Sample records for tantalum oxygen clusters

  1. Observation of oxide particles below the apparent oxygen solubility limit in tantalum

    NASA Technical Reports Server (NTRS)

    Stecura, S.

    1973-01-01

    The apparent solubility of oxygen in polycrystalline tantalum as determined by the X-ray diffraction lattice parameter technique is about 1.63 atomic percent at 820 C. However, oxide particles were identified in samples containing as low as 0.5 atomic percent of oxygen. These oxide particles were present at the grain boundaries and within the grains. The number of oxide particles increased with increasing oxygen concentration in tantalum. The presence of oxide particles suggests that the true solubility of oxygen in the polycrystalline tantalum metal is probably significantly lower than that reported in the literature.

  2. 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.

  3. Oxygen-Centered Hexatantalum Tetradecaimido Cluster Complexes

    PubMed Central

    Krinsky, Jamin L.; Anderson, Laura L.; Arnold, John; Bergman, Robert G.

    2008-01-01

    The syntheses and characterization of several octahedral hexatantalum cluster compounds of formula (ArN)14Ta6O are described (Ar = Ph, p-MeC6H4, p-MeOC6H4, p-t-BuC6H4, p-BrC6H4, m-ClC6H4). Treatment of Bn3Ta=N-t-Bu (Bn = CH2C6H5) or pentakis(dimethylamido)tantalum with an excess of the appropriate aniline and stoichiometric water or tantalum oxide afforded varying yields of arylimido clusters. The structures of two species were confirmed by X-ray diffraction (XRD), while the identity of the central oxygen atom was elucidated by electrospray mass spectrometry (MS) using 17O/18O-enriched material. The title species are very air- and moisture-sensitive but quite thermally stable in solution. Experimentally determined optical properties and oxidation/reduction potentials, as well as some computational results, indicate that they possess an electronic structure wherein the highest occupied molecular orbitals are ligand-centered, while the lowest unoccupied orbitals are metal-centered and delocalized throughout the tantalum cage. Whereas chemical oxidation resulted in cluster decomposition, reduction with decamethylcobaltocene yielded stable salts of formula [Cp*2Co][(ArN)14Ta6O] (Ar = Ph, Ar = p-MeC6H4). Small-molecule reactivity studies on one of these clusters showed that its imido functionalities are moderately reactive toward oxide donors but inert with respect to metallaheterocycle-forming processes. Clean imido/oxo exchange was observed with aldehydes and ketones, leading cleanly to organic imines with no soluble byproducts being observed. This exchange was also observed with a rhenium oxo compound (generating an imidorhenium complex as the only soluble species). All 14 imido groups were transferred in these reactions, and no mixed-ligand cluster intermediates were ever observed. PMID:18163614

  4. Addition of oxygen to and distribution of oxides in tantalum alloy T-111 at low concentrations

    NASA Technical Reports Server (NTRS)

    Stecura, S.

    1975-01-01

    Oxygen was added at 820 and 990 C at an oxygen pressure of about .0003 torr. The technique permitted predetermined and reproducible oxygen doping of the tantalum alloy (T-111). Based on the temperature dependency of the doping reaction, it was concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the tantalum and tungsten oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and oxygen from other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C but not at 820 C. The vaporization of WO3 has no apparent effect on the doping reaction.

  5. Effect of oxygen deficiency on electronic properties and local structure of amorphous tantalum oxide thin films

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

    Denny, Yus Rama; Firmansyah, Teguh; Oh, Suhk Kun

    2016-10-15

    Highlights: • The effect of oxygen flow rate on electronic properties and local structure of tantalum oxide thin films was studied. • The oxygen deficiency induced the nonstoichiometric state a-TaOx. • A small peak at 1.97 eV above the valence band side appeared on nonstoichiometric Ta{sub 2}O{sub 5} thin films. • The oxygen flow rate can change the local electronic structure of tantalum oxide thin films. - Abstract: The dependence of electronic properties and local structure of tantalum oxide thin film on oxygen deficiency have been investigated by means of X-ray photoelectron spectroscopy (XPS), Reflection Electron Energy Loss Spectroscopy (REELS),more » and X-ray absorption spectroscopy (XAS). The XPS results showed that the oxygen flow rate change results in the appearance of features in the Ta 4f at the binding energies of 23.2 eV, 24.4 eV, 25.8, and 27.3 eV whose peaks are attributed to Ta{sup 1+}, Ta{sup 2+}, Ta{sup 3+}/Ta{sup 4+}, and Ta{sup 5+}, respectively. The presence of nonstoichiometric state from tantalum oxide (TaOx) thin films could be generated by the oxygen vacancies. In addition, XAS spectra manifested both the increase of coordination number of the first Ta-O shell and a considerable reduction of the Ta-O bond distance with the decrease of oxygen deficiency.« less

  6. Electronic structure and charge transport in nonstoichiometric tantalum oxide

    NASA Astrophysics Data System (ADS)

    Perevalov, T. V.; Gritsenko, V. A.; Gismatulin, A. A.; Voronkovskii, V. A.; Gerasimova, A. K.; Aliev, V. Sh; Prosvirin, I. A.

    2018-06-01

    The atomic and electronic structure of nonstoichiometric oxygen-deficient tantalum oxide TaO x<2.5 grown by ion beam sputtering deposition was studied. The TaO x film content was analyzed by x-ray photoelectron spectroscopy and by quantum-chemistry simulation. TaO x is composed of Ta2O5, metallic tantalum clusters and tantalum suboxides. A method for evaluating the stoichiometry parameter of TaO x from the comparison of experimental and theoretical photoelectron valence band spectra is proposed. The charge transport properties of TaO x were experimentally studied and the transport mechanism was quantitatively analyzed with four theoretical dielectric conductivity models. It was found that the charge transport in almost stoichiometric and nonstoichiometric tantalum oxide can be consistently described by the phonon-assisted tunneling between traps.

  7. Direct observation of localized radial oxygen migration in functioning tantalum oxide memristors

    DOE PAGES

    Kumar, Suhas; Graves, Catherine E.; Strachan, John Paul; ...

    2016-02-02

    Oxygen migration in tantalum oxide, a promising next-generation storage material, is studied using in operando x-ray absorption spectromicroscopy and is used to microphysically describe accelerated evolution of conduction channel and device failure. Furthermore, the resulting ring-like patterns of oxygen concentration are modeled using thermophoretic forces and Fick diffusion, establishing the critical role of temperature-activated oxygen migration that has been under question lately.

  8. Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

    NASA Technical Reports Server (NTRS)

    Stecura, S.

    1976-01-01

    Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

  9. 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

  10. Effect of the oxygen content in a salt solution on the characteristics of sodium-reduced tantalum powders

    NASA Astrophysics Data System (ADS)

    Kolosov, V. N.; Orlov, V. M.; Miroshnichenko, M. N.; Prokhorova, T. Yu.; Masloboeva, S. M.; Belyaevskii, A. T.

    2009-02-01

    The characteristics of the tantalum powders produced by sodium thermal reduction from salt melts based on K2TaF7 and NaCl with various amounts of added oxycompounds K3TaOF6 and K2Ta2O3F6 are studied. At a molar ratio of oxygen to tantalum of 1.25 in the initial melt, capacitor tantalum powders with a specific surface area more than 3 m2/g are produced. The specific capacitance of the anodes made from these powders reaches 58 mC/g.

