael; Salters, Vincent

2010-05-01

The depleted upper mantle (DUM; the source of MORB) is thought to represent the complementary reservoir of continental crust extraction. Previous studies have calculated the "average" DUM composition based on the geochemistry of MORB. However the Nd isotope compositions of abyssal peridotites have been shown to extend to more depleted compositions than associated MORB. While this argues for the presence of both relatively depleted and enriched material within the upper mantle, the extent of compositional variability, length scales of heterogeneity and timescales of mixing in the upper mantle are not well constrained. Model calculations show that 2Ga is a reasonable mean age of depletion for DUM while Hf - Nd isotopes show the persistence of a depleted terrestrial reservoir by the early Archean (3.5-3.8Ga). U/Pb zircon ages of crustal rocks show three distinct peaks at 1.2, 1.9, and 2.7Ga and these are thought to represent the ages of three major crustal growth events. A fundamental question therefore is whether the present day upper mantle retains a memory of multiple ancient depletion events, or has been effectively homogenized. This has important implications for the nature of convection and time scales of survival of heterogeneities in the upper mantle. Here we compare published Os isotope data from abyssal peridotites and ophiolitic Os-Ir alloys with new data from Hawaiian spinel peridotite xenoliths. The Re-Os isotope system has been shown to yield useful depletion age information in peridotites, so we use it here to investigate the distribution of Re-depletion ages (TRD) in these mantle samples as a proxy for the variability of DUM. The probability density functions (PDF) of TRD from osmiridiums, abyssal and Hawaiian peridotites are all remarkably similar and show a distinct peak at 1.2-1.3 Ga (errors for TRD are set at 0.2Ga to suppress statistically spurious age peaks). The Hawaiian peridotites further show a distinct peak at 1.9-2Ga, but no oceanic mantle samples with TRD older than 2Ga have been reported. The TRD age peaks overlap with two major crustal building events recorded in the U/Pb crustal zircon ages. Therefore, peridotites from the convecting upper mantle can retain some memory of ancient depletion events, and these depletions are perhaps linked to major crustal building or large-scale mantle melting events. In the case of the Hawaiian peridotites, an ancient depletion event is further supported by some extremely radiogenic Hf isotope compositions. However, the vast majority of oceanic mantle samples show a narrow rage of Os isotope compositions (187Os/188Os = 0.123-0.126) with TRDs at 300-600 Ma. If the upper mantle has been produced continuously (or episodically) since at least the early Archean, it is then surprising that almost all oceanic mantle samples record such young depletion ages. We suggest that convective mixing in the mantle is rigorous enough that effectively re-homogenizes and resets the Os isotope composition of previously depleted peridotites within short time scales (<500Ma). Similarly recent ages have been derived from modeling the Sr, Nd, Hf, Pb isotopic composition of MORBs. This resetting and homogenization can be due to re-equilibration of depleted mantle with enriched components, e.g. recycled basaltic crust or more fertile mantle. Ancient depletion events are only effectively preserved in the sublithospheric mantle samples (e.g. Kaapval, Slave, Wyoming cratons) because they remain isolated from the convective mantle.

Efficient white-light-emitting diodes based on poly(N-vinylcarbazole) doped with blue fluorescent and orange phosphorescent materials

NASA Astrophysics Data System (ADS)

Shih, Ping-I.; Shu, Ching-Fong; Tung, Yung-Liang; Chi, Yun

2006-06-01

We have fabricated polymer white-light-emitting devices possessing a single emitting layer containing a hole-transporting host polymer, poly(N-vinylcarbazole), and an electron-transporting auxiliary, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, doped with a blue-light-emitting amino-substituted distyrylarylene fluorescent dye and an orange-light-emitting osmium phosphor. The doubly doped device exhibited an intense white emission having Commission Internationale de l'Eclairage coordinates of (0.33, 0.34), a high external quantum efficiency of 6.12% (13.2cd/A), and a maximum brightness of 11306cd/m2. The color coordinates remained unchanged over a range of operating voltages, even at luminance as high as 1×104cd/m2.

SILVER IMPREGNATION OF ULTRATHIN SECTIONS FOR ELECTRON MICROSCOPY

PubMed Central

Marinozzi, Vittorio

1961-01-01

A new procedure is described for silver impregnation of thin sections for electron microscopy. Sections of various tissues, fixed in OsO4 and embedded in methacrylate, were treated with an ammoniacal silver solution, directly or after oxidation with periodic acid or hydrogen peroxide. After OsO4 fixation all cellular membranous systems exhibit a primary argentaffinity probably due to the reduction of ammoniacal silver solution by the reduced osmium bound to unsaturated lipids. Bleaching the sections with hydrogen peroxide removes the argentaffinity of protoplasmic structures. Treatment of the sections with periodic acid results in decreased argentaffinity of protoplasmic components while the argentaffinity of metaplasmic structures is greatly enhanced. The latter procedure appears particularly useful for enhancing the contrast of basement membranes. PMID:13766855

Systematic investigation of structural, electronic, optical and thermal properties of ternary MoAlB; an ab initio approach

NASA Astrophysics Data System (ADS)

Rajpoot, Priyanka; Rastogi, Anugya; Verma, U. P.

2018-02-01

Structural, electronic, optical and thermal properties of molybdenum aluminum boride (MoAlB) have been analyzed systematically using the full potential linearized augmented plane wave method based on density functional theory at ambient condition as well as high pressure and high temperature. Density of states and band structure calculation reflect the metallic character of MoAlB. In addition to this, the electron charge density calculation reveals the strong covalent bonding, in between ‘B’ atoms as well as ‘Mo’ and ‘B’ atoms. Optical parameters exhibit anisotropic nature and MoAlB become transparent in ultraviolet region for the radiation of energy above 25 eV. The thermal properties were investigated by using the quasi-harmonic Debye model at high temperature and high pressure.