  11. Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

    PubMed

    Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

    2016-02-18

    Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

  12. Purification of tantalum by plasma arc melting

    DOEpatents

    Dunn, Paul S.; Korzekwa, Deniece R.

    1999-01-01

    Purification of tantalum by plasma arc melting. The level of oxygen and carbon impurities in tantalum was reduced by plasma arc melting the tantalum using a flowing plasma gas generated from a gas mixture of helium and hydrogen. The flowing plasma gases of the present invention were found to be superior to other known flowing plasma gases used for this purpose.

  13. Metastable tantalum oxide formation during the devitrification of amorphous tantalum thin films

    DOE PAGES

    Donaldson, Olivia K.; Hattar, Khalid; Trelewicz, Jason R.

    2016-07-04

    Microstructural evolution during the devitrification of amorphous tantalum thin films synthesized via pulsed laser deposition was investigated using in situ transmission electron microscopy (TEM) combined with ex situ isothermal annealing, bright-field imaging, and electron-diffraction analysis. The phases formed during crystallization and their stability were characterized as a function of the chamber pressure during deposition, devitrification temperature, and annealing time. A range of metastable nanocrystalline tantalum oxides were identified following devitrification including multiple orthorhombic oxide phases, which often were present with, or evolved to, the tetragonal TaO 2 phase. While the appearance of these phases indicated the films were evolving tomore » the stable form of tantalum oxide—monoclinic tantalum pentoxide—it was likely not achieved for the conditions considered due to an insufficient amount of oxygen present in the films following deposition. Nevertheless, the collective in situ and ex situ TEM analysis applied to thin film samples enabled the isolation of a number of metastable tantalum oxides. As a result, new insights were gained into the transformation sequence and stability of these nanocrystalline phases, which presents opportunities for the development of advanced tantalum oxide-based dielectric materials for novel memristor designs.« less

  14. Thermochemistry of tantalum-wall cooling system with lithium and sodium working fluids

    NASA Technical Reports Server (NTRS)

    Tower, L. K.

    1972-01-01

    Plots are presented which show the distribution of oxygen between liquid lithium and tantalum or niobium, and between liquid sodium and tantalum at elevated temperatures. Additional plots showing the composition of the gas phase above the solutions of oxygen and alkali metal are presented. The use of the plots is illustrated by an example tantalum heat pipe filled with lithium.

  15. The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules.

    PubMed

    Arakawa, Masashi; Ando, Kota; Fujimoto, Shuhei; Mishra, Saurabh; Patwari, G Naresh; Terasaki, Akira

    2018-05-10

    Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Tan+ (n = 2-10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Tan+, react with two molecules of NH3 and form TanN2+ with the release of three H2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal-nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides.

  16. The tantalum-cased tantalum capacitor

    NASA Technical Reports Server (NTRS)

    Moynihan, J. D.

    1977-01-01

    Tantalum-cased tantalum capacitors were tested with regard to temperature stability, capacitance ratio, surge current capabilities, shock, vibration, and thermal shock. They were found to be superior to the conventional wet slug tantalum capacitor cased in silver, since they are more resistant to sulfuric acid. The tantalum-cased tantalum capacitors are widely accepted for use in critical electronic equipment because of their excellent performance and reliability.

  17. Fabrication of a tantalum-clad tungsten target for LANSCE

    NASA Astrophysics Data System (ADS)

    Nelson, A. T.; O'Toole, J. A.; Valicenti, R. A.; Maloy, S. A.

    2012-12-01

    Development of a solid state bonding technique suitable to clad tungsten targets with tantalum was completed to improve operation of the Los Alamos Neutron Science Centers spallation target. Significant deterioration of conventional bare tungsten targets has historically resulted in transfer of tungsten into the cooling system through corrosion resulting in increased radioactivity outside the target and reduction of delivered neutron flux. The fabrication method chosen to join the tantalum cladding to the tungsten was hot isostatic pressing (HIP) given the geometry constraints of a cylindrical assembly and previous success demonstrated at KENS. Nominal HIP parameters of 1500 °C, 200 MPa, and 3 h were selected based upon previous work. Development of the process included significant surface engineering controls and characterization given tantalums propensity for oxide and carbide formation at high temperatures. In addition to rigorous acid cleaning implemented at each step of the fabrication process, a three layer tantalum foil gettering system was devised such that any free oxygen and carbon impurities contained in the argon gas within the HIP vessel was mitigated to the extent possible before coming into contact with the tantalum cladding. The result of the numerous controls and refined techniques was negligible coarsening of the native Ta2O5 surface oxide, no measureable oxygen diffusion into the tantalum bulk, and no detectable carburization despite use of argon containing up to 5 ppm oxygen and up to 40 ppm total CO, CO2, or organic contaminants. Post bond characterization of the interface revealed continuous bonding with a few microns of species interdiffusion.

  18. Packed bed carburization of tantalum and tantalum alloy

    DOEpatents

    Lopez, Peter C.; Rodriguez, Patrick J.; Pereyra, Ramiro A.

    1999-01-01

    Packed bed carburization of a tantalum or tantalum alloy object. A method for producing corrosion-resistant tantalum or tantalum alloy objects is described. The method includes the steps of placing the object in contact with a carburizing pack, heating the packed object in vacuum furnace to a temperature whereby carbon from the pack diffuses into the object forming grains with tantalum carbide along the grain boundaries, and etching the surface of the carburized object. This latter step removes tantalum carbides from the surface of the carburized tantalum object while leaving the tantalum carbide along the grain boundaries.

  19. Packed bed carburization of tantalum and tantalum alloy

    DOEpatents

    Lopez, P.C.; Rodriguez, P.J.; Pereyra, R.A.

    1999-06-29

    Packed bed carburization of a tantalum or tantalum alloy object is disclosed. A method for producing corrosion-resistant tantalum or tantalum alloy objects is described. The method includes the steps of placing the object in contact with a carburizing pack, heating the packed object in vacuum furnace to a temperature whereby carbon from the pack diffuses into the object forming grains with tantalum carbide along the grain boundaries, and etching the surface of the carburized object. This latter step removes tantalum carbides from the surface of the carburized tantalum object while leaving the tantalum carbide along the grain boundaries. 4 figs.

  20. Investigating the oxidation mechanism of tantalum nanoparticles at high heating rates

    NASA Astrophysics Data System (ADS)

    DeLisio, Jeffery B.; Wang, Xizheng; Wu, Tao; Egan, Garth C.; Jacob, Rohit J.; Zachariah, Michael R.

    2017-12-01

    Reduced diffusion length scales and increased specific surface areas of nanosized metal fuels have recently demonstrated increased reaction rates for these systems, increasing their relevance in a wide variety of applications. The most commonly employed metal fuel, aluminum, tends to oxidize rapidly near its melting point (660 °C) in addition to undergoing a phase change of the nascent oxide shell. To further expand on the understanding of nanosized metal fuel oxidation, tantalum nanoparticles were studied due to their high melting point (3017 °C) in comparison to aluminum. Both traditional slow heating rate and in-situ high heating rate techniques were used to probe the oxidation of tantalum nanoparticles in oxygen containing environments in addition to nanothermite mixtures. When oxidized by gas phase oxygen, the oxide shell of the tantalum nanoparticles rapidly crystallized creating cracks that may attribute to enhanced oxygen diffusion into the particle. In the case of tantalum based nanothermites, oxide shell crystallization was shown to induce reactive sintering with the metal oxide resulting in a narrow range of ignition temperatures independent of the metal oxide used. The oxidation mechanism was modeled using the Deal-Grove model to extract rate parameters, and theoretical burn times for tantalum based nanocomposites were calculated.

  1. Tantalum induced butterfly-like clusters on Si (111)-7 × 7 surface: STM/STS study at low coverage

    NASA Astrophysics Data System (ADS)

    Shukrynau, Pavel; Mutombo, Pingo; Švec, Martin; Hietschold, Michael; Cháb, Vladimír

    2012-02-01

    The adsorption of the small amounts of tantalum on Si (111)-7 × 7 reconstructed surface is investigated systematically using scanning tunneling microscopy and tunneling spectroscopy combined with first-principles density functional theory calculations. We find out that the moderate annealing of the Ta covered surface results in the formation of clusters of the butterfly-like shape. The clusters are sporadically distributed over the surface and their density is metal coverage dependent. Filled and empty state STM images of the clusters differ strongly suggesting the existence of covalent bonds within the cluster. Tunneling spectroscopy measurements reveal small energy gap, showing semiconductor-like behavior of the constituent atoms. The cluster model based on experimental images and theoretical calculations has been proposed and discussed. Presented results show that Ta joins the family of adsorbates, that are known to form magic clusters on Si (111)-7 × 7, but its magic cluster has the structural and electronic properties that are different from those reported before.

  2. METHOD OF FORMING TANTALUM SILICIDE ON TANTALUM SURFACES

    DOEpatents

    Bowman, M.G.; Krikorian, N.H.

    1961-10-01

    A method is described for forming a non-corrosive silicide coating on tantalum. The coating is made through the heating of trirhenium silicides in contact with the tantalum object to approximately 1400 deg C at which temperature trirhenium silicide decomposes into rhenium and gaseous silicons. The silicon vapor reacts with the tantalum surface to form a tantalum silicide layer approximately 10 microns thick. (AEC)

  3. Charge Transport and the Nature of Traps in Oxygen Deficient Tantalum Oxide.

    PubMed

    Gritsenko, Vladimir A; Perevalov, Timofey V; Voronkovskii, Vitalii A; Gismatulin, Andrei A; Kruchinin, Vladimir N; Aliev, Vladimir Sh; Pustovarov, Vladimir A; Prosvirin, Igor P; Roizin, Yakov

    2018-01-31

    Optical and transport properties of nonstoichiometric tantalum oxide thin films grown by ion beam deposition were investigated in order to understand the dominant charge transport mechanisms and reveal the nature of traps. The TaO x films composition was analyzed by X-ray photoelectron spectroscopy and by quantum-chemistry simulation. From the optical absorption and photoluminescence measurements and density functional theory simulations, it was concluded that the 2.75 eV blue luminescence excited in a TaO x by 4.45 eV photons, originates from oxygen vacancies. These vacancies are also responsible for TaO x conductivity. The thermal trap energy of 0.85 eV determined from the transport experiments coincides with the half of the Stokes shift of the blue luminescence band. It is argued that the dominant charge transport mechanism in TaO x films is phonon-assisted tunneling between the traps.

  4. Direct electroplating of copper on tantalum from ionic liquids in high vacuum: origin of the tantalum oxide layer.

    PubMed

    Schaltin, Stijn; D'Urzo, Lucia; Zhao, Qiang; Vantomme, André; Plank, Harald; Kothleitner, Gerald; Gspan, Christian; Binnemans, Koen; Fransaer, Jan

    2012-10-21

    In this paper, it is shown that high vacuum conditions are not sufficient to completely remove water and oxygen from the ionic liquid 1-ethyl-3-methylimidazolium chloride. Complete removal of water demands heating above 150 °C under reduced pressure, as proven by Nuclear Reaction Analysis (NRA). Dissolved oxygen gas can only be removed by the use of an oxygen scavenger such as hydroquinone, despite the fact that calculations show that oxygen should be removed completely by the applied vacuum conditions. After applying a strict drying procedure and scavenging of molecular oxygen, it was possible to deposit copper directly on tantalum without the presence of an intervening oxide layer.

  5. Mass Spectroscopy of Neutral Metal Oxide Clusters Using a Desk-Top Soft X-Ray Laser

    NASA Astrophysics Data System (ADS)

    Dong, F.; Heinbuch, S.; Bernstein, E. R.; Rocca, J. J.

    We report the use of a compact 46.9 nm capillary discharge soft x-ray laser in the study of metal-oxide nanoclusters using mass spectroscopy. Transition metal oxides are widely used as heterogeneous catalysts and catalytic supports in industrial processes. There are numerous applications for transition metal oxide catalysts, and although they are widely used, there is a lack of fundamental understanding of the complicated processes that occur on the metal oxide surface during catalysis. Conventional nanocluster spectroscopy techniques have used 193 nm radiation from an ArF excimer laser corresponding to a photon energy of 6.4 eV in order to photoionize a sample. Typical metal oxide nanocluster ionization energies fall into the range of 7-12 eV while some have even higher energies. Therefore a single 6.4 eV photon can not ionize the cluster making multiphoton processes the dominant ionization method. A major problem associated with mass spectroscopy can become evident during the multiphoton ionization of clusters. Specifically, the clusters may fragment during the ionization process and the identification of the neutral parent cluster can become difficult. In the present experiment neutral vanadium, niobium and tantalum oxide clusters are studied by single photon ionization with the 26.5 eV photons produced by a capillary discharge soft x-ray laser.1 During ionization, the metal oxide clusters are observed to be almost free of serious fragmentation. The most stable neutral cluster of vanadium, niobium, and tantalum oxide growth in a saturated oxygen condition are identified as MO2, M2O4/M2O5, M3O7, M4O10, M5O12, M6O15, M7O17, M8O20, and M9O22, which can be represented as a form (MO2)0,1(M2O5)y. M2O5 is identified as a basic unit to build-up the three kinds of metal oxide clusters. In the case of niobium and tantalum oxide clusters, the oxygen-deficient clusters with a structure of (MO2)2(M2O5)y are detected for groups that contain an even number of metal atoms. For

  6. Tungsten-reinforced tantalum

    NASA Technical Reports Server (NTRS)

    Bacigalupi, R. J.; Breitwieser, R.

    1972-01-01

    Method is described for producing tungsten-reinforced tantalum, a material possessing the high temperature strength of tungsten and room temperature ductility and weldability of tantalum. This material is produced by bonding together and overlaying structure of tungsten wires with chemical vapor deposited tantalum.

  7. Effects of substrate temperature on properties of pulsed dc reactively sputtered tantalum oxide films

    NASA Astrophysics Data System (ADS)

    Jain, Pushkar; Juneja, Jasbir S.; Bhagwat, Vinay; Rymaszewski, Eugene J.; Lu, Toh-Ming; Cale, Timothy S.

    2005-05-01

    The effects of substrate heating on the stoichiometry and the electrical properties of pulsed dc reactively sputtered tantalum oxide films over a range of film thickness (0.14 to 5.4 μm) are discussed. The film stoichiometry, and hence the electrical properties, of tantalum oxide films; e.g., breakdown field, leakage current density, dielectric constant, and dielectric loss are compared for two different cases: (a) when no intentional substrate/film cooling is provided, and (b) when the substrate is water cooled during deposition. All other operating conditions are the same, and the film thickness is directly related to deposition time. The tantalum oxide films deposited on the water-cooled substrates are stoichiometric, and exhibit excellent electrical properties over the entire range of film thickness. ``Noncooled'' tantalum oxide films are stoichiometric up to ~1 μm film thickness, beyond that the deposited oxide is increasingly nonstoichiometric. The presence of partially oxidized Ta in thicker (>~1 μm) noncooled tantalum oxide films causes a lower breakdown field, higher leakage current density, higher apparent dielectric constant, and dielectric loss. The growth of nonstoichiometric tantalum oxide in thicker noncooled films is attributed to decreased surface oxygen concentration due to oxygen recombination and desorption at higher film temperatures (>~100 °C). The quantitative results presented reflect experience with a specific piece of equipment; however, the procedures presented can be used to characterize deposition processes in which film stoichiometry can change.