Oxidation-induced contraction and strengthening of boron fibers

NASA Technical Reports Server (NTRS)

Dicarlo, J. A.; Wagner, T. C.

1981-01-01

An investigation was conducted to measure and understand the physical and mechanical effects that occur in boron fibers during and after thermal treatment in a controlled oxygen argon gaseous mixture. Of principal concern was the optimization of this treatment as a secondary processing method for significantly improving fiber tensile strength. Strengthening was accomplished by an oxidation induced axial contraction of the fiber and a resulting axial compression of strength limiting flaws within the fiber's tungsten boride core. Various physical observations were used to develop mechanistic models for oxidation, contraction, and flow formation. Processing guidelines are discussed for possibly exceeding the 5.5 GN/sq m strength limit and also for achieving fiber strengthening during application of boron containing diffusion barrier coatings.

Characterization and Computational Modeling of Minor Phases in Alloy LSHR

NASA Technical Reports Server (NTRS)

Jou, Herng-Jeng; Olson, Gregory; Gabb, Timothy; Garg, Anita; Miller, Derek

2012-01-01

The minor phases of powder metallurgy disk superalloy LSHR were studied. Samples were consistently heat treated at three different temperatures for long times to approach equilibrium. Additional heat treatments were also performed for shorter times, to assess minor phase kinetics in non-equilibrium conditions. Minor phases including MC carbides, M23C6 carbides, M3B2 borides, and sigma were identified. Their average sizes and total area fractions were determined. CALPHAD thermodynamics databases and PrecipiCalc(TradeMark), a computational precipitation modeling tool, were employed with Ni-base thermodynamics and diffusion databases to model and simulate the phase microstructural evolution observed in the experiments with an objective to identify the model limitations and the directions of model enhancement.

High-Entropy Metal Diborides: A New Class of High-Entropy Materials and a New Type of Ultrahigh Temperature Ceramics

NASA Astrophysics Data System (ADS)

Gild, Joshua; Zhang, Yuanyao; Harrington, Tyler; Jiang, Sicong; Hu, Tao; Quinn, Matthew C.; Mellor, William M.; Zhou, Naixie; Vecchio, Kenneth; Luo, Jian

2016-11-01

Seven equimolar, five-component, metal diborides were fabricated via high-energy ball milling and spark plasma sintering. Six of them, including (Hf0.2Zr0.2Ta0.2Nb0.2Ti0.2)B2, (Hf0.2Zr0.2Ta0.2Mo0.2Ti0.2)B2, (Hf0.2Zr0.2Mo0.2Nb0.2Ti0.2)B2, (Hf0.2Mo0.2Ta0.2Nb0.2Ti0.2)B2, (Mo0.2Zr0.2Ta0.2Nb0.2Ti0.2)B2, and (Hf0.2Zr0.2Ta0.2Cr0.2Ti0.2)B2, possess virtually one solid-solution boride phase of the hexagonal AlB2 structure. Revised Hume-Rothery size-difference factors are used to rationalize the formation of high-entropy solid solutions in these metal diborides. Greater than 92% of the theoretical densities have been generally achieved with largely uniform compositions from nanoscale to microscale. Aberration-corrected scanning transmission electron microscopy (AC STEM), with high-angle annular dark-field and annular bright-field (HAADF and ABF) imaging and nanoscale compositional mapping, has been conducted to confirm the formation of 2-D high-entropy metal layers, separated by rigid 2-D boron nets, without any detectable layered segregation along the c-axis. These materials represent a new type of ultra-high temperature ceramics (UHTCs) as well as a new class of high-entropy materials, which not only exemplify the first high-entropy non-oxide ceramics (borides) fabricated but also possess a unique non-cubic (hexagonal) and layered (quasi-2D) high-entropy crystal structure that markedly differs from all those reported in prior studies. Initial property assessments show that both the hardness and the oxidation resistance of these high-entropy metal diborides are generally higher/better than the average performances of five individual metal diborides made by identical fabrication processing.

Photo-electrochemical communication between cyanobacteria (Leptolyngbia sp.) and osmium redox polymer modified electrodes.

PubMed

Hasan, Kamrul; Bekir Yildiz, Huseyin; Sperling, Eva; Conghaile, Peter Ó; Packer, Michael A; Leech, Dónal; Hägerhäll, Cecilia; Gorton, Lo

2014-12-07

Photosynthetic microbial fuel cells (PMFCs) are an emerging technology for renewable solar energy conversion. Major efforts have been made to explore the electrogenic activity of cyanobacteria, mostly using practically unsustainable reagents. Here we report on photocurrent generation (≈8.64 μA cm(-2)) from cyanobacteria immobilized on electrodes modified with an efficient electron mediator, an Os(2+/3+) redox polymer. Upon addition of ferricyanide to the electrolyte, cyanobacteria generate the maximum current density of ≈48.2 μA cm(-2).

New osmium isotope evidence for intracrustal recycling of crustal domains with discrete ages

USGS Publications Warehouse

Hart, G.L.; Johnson, C.M.; Hildreth, W.; Shirey, S.B.

2003-01-01

New 187Os/188Os ratios of Quaternary Mount Adams volcanic rocks from the Cascade arc in southern Washington vary by >300% (187Os/188Os = 0.165-0.564) and fall into high (>0.319) and low (0.166 to 0.281) groups of 187Os/188Os ratios that are substantially more radiogenic than mantle values. These Os isotope compositions and groupings are interpreted to reflect recycling of discrete intracrustal domains with high 187Os/188Os ratios but differing ages, thus recording the process of crustal hybridization and homogenization. Os isotope compositions provide new constraints on amounts of intracrustal recycling in young subduction-zone environments that reflect the magmatic history of the arc. Sr, Nd, Hf, and Pb isotope variations in this young, mafic are complex are too small to allow such constraints.

Osmium Isotope and Highly Siderophile Element Compositions of Lunar Orange and Green Glasses

NASA Technical Reports Server (NTRS)

Walker, R. J.; Horan, M. F.; Shearer, C. K.; Papike, J. J.

2003-01-01

The absolute and relative abundances of the highly siderophile elements (HSE) present in planetary mantles are primarily controlled by: 1) silicate-metal partitioning during core-mantle differentiation, 2) the subsequent addition of HSE to mantles via continued planetary accretion. Consequently, constraints on the absolute and relative abundances of the HSE in the lunar mantle will provide unique insights to the formation and late accretionary history of not only the Moon, but also Earth. Determining the HSE content of the lunar mantle, however, has proven difficult, because no bona fide mantle rocks have been collected from the moon. The only materials presently available for constraining mantle abundances are lunar volcanic rocks. Lunar basalts typically have very low concentrations of HSE and highly fractionated HSE patterns. Because of our extremely limited understanding of mantle melt partitioning of the HSE, even for terrestrial systems, extrapolations to mantle compositions from basaltic compositions are difficult, except possibly for the less compatible HSE Pt and Pd. Primitive, presumably less fractionated materials, such as picritic glasses are potentially more diagnostic of the lunar interior. Here we report Os isotopic composition data and Re, Os, Ir, Ru, Pt and Pd concentration data for green glass (15426,164) and orange glass (74001,1217). As with previous studies utilizing neutron activation analysis, we are examining different size fractions of the spherules to assess the role of surface condensation in the generation of the HSE abundances.

Suppression of radiation-induced point defects by rhenium and osmium interstitials in tungsten

PubMed Central

Suzudo, Tomoaki; Hasegawa, Akira

2016-01-01

Modeling the evolution of radiation-induced defects is important for finding radiation-resistant materials, which would be greatly appreciated in nuclear applications. We apply the density functional theory combined with comprehensive analyses of massive experimental database to indicate a mechanism to mitigate the effect of radiation on W crystals by adding particular solute elements that change the migration property of interstitials. The resultant mechanism is applicable to any body-centered-cubic (BCC) metals whose self-interstitial atoms become a stable crowdion and is expected to provide a general guideline for computational design of radiation-resistant alloys in the field of nuclear applications. PMID:27824134

Potential bile acid metabolites. XV. Synthesis of 4 beta-hydroxylated bile acids; unique bile acids in human fetal bile.

PubMed

Iida, T; Momose, T; Chang, F C; Goto, J; Nambara, T

1989-12-01

The 4 beta-hydroxylated derivatives of lithocholic, deoxycholic, chenodeoxycholic, and cholic acids were synthesized from their respective parent compounds. The principal reactions employed were 1) beta-face cis-dihydroxylation of delta 3 intermediates with osmium tetroxide-N-methylmorpholine N-oxide, 2) selective cathylation of vicinal 3 beta,4 beta-diols followed by oxidation of the resulting 4 beta-monocathylates, or direct selective oxidation at C-3 of 3 beta,4 beta-diols with pyridinium chlorochromate, and 3) stereoselective reduction of the 3-oxo compounds with tert-butylamine-borane complex. The results of analysis of the prepared 4 beta-hydroxylated bile acids with a diequatorial trans-glycol structure and their 3 beta-epimers by proton and carbon-13 nuclear magnetic resonance spectroscopies are briefly discussed along with the mass spectrometric properties.

Cretaceous-Tertiary findings, paradigms and problems

NASA Technical Reports Server (NTRS)

Officer, C. B.; Drake, C. L.

1988-01-01

The asteroid hypothesis has stimulated numerous studies of the paleontological record at Cretaceous/Tertiary time as well as of geological indicators of environmental crisis preserved in the rock record. Both extinctions and geological anomalies often occur at times that do not appear to be synchronous or instantaneous. The record includes paleontological indicators of dinosaurs, terrestrial flora, marine planktonic organisms, and shallow water marine macrofauna and geological phenomena include occurrences of iridium and other platinum metals, trace elements, clay mineralogy, shocked minerals, soot, microspherules, and isotopes of osmium, strontium and carbon. These findings are reviewed in the context of the alternate hypotheses of an exogenic cause, involving either a single asteroid impact or multiple commentary impacts, and an endogenic cause, involving intense global volcanism and major sea level regression.

Staining Methods for Normal and Regenerative Myelin in the Nervous System.

PubMed

Carriel, Víctor; Campos, Antonio; Alaminos, Miguel; Raimondo, Stefania; Geuna, Stefano

2017-01-01

Histochemical techniques enable the specific identification of myelin by light microscopy. Here we describe three histochemical methods for the staining of myelin suitable for formalin-fixed and paraffin-embedded materials. The first method is conventional luxol fast blue (LFB) method which stains myelin in blue and Nissl bodies and mast cells in purple. The second method is a LBF-based method called MCOLL, which specifically stains the myelin as well the collagen fibers and cells, giving an integrated overview of the histology and myelin content of the tissue. Finally, we describe the osmium tetroxide method, which consist in the osmication of previously fixed tissues. Osmication is performed prior the embedding of tissues in paraffin giving a permanent positive reaction for myelin as well as other lipids present in the tissue.