  8. Copper-tantalum alloy

    DOEpatents

    Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

    1986-07-15

    A tantalum-copper alloy can be made by preparing a consumable electrode consisting of an elongated copper billet containing at least two spaced apart tantalum rods extending longitudinally the length of the billet. The electrode is placed in a dc arc furnace and melted under conditions which co-melt the copper and tantalum to form the alloy.

  9. Oxygen Vacancy Linear Clustering in a Perovskite Oxide

    DOE PAGES

    Eom, Kitae; Choi, Euiyoung; Choi, Minsu; ...

    2017-07-14

    Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

  10. Oxygen Vacancy Linear Clustering in a Perovskite Oxide

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

    Eom, Kitae; Choi, Euiyoung; Choi, Minsu

    Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO 3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti 2+ valence state or corresponding Ti 3d 2 electronic configuration along with divacancymore » cluster model analysis and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO 3 was verified by further X-ray diffuse scattering analysis. And because SrTiO 3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

  11. Prescribing Oxygen for Cluster Headache: A Guide for the Provider.

    PubMed

    Tepper, Stewart J; Duplin, Jessica; Nye, Barbara; Tepper, Deborah E

    2017-10-01

    Oxygen is the standard of care for acute treatment of cluster headache. CMS, the US Centers for Medicaid and Medicare Services, has made the indefensible decision to not cover oxygen for cluster headache for patients with Medicaid and Medicare insurance, despite the evidence and professional guidelines. Commercial insurance generally covers oxygen for cluster headache. This is a "how-to" guide for successfully prescribing oxygen in the US. Prescription information is provided that can be incorporated as dot phrases, smart sets, or other standard templates for prescribing oxygen for cluster patients. In many states, oxygen is affordable and can be prescribed for Medicaid and Medicare patients who wish to pay cash. Welding or nonmedical grade industrial oxygen is almost the same cost as medical oxygen. However, it is less pure, lacks the same inspection of tanks, and is delivered without regulators to provide appropriate flow rates. Patients who pay cash should be strongly encouraged to buy medical oxygen. © 2017 American Headache Society.

  12. All-tantalum electrolytic capacitor

    NASA Technical Reports Server (NTRS)

    Green, G. E., Jr.

    1977-01-01

    Device uses single-compression tantalum-to-tantalum seal. Single-compression seal allows better utilization of volume within device. As result of all-tantalum case and lengthened cathode, electrical parameters, particularly equivalent series resistance and capacitance stability, improved over silver-cased capacitor.

  13. Effect of Post-HALT Annealing on Leakage Currents in Solid Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2010-01-01

    Degradation of leakage currents is often observed during life testing of tantalum capacitors and is sometimes attributed to the field-induced crystallization in amorphous anodic tantalum pentoxide dielectrics. However, degradation of leakage currents and the possibility of annealing of degraded capacitors have not been investigated yet. In this work the effect of annealing after highly accelerated life testing (HALT) on leakage currents in various types of solid tantalum capacitors was analyzed. Variations of leakage currents with time during annealing at temperatures from 125 oC to 180 oC, thermally stimulated depolarization (TSD) currents, and I-V characteristics were measured to understand the conduction mechanism and the reason for current degradation. Annealing resulted in a gradual decrease of leakage currents and restored their initial values. Repeat HALT after annealing resulted in reproducible degradation of leakage currents. The observed results are explained based on ionic charge instability (drift/diffusion of oxygen vacancies) in the tantalum pentoxide dielectrics using a modified Schottky conduction mechanism.

  14. Niobium and tantalum

    USGS Publications Warehouse

    Schulz, Klaus J.; Piatak, Nadine M.; Papp, John F.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Niobium and tantalum are transition metals that are almost always found together in nature because they have very similar physical and chemical properties. Their properties of hardness, conductivity, and resistance to corrosion largely determine their primary uses today. The leading use of niobium (about 75 percent) is in the production of high-strength steel alloys used in pipelines, transportation infrastructure, and structural applications. Electronic capacitors are the leading use of tantalum for high-end applications, including cell phones, computer hard drives, and such implantable medical devices as pacemakers. Niobium and tantalum are considered critical and strategic metals based on the potential risks to their supply (because current production is restricted to only a few countries) and the significant effects that a restriction in supply would have on the defense, energy, high-tech industrial, and medical sectors.The average abundance of niobium and tantalum in bulk continental crust is relatively low—8.0 parts per million (ppm) niobium and 0.7 ppm tantalum. Their chemical characteristics, such as small ionic size and high electronic field strength, significantly reduce the potential for these elements to substitute for more common elements in rock-forming minerals and make niobium and tantalum essentially immobile in most aqueous solutions. Niobium and tantalum do not occur naturally as pure metals but are concentrated in a variety of relatively rare oxide and hydroxide minerals, as well as in a few rare silicate minerals. Niobium is primarily derived from the complex oxide minerals of the pyrochlore group ((Na,Ca,Ce)2(Nb,Ti,Ta)2(O,OH,F)7), which are found in some alkaline granite-syenite complexes (that is, igneous rocks containing sodium- or potassium-rich minerals and little or no quartz) and carbonatites (that is, igneous rocks that are more than 50 percent composed of primary carbonate minerals, by volume). Tantalum is derived mostly from the

  15. Electrodeposition of Tantalum and Tantalum-Chromium Alloys

    DTIC Science & Technology

    1980-05-01

    Electrochem Soc, 112, 840 (1965). 7Ibid, 113,60 (1966). 8Ibid, 113.66 (1966). J. Wurm, "European Conference on the Development of Molten Salts Applica...Chem. 35, 161-3 (1887). 16. J. Wurm, "European Conference on the Development of Molten Salts Applica- tions," Extended Abstracts and Proceedings, pp...Metals Tantalum Tantalum-Chromium Alloys Chromium Coating Fused Salt Electrolyte Electrodeposition FLINAK 20. ABSTRACT (Continue on reverse

  16. Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

    2018-03-01

    Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

  17. High-acoustic-impedance tantalum oxide layers for insulating acoustic reflectors.

    PubMed

    Capilla, Jose; Olivares, Jimena; Clement, Marta; Sangrador, Jesús; Iborra, Enrique; Devos, Arnaud

    2012-03-01

    This work describes the assessment of the acoustic properties of sputtered tantalum oxide films intended for use as high-impedance films of acoustic reflectors for solidly mounted resonators operating in the gigahertz frequency range. The films are grown by sputtering a metallic tantalum target under different oxygen and argon gas mixtures, total pressures, pulsed dc powers, and substrate biases. The structural properties of the films are assessed through infrared absorption spectroscopy and X-ray diffraction measurements. Their acoustic impedance is assessed by deriving the mass density from X-ray reflectometry measurements and the acoustic velocity from picosecond acoustic spectroscopy and the analysis of the frequency response of the test resonators.