Two phase titanium aluminide alloy

DOEpatents

Deevi, Seetharama C.; Liu, C. T.

2001-01-01

A two-phase titanic aluminide alloy having a lamellar microstructure with little intercolony structures. The alloy can include fine particles such as boride particles at colony boundaries and/or grain boundary equiaxed structures. The alloy can include alloying additions such as .ltoreq.10 at % W, Nb and/or Mo. The alloy can be free of Cr, V, Mn, Cu and/or Ni and can include, in atomic %, 45 to 55% Ti, 40 to 50% Al, 1 to 5% Nb, 0.3 to 2% W, up to 1% Mo and 0.1 to 0.3% B. In weight %, the alloy can include 57 to 60% Ti, 30 to 32% Al, 4 to 9% Nb, up to 2% Mo, 2 to 8% W and 0.02 to 0.08% B.

High-pressure, high-temperature synthesis of superhard boron suboxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hubert, H.; Garvie, L.A.J.; Leinenweber, K.

A multianvil device was used to investigate the formation of B{sub x}O phases produced in the 2 to 10 GPa pressure range with temperatures between 1,000 and 1,800 C. Amorphous and crystalline B and BP were oxidized using B{sub 2}O{sub 3} and CrO{sub 3}. Using powder X-ray diffraction and parallel electron energy-loss spectroscopy (PEELS), the authors were unable to detect graphitic or diamond-structured B{sub 2}O, reported in previous studies. The refractory boride B{sub 6}O, which has the {alpha}-rhombohedral boron structure, is the dominant suboxide in the P and T range of the investigation. PEELS with a transmission electron microscope wasmore » used to characterize the boron oxides.« less

Oxidation-induced contraction and strengthening of boron fibers

NASA Technical Reports Server (NTRS)

Dicarlo, J. A.; Wagner, T. C.

1981-01-01

An investigation of the physical and mechanical effects of thermal treatment in a controlled oxygen-argon atmosphere on boron fibers is reported, with attention to the optimization of such treatment as a secondary processing method for improvement of fiber strength. The strengthening mechanism is comprised of an oxidation-induced axial contraction of the fiber, accompanied by axial compression of strength-limiting flaws within the fiber's tungsten boride core. It was found that after an oxidation contraction of 0.3% near 900 C, and a slight surface etch near 100 C, the average tensile strength of 203-micron fibers increased from 500 to 800 ksi. Various physical observations are used to develop mechanistic models of oxidation, contraction, and the formation of new flaws in the boron sheath at contractions greater than 0.3%.

Direct synthesis of calcium borohydride

DOEpatents

Ronnebro, Ewa Carin Ellinor [Dublin, CA; Majzoub, Eric H [Pleasanton, CA

2009-10-27

A method is disclosed for directly preparing an alkaline earth metal borohydride, i.e. Ca(BH.sub.4).sub.2, from the alkaline earth metal hydride and the alkaline earth metal boride. The borohydride thus prepared is doped with a small portion of a metal chloride catalyst compound, such as RuCl.sub.3, TiCl.sub.3, or a mixture of TiCl.sub.3 and palladium metal. The process provides for mechanically mixing the dry reagents under an inert atmosphere followed by charging the mixed materials with high pressure hydrogen at about 70 MPa while heating the mixture to about 400.degree. C. The method is relatively simple and inexpensive and provides reversible hydride compounds which are free of the usual contamination introduced by prior art wet chemical methods.

Preparation of actinide boride materials via solid-state metathesis reactions and actinide dicarbollide precursors

NASA Astrophysics Data System (ADS)

Lupinetti, Anthony J.; Fife, Julie; Garcia, Eduardo; Abney, Kent D.

2000-07-01

Information gaps exist in the knowledge base needed for choosing among the alternate processes to be used in the safe conversion of fissile materials to optimal forms for safe interim storage, long-term storage, and ultimate disposition. The current baseline storage technology for various wastes uses borosilicate glasses.1 The focus of this paper is the synthesis of actinide-containing ceramic materials at low and moderate temperatures (200 °C-1000 °C) using molecular and polymeric actinide borane and carborane complexes.

Subcellular localization of pituitary enzymes

NASA Technical Reports Server (NTRS)

Smith, R. E.

1970-01-01

A cytochemical procedure is reported for identifying subcellular sites of enzymes hydrolyzing beta-naphthylamine substrates, and to study the sites of reaction product localization in cells of various tissues. Investigations using the substrate Leu 4-methoxy-8-naphthylamine, a capture with hexonium pararosaniline, and the final chelation of osmium have identified the hydrolyzing enzyme of rat liver cells; this enzyme localized on cell membranes with intense deposition in the areas of the parcanaliculi. The study of cells in the anterior pituitary of the rat showed the deposition of reaction product on cell membrane; and on the membranes of secretion granules contained within the cell. The deposition of reaction product on the cell membrane however showed no increase or decrease with changes in the physiological state of the gland and release of secretion granules from specific cells.

Thermal decomposition of ammonium hexachloroosmate.

PubMed

Asanova, T I; Kantor, I; Asanov, I P; Korenev, S V; Yusenko, K V

2016-12-07

Structural changes of (NH 4 ) 2 [OsCl 6 ] occurring during thermal decomposition in a reduction atmosphere have been studied in situ using combined energy-dispersive X-ray absorption spectroscopy (ED-XAFS) and powder X-ray diffraction (PXRD). According to PXRD, (NH 4 ) 2 [OsCl 6 ] transforms directly to metallic Os without the formation of any crystalline intermediates but through a plateau where no reactions occur. XANES and EXAFS data by means of Multivariate Curve Resolution (MCR) analysis show that thermal decomposition occurs with the formation of an amorphous intermediate {OsCl 4 } x with a possible polymeric structure. Being revealed for the first time the intermediate was subjected to determine the local atomic structure around osmium. The thermal decomposition of hexachloroosmate is much more complex and occurs within a minimum two-step process, which has never been observed before.

Correlation between microstructure and thermionic electron emission from Os-Ru thin films on dispenser cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swartzentruber, Phillip D.; John Balk, Thomas, E-mail: john.balk@uky.edu; Effgen, Michael P.

2014-07-01

Osmium-ruthenium films with different microstructures were deposited onto dispenser cathodes and subjected to 1000 h of close-spaced diode testing. Tailored microstructures were achieved by applying substrate biasing during deposition, and these were evaluated with scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray spectroscopy before and after close-spaced diode testing. Knee temperatures determined from the close-spaced diode test data were used to evaluate cathode performance. Cathodes with a large (10-11) Os-Ru film texture possessed comparatively low knee temperatures. Furthermore, a low knee temperature correlated with a low effective work function as calculated from the close-spaced diode data. It is proposedmore » that the formation of strong (10-11) texture is responsible for the superior performance of the cathode with a multilayered Os-Ru coating.« less

Improved materials and processes of dispenser cathodes

NASA Astrophysics Data System (ADS)

Longo, R. T.; Sundquist, W. F.; Adler, E. A.

1984-08-01

Several process variables affecting the final electron emission properties of impregnated dispenser cathodes were investigated. In particular, the influence of billet porosity, impregnant composition and purity, and osmium-ruthenium coating were studied. Work function and cathode evaporation data were used to evaluate cathode performance and to formulate a model of cathode activation and emission. Results showed that sorted tungsten powder can be reproducibly fabricated into cathode billets. Billet porosity was observed to have the least effect on cathode performance. Use of the 4:1:1 aluminate mixture resulted in lower work functions than did use of the 5:3:2 mixture. Under similar drawout conditions, the coated cathodes showed superior emission relative to uncoated cathodes. In actual Pierce gun structures under accelerated life test, the influence of impregnated sulfur is clearly shown to reduce cathode performance.

The use of moments of momentum to account for crystal habits

NASA Technical Reports Server (NTRS)

Barber, P. G.

1985-01-01

A three-step theory of crystal growth is proposed which involves first an association of molecules or ions in solution to form an impinging growth unit, then second the orientation of this unit prior to its impact on the surface of a crystal, and finally the attachment of this unit to the crystal face. From this theory the habit of a crystal is dependent upon the moments of momentum of the impinging growth unit. The results of sample calculations are presented or sodium chloride, succinic acid, sucrose, and chromium boride. The faces predicted by this proposed theory are compared with those predicted by other, energy-based calculations and with those experimentally observed. The proposed theory suggests alternative strategies for crystallization and habit modification which may be of technological importance. Listings of the two computer programs that were used are provided.

Impact of B 4C co-sputtering on structure and optical performance of Cr/Sc multilayer X-ray mirrors

DOE PAGES

Ghafoor, Naureen; Eriksson, Fredrik; Aquila, Andrew; ...

2017-01-01

We investigate the influence of B 4C incorporation during magnetron sputter deposition of Cr/Sc multilayers intended for soft X-ray reflective optics. Chemical analysis suggests formation of metal: boride and carbide bonds which stabilize an amorphous layer structure, resulting in smoother interfaces and an increased reflectivity. A near-normal incidence reflectivity of 11.7%, corresponding to a 67% increase, is achieved at λ = 3.11 nm upon adding 23 at.% (B + C). The advantage is significant for the multilayer periods larger than 1.8 nm, where amorphization results in smaller interface widths, for example, giving 36% reflectance and 99.89% degree of polarization nearmore » Brewster angle for a multilayer polarizer. The modulated ion-energy-assistance during the growth is considered vital to avoid intermixing during the interface formation even when B + C are added.« less

Review of Thermal Spray Coating Applications in the Steel Industry: Part 2—Zinc Pot Hardware in the Continuous Galvanizing Line

NASA Astrophysics Data System (ADS)

Matthews, S.; James, B.

2010-12-01

This two-part article series reviews the application of thermal spray coating technology in the production of steel and steel sheet products. Part 2 of this article series is dedicated to coating solutions in the continuous galvanizing line. The corrosion mechanisms of Fe- and Co-based bulk materials are briefly reviewed as a basis for the development of thermal spray coating solutions. WC-Co thermal spray coatings are commonly applied to low Al-content galvanizing hardware due to their superior corrosion resistance compared to Fe and Co alloys. The effect of phase degradation, carbon content, and WC grain size are discussed. At high Al concentrations, the properties of WC-Co coatings degrade significantly, leading to the application of oxide-based coatings and corrosion-resistant boride containing coatings. The latest results of testing are summarized, highlighting the critical coating parameters.

Microstructural observations in rapidly-solidified and heat-treated Ni3Al-Cr alloys

NASA Technical Reports Server (NTRS)

Carro, G.; Flanagan, W. F.