  18. Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

    DOE PAGES

    Yu, Jianguo; Bai, Xian -Ming; El-Azab, Anter; ...

    2015-03-05

    In this study, oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO 2) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo (KMC) method has been used to investigate the kinetics of oxygen transport in UO 2 under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable offstoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO 2-x, oxygenmore » transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO 2+x, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that diinterstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing a explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.« less

  19. Gettering capsule for removing oxygen from liquid lithium systems

    NASA Technical Reports Server (NTRS)

    Tower, L. K.; Breitwieser, R.

    1973-01-01

    Capsule consisting of tantalum shell lined with tantalum screen and partially filled with lithium and pieces of yttrium is immersed in hot lithium stream. Oxygen is removed from stream by being absorbed by gettering capsule. Oxygen passes through capsule wall and into lithium inside capsule where it reacts with yttrium to form Y2O3.

  20. Tantalum recycling in the United States in 1998

    USGS Publications Warehouse

    Cunningham, Larry D.

    2001-01-01

    This report describes the flow of tantalum in the United States in 1998 with emphasis on the extent to which tantalum was recycled/reused. Tantalum was mostly recycled from new scrap that was generated during the manufacture of tantalum-related electronic components and new and old scrap products of tantalum-containing cemented carbides and superalloys. In 1998, about 210 metric tons of tantalum was recycled/reused, with about 43% derived from old scrap. The tantalum recycling rate was calculated to be 21%, and tantalum scrap recycling efficiency, 35%.

  1. Semimicrodetermination of tantalum with selenous acid

    USGS Publications Warehouse

    Grimaldi, F.S.; Schnepfe, M.M.

    1958-01-01

    Tantalum is separated and determined gravimetrically by precipitation with selenous acid from a highly acidic solution containing oxalic and tartaric acids. The method is selective for the determination of up to 30 mg. of tantalum pentoxide, and tolerates relatively large amounts of scandium, yttrium, cerium, titanium, zirconium, thorium, vanadium, niobium, molybdenum, tungsten, uranium, iron, aluminum, gallium, tin, lead, antimony, and bismuth. The separation of tantalum from niobium and titanium is not strictly quantitative, and correction is made colorimetrically for the small amounts of niobium and titanium co-precipitating with the tantalum. The method was applied to the determination of tantalum in tantaloniobate ores.

  2. Method of making tantalum capacitors

    DOEpatents

    McMillan, April D.; Clausing, Robert E.; Vierow, William F.

    1998-01-01

    A method for manufacturing tantalum capacitors includes preparing a tantalum compact by cold pressing tantalum powder, placing the compact, along with loose refractory metal powder, in a microwave-transparent casket to form an assembly, and heating the assembly for a time sufficient to effect at least partial sintering of the compact and the product made by the method.

  3. Process for manufacturing tantalum capacitors

    DOEpatents

    Lauf, Robert J.; Holcombe, Cressie E.; Dykes, Norman L.

    1993-01-01

    A process for manufacturing tantalum capacitors in which microwave energy is used to sinter a tantalum powder compact in order to achieve higher surface area and improved dielectric strength. The process comprises cold pressing tantalum powder with organic binders and lubricants to form a porous compact. After removal of the organics, the tantalum compact is heated to 1300.degree. to 2000.degree. C. by applying microwave radiation. Said compact is then anodized to form a dielectric oxide layer and infiltrated with a conductive material such as MnO.sub.2. Wire leads are then attached to form a capacitor to said capacitor is hermetically packaged to form the finished product.

  4. Process for manufacturing tantalum capacitors

    DOEpatents

    Lauf, R.J.; Holcombe, C.E.; Dykes, N.L.

    1993-02-02

    A process for manufacturing tantalum capacitors in which microwave energy is used to sinter a tantalum powder compact in order to achieve higher surface area and improved dielectric strength. The process comprises cold pressing tantalum powder with organic binders and lubricants to form a porous compact. After removal of the organics, the tantalum compact is heated to 1,300 to 2,000 C by applying microwave radiation. Said compact is then anodized to form a dielectric oxide layer and infiltrated with a conductive material such as MnO[sub 2]. Wire leads are then attached to form a capacitor to said capacitor is hermetically packaged to form the finished product.

  5. Effects of low-pressure air on oxygen contamination and lithium corrosion of a tantalum alloy, T-111, at 980 and 1260 C

    NASA Technical Reports Server (NTRS)

    Gahn, R. F.

    1974-01-01

    The effects were studied of low-pressure air on contamination and corrosion in the tantalum alloy T-111/lithium system at 980 and 1260 C. Capsules of T-111 containing lithium were exposed to six vacuum levels between 1 x 10 to the 8th power and 0.0003 torr by controlled air leakage into a vacuum system. Capsules exposed at 980 C and 0.0002 torr failed from intragranular oxidation. The remainder of the capsules completed the 96-hour tests. The depth of oxygen contamination was greater at 980 C than at 1260 C. Tests made at 0.0001 and 0.00001 torr levels caused large increases in the oxygen content of the T-111. Tests at 0.000001 torr or less produced no significant contamination. No lithium corrosion of the T-111 was observed under any of the conditions.

  6. New iron-sulfur clusters help hydrogenases tolerate oxygen.

    PubMed

    Grubel, Katarzyna; Holland, Patrick L

    2012-04-02

    One S less: recent crystallographic studies have revealed a new, oxygen-tolerant kind of iron-sulfide cluster [4Fe-3S], which contains only three rather than four sulfur atoms in its cage (see picture; yellow=S, red=Fe, blue=N, green=cysteine). It is proposed that the cluster's ability to transfer multiple electrons increases the oxygen tolerance by enabling the enzyme to reduce O(2) rapidly, converting the dioxygen into harmless water before it can damage the protein. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. X-ray analyses of thermally grown and reactively sputtered tantalum oxide films on NiTi alloy

    NASA Astrophysics Data System (ADS)

    McNamara, Karrina; Tofail, Syed A. M.; Conroy, Derek; Butler, James; Gandhi, Abbasi A.; Redington, Wynette

    2012-08-01

    Sputter deposition of tantalum (Ta) on the surface of NiTi alloy is expected to improve the alloy's corrosion resistance and biocompatibility. Tantalum is a well-known biomaterial which is not affected by body fluids and is not irritating to human tissue. Here we compare the oxidation chemistry crystal structure evolution of tantalum oxide films grown on NiTi by reactive O2 sputtering and by thermal oxidation of sputter deposited Ta films. The effect of sputtering parameters and post-sputtering treatments on the morphology, oxidation state and crystal structure of the tantalum oxide layer have been investigated by field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The study has found that it may be better to avoid oxidation at and above 600 °C. The study establishes that reactive sputtering in presence of low oxygen mixture yields thicker film with better control of the film quality except that the surface oxidation state of Ta is slightly lower.