1992-01-01

The microstructural development following heat treatments of several rapidly-solidified Ni3Al-Cr and Ni3Al-Cr-B alloys is presented. Depending on composition, the as-solidified samples were either 100 percent gamma-prime phase - in the form of fine antiphase domains (APD) - or a mixture of gamma-prime (APDs) and beta phases. Upon annealing, the as-solidified microstructures transform to either APD-free gamma-prime or mixtures of gamma and gamma-prime phases. For those compositions where the quenched microstructures were 100 percent gamma-prime it was observed that APD coarsening followed conventional grain-growth kinetics, but when gamma phase precipitated on the APD boundaries the rate constant changed abruptly while the time exponent remained unaffected. It was also found that alloys containing critical amounts of chromium and boron are susceptible to precipitation of the boride Cr5B3.

Superconductivity between standard types: Multiband versus single-band materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vagov, A.; Shanenko, A. A.; Milošević, M. V.

In the nearest vicinity of the critical temperature, types I and II of conventional single-band superconductors interchange at the Ginzburg-Landau parameter κ = 1/√2. At lower temperatures this point unfolds into a narrow but finite interval of κ’s, shaping an intertype (transitional) domain in the (κ,T ) plane. In the present work, based on the extended Ginzburg-Landau formalism, we show that the same picture of the two standard types with the transitional domain in between applies also to multiband superconductors. However, the intertype domain notably widens in the presence of multiple bands and can become extremely large when the systemmore » has a significant disparity between the band parameters. It is concluded that many multiband superconductors, such as recently discovered borides and iron-based materials, can belong to the intertype regime.« less

Liner for extrusion billet containers. Interim Technical Documentary Progress Report, February 1--April 30, 1963

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spachner, S. A.

1963-05-01

A shrink-fit assembly device for buildup of ceramiccoated liner and sleeve assemblies was tested and modified to develop desired temperatures and suitable heat distribution in sleeves, which were heated. Nine different compositions of fiber metal reinforced ceramic compacts were produced for preliminary evaluation of suitability for extrusion liner use. Procedures were developed for welding short, hollow ceramic cylinders of high-strength metal carbides and borides to form a ceramic extrusion liner of suitable length. Dissassembly tooling for rapid separation of shrink-fitted sleeves from a worn liner was designed, fabricated, and tested. Preliminary extrusion testing of an alumina-coated liner was carried out,more » using SAE 4340 steel billets extruded to rod at 12 : 1 and 16 : 1 ratios. No coating wear was noted after extrusion of 3 billets. (auth)« less

NASA research on refractory compounds.

NASA Technical Reports Server (NTRS)

Gangler, J. J.

1971-01-01

The behavior and properties of the refractory carbides, nitrides, and borides are being investigated by NASA as part of its research aimed at developing superior heat resistant materials for aerospace applications. Fundamental studies on the electronic and defect structures of the carbides indicate that there is promise for improving the strength and ductility of these materials. Studies of the zirconium-carbon-oxygen system show that zirconium oxycarbides of different compositions and lattice parameters can be formed between 1500 and 1900 C and are stable below 1500 C. More applied studies show that hot working generally improves the microstructure and therefore the strength of TiC and NbC. Sintering studies on UN indicate that very high densities can be achieved. Hot pressing of cermets of HfN and HfC produces good mechanical properties for high temperature bearing applications.

Longitudinal residual stresses in boron fibers

NASA Technical Reports Server (NTRS)

Behrendt, D. R.

1976-01-01

A method of measuring the longitudinal residual stress distribution in boron fibers is presented. The residual stresses in commercial CVD boron on tungsten fibers of 102, 142, and 203 microns (4, 5.6, and 8 mil) diameters were determined. Results for the three sizes show a compressive stress at the surface 800 to -1400 MN/sq m 120 to -200 ksi), changing monotonically to a region of tensile stress within the boron. At approximately 25 percent of the original radius, the stress reaches a maximum tensile 600 to 1000 MN/sq m(90 to 150 ksi) and then decreases to compressive near the tungsten boride core. The core itself is under a compressive stress of approximately -1300 MN/sq m (-190 ksi). The effects of surface removal on core residual stress and core-initiated fracture are discussed.

Impact of B 4C co-sputtering on structure and optical performance of Cr/Sc multilayer X-ray mirrors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghafoor, Naureen; Eriksson, Fredrik; Aquila, Andrew

We investigate the influence of B 4C incorporation during magnetron sputter deposition of Cr/Sc multilayers intended for soft X-ray reflective optics. Chemical analysis suggests formation of metal: boride and carbide bonds which stabilize an amorphous layer structure, resulting in smoother interfaces and an increased reflectivity. A near-normal incidence reflectivity of 11.7%, corresponding to a 67% increase, is achieved at λ = 3.11 nm upon adding 23 at.% (B + C). The advantage is significant for the multilayer periods larger than 1.8 nm, where amorphization results in smaller interface widths, for example, giving 36% reflectance and 99.89% degree of polarization nearmore » Brewster angle for a multilayer polarizer. The modulated ion-energy-assistance during the growth is considered vital to avoid intermixing during the interface formation even when B + C are added.« less

Formation of Minor Phases in a Nickel-Based Disk Superalloy

NASA Technical Reports Server (NTRS)

Gabb, T. P.; Garg, A.; Miller, D. R.; Sudbrack, C. K.; Hull, D. R.; Johnson, D.; Rogers, R. B.; Gayda, J.; Semiatin, S. L.