  8. Additively manufactured porous tantalum implants.

    PubMed

    Wauthle, Ruben; van der Stok, Johan; Amin Yavari, Saber; Van Humbeeck, Jan; Kruth, Jean-Pierre; Zadpoor, Amir Abbas; Weinans, Harrie; Mulier, Michiel; Schrooten, Jan

    2015-03-01

    The medical device industry's interest in open porous, metallic biomaterials has increased in response to additive manufacturing techniques enabling the production of complex shapes that cannot be produced with conventional techniques. Tantalum is an important metal for medical devices because of its good biocompatibility. In this study selective laser melting technology was used for the first time to manufacture highly porous pure tantalum implants with fully interconnected open pores. The architecture of the porous structure in combination with the material properties of tantalum result in mechanical properties close to those of human bone and allow for bone ingrowth. The bone regeneration performance of the porous tantalum was evaluated in vivo using an orthotopic load-bearing bone defect model in the rat femur. After 12 weeks, substantial bone ingrowth, good quality of the regenerated bone and a strong, functional implant-bone interface connection were observed. Compared to identical porous Ti-6Al-4V structures, laser-melted tantalum shows excellent osteoconductive properties, has a higher normalized fatigue strength and allows for more plastic deformation due to its high ductility. It is therefore concluded that this is a first step towards a new generation of open porous tantalum implants manufactured using selective laser melting. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  9. Degradation of Leakage Currents in Solid Tantalum Capacitors Under Steady-State Bias Conditions

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2010-01-01

    Degradation of leakage currents in various types of solid tantalum capacitors under steady-state bias conditions was investigated at temperatures from 105 oC to 170 oC and voltages up to two times the rated voltage. Variations of leakage currents with time under highly accelerated life testing (HALT) and annealing, thermally stimulated depolarization currents, and I-V characteristics were measured to understand the conduction mechanism and the reason for current degradation. During HALT the currents increase gradually up to three orders of magnitude in some cases, and then stabilize with time. This degradation is reversible and annealing can restore the initial levels of leakage currents. The results are attributed to migration of positively charged oxygen vacancies in tantalum pentoxide films that diminish the Schottky barrier at the MnO2/Ta2O5 interface and increase electron injection. A simple model allows for estimation of concentration and mobility of oxygen vacancies based on the level of current degradation.

  10. Interplay between oxygen and Fe-S cluster biogenesis: insights from the Suf pathway.

    PubMed

    Boyd, Eric S; Thomas, Khaleh M; Dai, Yuyuan; Boyd, Jeff M; Outten, F Wayne

    2014-09-23

    Iron-sulfur (Fe-S) cluster metalloproteins conduct essential functions in nearly all contemporary forms of life. The nearly ubiquitous presence of Fe-S clusters and the fundamental requirement for Fe-S clusters in both aerobic and anaerobic Archaea, Bacteria, and Eukarya suggest that these clusters were likely integrated into central metabolic pathways early in the evolution of life prior to the widespread oxidation of Earth's atmosphere. Intriguingly, Fe-S cluster-dependent metabolism is sensitive to disruption by oxygen because of the decreased bioavailability of ferric iron as well as direct oxidation of sulfur trafficking intermediates and Fe-S clusters by reactive oxygen species. This fact, coupled with the ubiquity of Fe-S clusters in aerobic organisms, suggests that organisms evolved with mechanisms that facilitate the biogenesis and use of these essential cofactors in the presence of oxygen, which gradually began to accumulate around 2.5 billion years ago as oxygenic photosynthesis proliferated and reduced minerals that buffered against oxidation were depleted. This review highlights the most ancient of the Fe-S cluster biogenesis pathways, the Suf system, which likely was present in early anaerobic forms of life. Herein, we use the evolution of the Suf pathway to assess the relationships between the biochemical functions and physiological roles of Suf proteins, with an emphasis on the selective pressure of oxygen toxicity. Our analysis suggests that diversification into oxygen-containing environments disrupted iron and sulfur metabolism and was a main driving force in the acquisition of accessory Suf proteins (such as SufD, SufE, and SufS) by the core SufB-SufC scaffold complex. This analysis provides a new framework for the study of Fe-S cluster biogenesis pathways and Fe-S cluster-containing metalloenzymes and their complicated patterns of divergence in response to oxygen.

  11. Interplay between Oxygen and Fe–S Cluster Biogenesis: Insights from the Suf Pathway

    PubMed Central

    2015-01-01

    Iron–sulfur (Fe–S) cluster metalloproteins conduct essential functions in nearly all contemporary forms of life. The nearly ubiquitous presence of Fe–S clusters and the fundamental requirement for Fe–S clusters in both aerobic and anaerobic Archaea, Bacteria, and Eukarya suggest that these clusters were likely integrated into central metabolic pathways early in the evolution of life prior to the widespread oxidation of Earth’s atmosphere. Intriguingly, Fe–S cluster-dependent metabolism is sensitive to disruption by oxygen because of the decreased bioavailability of ferric iron as well as direct oxidation of sulfur trafficking intermediates and Fe–S clusters by reactive oxygen species. This fact, coupled with the ubiquity of Fe–S clusters in aerobic organisms, suggests that organisms evolved with mechanisms that facilitate the biogenesis and use of these essential cofactors in the presence of oxygen, which gradually began to accumulate around 2.5 billion years ago as oxygenic photosynthesis proliferated and reduced minerals that buffered against oxidation were depleted. This review highlights the most ancient of the Fe–S cluster biogenesis pathways, the Suf system, which likely was present in early anaerobic forms of life. Herein, we use the evolution of the Suf pathway to assess the relationships between the biochemical functions and physiological roles of Suf proteins, with an emphasis on the selective pressure of oxygen toxicity. Our analysis suggests that diversification into oxygen-containing environments disrupted iron and sulfur metabolism and was a main driving force in the acquisition of accessory Suf proteins (such as SufD, SufE, and SufS) by the core SufB–SufC scaffold complex. This analysis provides a new framework for the study of Fe–S cluster biogenesis pathways and Fe–S cluster-containing metalloenzymes and their complicated patterns of divergence in response to oxygen. PMID:25153801

  12. Radiopharmaceutical composition containing tantalum-178 and process therefor

    DOEpatents

    Neirinckx, Rudi D.; Holman, B. Leonard; Davis, Michael A.; Harris, Gale I.

    1989-05-16

    A physiologically acceptable solution of tantalum-178 having an activity of 0.1 to 200 millicuries per milliliter of tantalum-178 solution is provided. The solution is obtained from tungsten-178 bound to a column of an anion exchange resin which forms tantalum-178 in situ by eluting the column with a hydrochloric acid solution containing hydrogen peroxide to form an acidic solution of tantalum-178. The acidic solution of tantalum-178 then is neutralized.

  13. Reliability Effects of Surge Current Testing of Solid Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2007-01-01

    Solid tantalum capacitors are widely used in space applications to filter low-frequency ripple currents in power supply circuits and stabilize DC voltages in the system. Tantalum capacitors manufactured per military specifications (MIL-PRF-55365) are established reliability components and have less than 0.001% of failures per 1000 hours (the failure rate is less than 10 FIT) for grades D or S, thus positioning these parts among electronic components with the highest reliability characteristics. Still, failures of tantalum capacitors do happen and when it occurs it might have catastrophic consequences for the system. This is due to a short-circuit failure mode, which might be damaging to a power supply, and also to the capability of tantalum capacitors with manganese cathodes to self-ignite when a failure occurs in low-impedance applications. During such a failure, a substantial amount of energy is released by exothermic reaction of the tantalum pellet with oxygen generated by the overheated manganese oxide cathode, resulting not only in destruction of the part, but also in damage of the board and surrounding components. A specific feature of tantalum capacitors, compared to ceramic parts, is a relatively large value of capacitance, which in contemporary low-size chip capacitors reaches dozens and hundreds of microfarads. This might result in so-called surge current or turn-on failures in the parts when the board is first powered up. Such a failure, which is considered as the most prevalent type of failures in tantalum capacitors [I], is due to fast changes of the voltage in the circuit, dV/dt, producing high surge current spikes, I(sub sp) = Cx(dV/dt), when current in the circuit is unrestricted. These spikes can reach hundreds of amperes and cause catastrophic failures in the system. The mechanism of surge current failures has not been understood completely yet, and different hypotheses were discussed in relevant literature. These include a sustained scintillation

  14. Mineral resource of the month: tantalum

    USGS Publications Warehouse

    ,

    2011-01-01

    The article offers information on a rare transition metal called tantalum. It says that the blue-gray mineral resource was discovered in 1801 or 1802 and was used for capacitors in 1940. It adds that the tantalite ore and other minerals in the ore should be separated in order to generate concentrates of tantalum. The use of tantalum are also cited.