2012-01-01

The minor phases of powder metallurgy disk superalloy LSHR were studied. Samples were consistently heat treated at three different temperatures for long times to approximate equilibrium. Additional heat treatments were also performed for shorter times, to then assess non-equilibrium conditions. Minor phases including MC carbides, M23C6 carbides, M3B2 borides, and sigma were identified. Their transformation temperatures, lattice parameters, compositions, average sizes and total area fractions were determined, and compared to estimates of an existing phase prediction software package. Parameters measured at equilibrium sometimes agreed reasonably well with software model estimates, with potential for further improvements. Results for shorter times representing non-equilibrium indicated significant potential for further extension of the software to such conditions, which are more commonly observed during heat treatments and service at high temperatures for disk applications.

Development and Characterization of Titanium Compound N anostructures

NASA Astrophysics Data System (ADS)

Zhou, Zhou

The development and characterization of titanium compound nanostructures have been achieved, for potential applications in energy industry. Oil and gas, one of the traditional industry fields, observes accumulating demands on active implementations of nanotechnology, for the numerous advantages that nanomaterials can introduce to both product performances and field operations. By using chemical vapor deposition and liquid exfoliation, various titanium compound nanostructures have been synthesized through this project. Attractively, these two material fabrication methods have been recognized to be industrial friendly in terms of cost efficiency and productivity. The development of nanostructures, aiming at oil and gas field applications, presents novel solutions for existing issues, such as low durability of drilling tools, high friction in mechanical operations and ineffective heat dissipation. Titanium compound nanostructures, including titanium borides, nitrides and sulfides are therefore investigated for such applications as protective coating, lubrication and thermal management.

Ruthenium and osmium complexes that bear functional azolate chelates for dye-sensitized solar cells.

PubMed

Chi, Yun; Wu, Kuan-Lin; Wei, Tzu-Chien

2015-05-01

The preparation of sensitizers for dye-sensitized solar cells (DSSCs) represents an active area of research for both sustainability and renewable energy. Both Ru(II) and Os(II) metal sensitizers offer unique photophysical and electrochemical properties that arise from the intrinsic electronic properties, that is, the higher propensity to form the lower-energy metal-to-ligand charge-transfer (MLCT) transition, and their capability to support chelates with multiple carboxy groups, which serve as a bridge to the metal oxide and enable efficient injection of the photoelectron. Here we present an overview of the synthesis and testing of these metal sensitizers that bear functional azolate chelates (both pyrazolate and triazolate), which are capable of modifying the metal sensitizers in a systematic and beneficial manner. Basic principles of the molecular designs, the structural relationship to the photophysical and electrochemical properties, and performances of the as-fabricated DSSCs are highlighted. The success in the breakthrough of the synthetic protocols and potential applications might provide strong stimulus for the future development of technologies such as DSSCs, organic light-emitting diodes, solar water splitting, and so forth. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhenium-osmium isotope systematics in meteorites I: Magmatic iron meteorite groups IIAB and IIIAB

USGS Publications Warehouse

Morgan, J.W.; Walker, R.J.; Grossman, J.N.

1992-01-01

Using resonance ionization mass spectrometry (RIMS), Re and Os abundances were determined by isotope dilution (ID) and 187Os 186Os ratios measured in nineteen iron meteorites: eight from group IIAB, ten from group IIIAB, and Treysa (IIIB anomalous). Abundances range from 1.4 to 4800 ppb Re, and from 13 to 65000 ppb Os, and generally agree well with previous ID and neutron activation (NAA) results. The Re and Os data suggest that abundance trends in these iron groups may be entirely explained by fractional crystallization. Addition of late-formed metal to produce ReOs variation in the B subgroups is not essential but cannot be excluded. Whole-rock isochrons for the IIAB and IIIAB groups are statistically indistinguishable. Pooled data yield an initial 187Os 186Os of 0.794 ?? 0.010, with a slope of (7.92 ?? 0.20) ?? 10-2 corresponding to a magmatic iron meteorite age of 4.65 ?? 0.11 Ga (using a decay constant of 1.64 ?? 10-11 a-1). Given the errors in the slope and half life, this age does not differ significantly from the canonical chondrite age of 4.56 Ga, but could be as young as 4.46 Ga. ?? 1992.

Osmium Stable Isotope Composition of Chondrites and Iron Meteorites: Implications for Planetary Core Formation

NASA Astrophysics Data System (ADS)

Nanne, J. A. M.; Millet, M. A.; Burton, K. W.; Dale, C. W.; Nowell, G. M.; Williams, H. M.

2016-12-01

Mass-dependent Os stable isotope fractionation is expected to occur during metal-silicate segregation as well as during crystallization of metal alloys due to the different bonding environment between silicate and metals. As such, Os stable isotopes have the potential to resolve questions pertaining to planetary accretion and differentiation. Here, we present stable Os isotope data for a set of chondrites and iron meteorites to examine the processes associated with core solidification. Carbonaceous, ordinary, and enstatite chondrites show no detectable stable isotope variation with a δ190Os weighted average of +0.12±0.04 (n=37). The uniform composition observed for chondrites implies Os stable isotope homogeneity of the bulk solar nebula. Contrary to chondrites, iron meteorites display a large range in Os stable isotope compositions from δ190Os of +0.05 up to +0.49‰. Variation is only observed in the IIAB and IIIAB irons. Type IVB irons display values similar to chondrites (+0.107±0.047 [n=3]) and IVA compositions are slightly different +0.187±0.004 (n=2). The type IIAB and IIIAB groups show values both within the chondritic range and up to heavier values extending up to +0.49‰. Since core formation in small planetary bodies is expected to quantitatively sequester Os in metal phases, bulk planetary cores are expected to display chondritic δ190Os values. Conversely, samples of the IIAB and IIIAB group display significant variation, possibly indicating that stable isotope fractionation occurred during solidification of the parent-body core. However, no covariation is observed between δ190Os and either Os abundance or radiogenic Os isotope ratios. Instead, liquid immiscibility during core crystallization, where the liquid metal splits into separate S- and P-rich liquids, may be a source of Os stable isotope fractionation.

A model for osmium isotopic evolution of metallic solids at the core-mantle boundary

NASA Astrophysics Data System (ADS)

Humayun, Munir

2011-03-01

Some plumes are thought to originate at the core-mantle boundary, but geochemical evidence of core-mantle interaction is limited to Os isotopes in samples from Hawaii, Gorgona (89 Ma), and Kostomuksha (2.7 Ga). The Os isotopes have been explained by physical entrainment of Earth's liquid outer core into mantle plumes. This model has come into conflict with geophysical estimates of the timing of core formation, high-pressure experimental determinations of the solid metal-liquid metal partition coefficients (D), and the absence of expected 182W anomalies. A new model is proposed where metallic liquid from the outer core is partially trapped in a compacting cumulate pile of Fe-rich nonmetallic precipitates (FeO, FeS, Fe3Si, etc.) at the top of the core and undergoes fractional crystallization precipitating solid metal grains, followed by expulsion of the residual metallic liquid back to the outer core. The Os isotopic composition of the solids and liquids in the cumulate pile is modeled as a function of the residual liquid remaining and the emplacement age using 1 bar D values, with variable amounts of oxygen (0-10 wt %) as the light element. The precipitated solids evolve Os isotope compositions that match the trends for Hawaii (at an emplacement age of 3.5-4.5 Ga; 5%-10% oxygen) and Gorgona (emplacement age < 1.5 Ga; 0%-5% oxygen). The Fe-rich matrix of the cumulate pile dilutes the precipitated solid metal decoupling the Fe/Mn ratio from Os and W isotopes. The advantages to using precipitated solid metal as the Os host include a lower platinum group element and Ni content to the mantle source region relative to excess iron, miniscule anomalies in 182W (<0.1 ɛ), and no effects for Pb isotopes, etc. A gradual thermomechanical erosion of the cumulate pile results in incorporation of this material into the base of the mantle, where mantle plumes subsequently entrain it. Fractional crystallization of metallic liquids within the CMB provides a consistent explanation of both Os isotope correlations, Os-W isotope systematics, and Fe/Mn evidence for core-mantle interaction over the entire Hawaiian source.

Marine and Lacustrine Organic-rich Sedimentary Unit Time Markers: Implications from Rhenium-Osmium Geochronology

NASA Astrophysics Data System (ADS)

Selby, D.

2011-12-01

Geochronology is fundamental to understand the age, rates and durations of Earth processes. This concerned Arthur Holmes who, for much of his career, attempted to define a geological time scale. This is a topic still important to Earth Scientists today, specifically the chronostratigraphy of sedimentary rocks. Here I explore the Re-Os geochronology of marine and lacustrine sedimentary rocks and its application to yield absolute time constraints for stratigraphy. The past decade has seen the pioneering research of Re-Os organic-rich sedimentary rock geochronology blossom into a tool that can now to be used to accurately and precisely determine depositional ages of organic-rich rock units that have experienced up to low grade greenschist metamorphism. This direct dating of sedimentary rocks is critical where volcanic horizons are absent. As a result, this tool has been applied to timescale calibration, basin correlation, formation duration and the timing of key Earth events (e.g., Neoproterozoic glaciations). The application of Re-Os chronometer to the Devonian-Mississippian boundary contained within the Exshaw Formation, Canada, determined an age of 361.3 ± 2.4 Ma. This age is in accord with U-Pb dates of interbedded tuff horizons and also U-Pb zircon date for the type Devonian-Mississippian Hasselbachtal section, Germany. The agreement of the biostratigraphic and U-Pb constraints of the Exshaw Formation with the Re-Os date illustrated the potential of the Re-Os chronometer to yield age determinations for sedimentary packages, especially in the absence of interbedd tuff horizons and biozones. A Re-Os date for the proposed type section of the Oxfordian-Kimmeridgian boundary, Staffin Bay, Isle of Skye, U.K., gave an age of 154.1 ± 2.2 Ma. This Re-Os age presents a 45 % (1.8 Ma) improvement in precision for the basal Kimmeridgian. It also demonstrated that the duration of the Kimmeridgian is nominally 3.3 Ma and thus is 1.6 Ma shorter than previously indicated. In addition to these examples, several studies have presented precise dates for Phanerozoic marine organic-rich units that are in excellent agreement with biostratigraphic determinations. A recent Re-Os study of the Woodford Shale (that was deposited throughout the Frasnian and Famennian) has provided important time markers as well as suggesting that the sedimentation rate of the Formation was relatively constant for ~20 Ma. To date only marine organic-rich sedimentary rocks have been utilized for Re-Os geochronology. However, lacustrine sedimentary rocks provide an invaluable archive of continental geological processes responding to tectonic, climatic and magmatic influences. Correlating these rocks to global geological phenomena requires accurate geochronological frameworks. The organic-rich lacustrine sedimentary units of the Eocene Green River Formation are enriched is Re and Os comparable to that of marine units. The Re-Os dates for the Green River Formation from the Uinta basin are 48.5 ± 0.6 Ma and 49.2 ± 1.0 Ma. These dates are in excellent agreement with Ar/Ar and U/Pb dates of interbedded tuffs in the GRF, therefore demonstrating that lacustrine units can be used for Re-Os geochronology in addition to marine organic-rich units.