  15. Ab initio metadynamics simulations of oxygen/ligand interactions in organoaluminum clusters

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

    Alnemrat, Sufian; Hooper, Joseph P., E-mail: jphooper@nps.edu

    2014-10-14

    Car-Parrinello molecular dynamics combined with a metadynamics algorithm is used to study the initial interaction of O{sub 2} with the low-valence organoaluminum clusters Al{sub 4}Cp{sub 4} (Cp=C{sub 5}H{sub 5}) and Al{sub 4}Cp{sub 4}{sup *} (Cp{sup *}=C{sub 5}[CH{sub 3}]{sub 5}). Prior to reaction with the aluminum core, simulations suggest that the oxygen undergoes a hindered crossing of the steric barrier presented by the outer ligand monolayer. A combination of two collective variables based on aluminum/oxygen distance and lateral oxygen displacement was found to produce distinct reactant, product, and transition states for this process. In the methylated cluster with Cp{sup *} ligands,more » a broad transition state of 45 kJ/mol was observed due to direct steric interactions with the ligand groups and considerable oxygen reorientation. In the non-methylated cluster the ligands distort away from the oxidizer, resulting in a barrier of roughly 34 kJ/mol with minimal O{sub 2} reorientation. A study of the oxygen/cluster system fixed in a triplet multiplicity suggests that the spin state does not affect the initial steric interaction with the ligands. The metadynamics approach appears to be a promising means of analyzing the initial steps of such oxidation reactions for ligand-protected clusters.« less

  16. Performance comparison: Aluminum electrolytic and solid tantalum capacitor

    NASA Technical Reports Server (NTRS)

    Hawthornthwaite, B. G.; Piper, J.; Holland, H. W.

    1981-01-01

    Several key electrical and environmental parameters of latest technology aluminum electrolytic and solid tantalum capacitors were evaluated in terms of price fluctuations of tantalum metal. Performance differences between solid tantalums and aluminum electrolytics are examined.

  17. High strength forgeable tantalum base alloy

    NASA Technical Reports Server (NTRS)

    Buckman, R. W., Jr.

    1975-01-01

    Increasing tungsten content of tantalum base alloy to 12-15% level will improve high temperature creep properties of existing tantalum base alloys while retaining their excellent fabrication and welding characteristics.

  18. Tantalum-based semiconductors for solar water splitting.

    PubMed

    Zhang, Peng; Zhang, Jijie; Gong, Jinlong

    2014-07-07

    Solar energy utilization is one of the most promising solutions for the energy crises. Among all the possible means to make use of solar energy, solar water splitting is remarkable since it can accomplish the conversion of solar energy into chemical energy. The produced hydrogen is clean and sustainable which could be used in various areas. For the past decades, numerous efforts have been put into this research area with many important achievements. Improving the overall efficiency and stability of semiconductor photocatalysts are the research focuses for the solar water splitting. Tantalum-based semiconductors, including tantalum oxide, tantalate and tantalum (oxy)nitride, are among the most important photocatalysts. Tantalum oxide has the band gap energy that is suitable for the overall solar water splitting. The more negative conduction band minimum of tantalum oxide provides photogenerated electrons with higher potential for the hydrogen generation reaction. Tantalates, with tunable compositions, show high activities owning to their layered perovskite structure. (Oxy)nitrides, especially TaON and Ta3N5, have small band gaps to respond to visible-light, whereas they can still realize overall solar water splitting with the proper positions of conduction band minimum and valence band maximum. This review describes recent progress regarding the improvement of photocatalytic activities of tantalum-based semiconductors. Basic concepts and principles of solar water splitting will be discussed in the introduction section, followed by the three main categories regarding to the different types of tantalum-based semiconductors. In each category, synthetic methodologies, influencing factors on the photocatalytic activities, strategies to enhance the efficiencies of photocatalysts and morphology control of tantalum-based materials will be discussed in detail. Future directions to further explore the research area of tantalum-based semiconductors for solar water splitting

  19. Tantalum-copper alloy and method for making

    DOEpatents

    Schmidt, Frederick A.; Verhoeven, John D.; Gibson, Edwin D.

    1984-11-06

    A tantalum-copper alloy can be made by preparing a consumable electrode consisting of an elongated copper billet containing at least two spaced apart tantalum rods extending longitudinally the length of the billet. The electrode is placed in a dc arc furnace and melted under conditions which co-melt the copper and tantalum to form the alloy.

  20. Tantalum-copper alloy and method for making

    DOEpatents

    Schmidt, F.A.; Verhoeven, J.D.; Gibson, E.D.

    1983-06-01

    A tantalum-copper alloy can be made by preparing a consumable electrode consisting of an elongated copper billet containing at least two spaced apart tantalum rods extending longitudinally the length of the billet. The electrode is placed in a dc arc furnace and melted under conditions which co-melt the copper and tantalum to form the alloy.

  1. Feasibility study of oxygen-dispensing emitters for thermionic converters, phase 1

    NASA Technical Reports Server (NTRS)

    Desteese, J. G.

    1972-01-01

    A metal/ceramic Marchuk tube was used to measure work functions of oxygen-doped tantalum, to determine applicability of the material to plasma-mode thermionic converters. Oxygen-doped tantalum was shown to increase in work function monotonically with oxygen doping in the range 0.1 to 0.3 atomic percent. Oxygenated test emitters were run at an average temperature of 2165 K and a T/T sub Cs ratio -5.8 to observe the influence of oxygen depletion. Bare work function decreased with outgassing of oxygen. Projections were made based on outgassing kinetics and area/volume ratios to calculate the longevity of oxygen doping in a practical converter. Calculations indicated that the program goal of 10,000 hr could be achieved at 1800 K with an initial oxygen doping of 1 atomic percent and a practical emitter area/volume ratio.

  2. Interaction of Boron Clusters with Oxygen: a DFT Study

    NASA Astrophysics Data System (ADS)

    Salavitabar, Kamron; Boggavarapu, Kiran; Kandalam, Anil

    A controlled combustion involving aluminum nanoparticles has often been the focus of studies in the field of solid fuel propellants. However very little focus has been given to the study of boron nanoparticles in controlled combustion. In contrast to aluminum nanoclusters, boron nanoclusters (Bn) are known to exhibit a planar geometries even at the size of n = 19 - 20, and thus offer a greater surface area for interaction with oxygen. Earlier experimental studies have shown that boron nanoclusters exhibit different reactivity with oxygen depending on their size and charge. In this poster, we present our recent density functional theory based results, focusing on the reactivity patterns of neutral and negatively charged B5 cluster with On, where n = 1 - 5; and B6 cluster with On (n = 1 - 2). The effect of charge on the reactivity of boron cluster, variation in the stability of product clusters, i e., neutral and negatively charged B5On (n = 1 - 5) and B6On (n = 1 - 2) are also examined. Financial Support from West Chester University Foundation under FaStR grant is acknowledged.

  3. Ultraviolet spectrophotometric determination of tantalum with pyrogallol

    USGS Publications Warehouse

    Dinnin, J.I.

    1953-01-01

    In a search for a more rapid method for the determination of tantalum in rocks and minerals, an intensive study was made of the tantalum-pyrogallol reaction recommended by Platanov and Krivoshlikov, and a better modified spectrophotometric procedure is given. The improved method consists in measuring the absorbancy of the tantalum-pyrogallol complex at 325 m?? in 4N hydrochloric acid and a fixed concentration (0.0175M) of ammonium oxalate. Beer's law is followed for the concentration range up to 40 ?? per ml. Sensitivity in terms of molar absorbancy index is 4775. Most interferences are additive in character and readily correctable. Separations or major corrections are required in the presence of significant amounts of molybdenum, tungsten, antimony, and uranium. The method has been successfully applied to three ores previously analyzed by gravimetric techniques. The method affords greater speed, sensitivity, and reproducibility in the determination of tantalum in rocks and minerals. A more reliable technique for preparing standard solutions of tantalum has been developed.

  4. Study of constitution diagram aluminum-tantalum

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

    Glazov, V.M.; Mal'tsev, M.V.; Chistyakov, Y.D.

    1988-10-20

    Alloys of aluminum with tantalum were for the first time obtained by aluminothermic method in 1868 by Moriniak. Later these alloys were studied in the works of Schirmeister (1915) and Brouwer (1938), moreover Brouwer established that tantalum with aluminum forms the chemical compound TaA1, which has tetragonal crystal lattice with parameters a=5.422 angstroms and c=8.536 angstroms (1). However despite the fact that alloys of aluminum with tantalum long ago are obtained already, constitution diagram of this system is not studied until recently. In connection with the application of tantalum as the modifying additive in aluminum alloys an emergency in themore » construction of this diagram, without the knowledge by which it is not possible to give the correct explanation of the mechanism of the very process of the modification of primary grain. For this purpose was undertaken this work. Russian translations.« less

  5. Niobium and tantalum: indispensable twins

    USGS Publications Warehouse

    Schulz, Klaus; Papp, John

    2014-01-01

    Niobium and tantalum are transition metals almost always paired together in nature. These “twins” are difficult to separate because of their shared physical and chemical properties. In 1801, English chemist Charles Hatchett uncovered an unknown element in a mineral sample of columbite; John Winthrop found the sample in a Massachusetts mine and sent it to the British Museum in London in 1734. The name columbium, which Hatchet named the new element, came from the poetic name for North America—Columbia—and was used interchangeably for niobium until 1949, when the name niobium became official. Swedish scientist Anders Ekberg discovered tantalum in 1802, but it was confused with niobium, because of their twinned properties, until 1864, when it was recognized as a separate element. Niobium is a lustrous, gray, ductile metal with a high melting point, relatively low density, and superconductor properties. Tantalum is a dark blue-gray, dense, ductile, very hard, and easily fabricated metal. It is highly conductive to heat and electricity and renowned for its resistance to acidic corrosion. These special properties determine their primary uses and make niobium and tantalum indispensable.

  6. Ion beam and dual ion beam sputter deposition of tantalum oxide films

    NASA Astrophysics Data System (ADS)

    Cevro, Mirza; Carter, George

    1994-11-01

    Ion beam sputter deposition (IBS) and dual ion beam sputter deposition (DIBS) of tantalum oxide films was investigated at room temperature and compared with similar films prepared by e-gun deposition. Optical properties ie refractive index and extinction coefficient of IBS films were determined in the 250 - 1100 nm range by transmission spectrophotometry and at (lambda) equals 632.8 nm by ellipsometry. They were found to be mainly sensitive to the partial pressure of oxygen used as a reactive gas in the deposition process. The maximum value of the refractive index of IBS deposited tantalum oxide films was n equals 2.15 at (lambda) equals 550 nm and the extinction coefficient of order k equals 2 X 10-4. Films deposited by e-gun deposition had refractive index n equals 2.06 at (lambda) equals 550 nm. Films deposited using DIBS ie deposition assisted by low energy Ar and O2 ions (Ea equals 0 - 300 eV) and low current density (Ji equals 0 - 40 (mu) A/cm2) showed no improvement in the optical properties of the films. Preferential sputtering occurred at Ea(Ar) equals 300 eV and Ji equals 20 (mu) A/cm2 and slightly oxygen deficient films were formed. Different bonding states in the tantalum-oxide films were determined by x-ray spectroscopy while composition of the film and contaminants were determined by Rutherford scattering spectroscopy. Tantalum oxide films formed by IBS contained relatively high Ar content (approximately equals 2.5%) originating from the reflected argon neutrals from the sputtering target while assisted deposition slightly increased the Ar content. Stress in the IBS deposited films was measured by the bending technique. IBS deposited films showed compressive stress with a typical value of s equals 3.2 X 109 dyn/cm2. Films deposited by concurrent ion bombardment showed an increase in the stress as a function of applied current density. The maximum was s approximately equals 5.6 X 109 dyn/cm2 for Ea equals 300 eV and Ji equals 35 (mu) A/cm2. All

  7. Ion-beam and dual-ion-beam sputter deposition of tantalum oxide films

    NASA Astrophysics Data System (ADS)

    Cevro, Mirza; Carter, George

    1995-02-01

    Ion-beam sputter deposition (IBS) and dual-ion-beam sputter deposition (DIBS) of tantalum oxide films was investigated at room temperature and compared with similar films prepared by e-gun deposition. The optical properties, i.e., refractive index and extinction coefficient, of IBS films were determined in the 250- to 1100-nm range by transmission spectrophotometry and at (lambda) equals 632.8 nm by ellipsometry. They were found to be mainly sensitive to the partial pressure of oxygen used as a reactive gas in the deposition process. The maximum value of the refractive index of IBS deposited tantalum oxide films was n equals 2.15 at (lambda) equals 550 nm and the extinction coefficient of order k equals 2 X 10-4. Films deposited by e-gun deposition had refractive index n 2.06 at (lambda) equals 550 nm. Films deposited using DIBS, i.e., deposition assisted by low energy Ar and O2 ions (Ea equals 0 to 300 eV) and low current density (Ji equals 0 to 40 (mu) A/cm2), showed no improvement in the optical properties of the films. Preferential sputtering occurred at Ea(Ar) equals 300 eV and Ji equals 20 (mu) A/cm2 and slightly oxygen deficient films were formed. Different bonding states in the tantalum-oxide films were determined by x-ray spectroscopy, whereas composition of the film and contaminants were determined by Rutherford backscattering spectroscopy (RBS). Tantalum oxide films formed by IBS contained relatively high Ar content (approximately equals 2.5%) originating from the reflected argon neutrals from the sputtering target whereas assisted deposition slightly increased the Ar content. Stress in the IBS-deposited films was measured by the bending technique. IBS-deposited films showed compressive stress with a typical value of s equals 3.2 X 109 dyn/cm2. Films deposited by concurrent ion bombardment showed an increase in the stress as a function of applied current density. The maximum was s approximately equals 5.6 X 109 dyn/cm2 for Ea equals 300 eV and Ji equals

  8. The use of oxygen in cluster headache treatment worldwide - a survey of the International Headache Society (IHS).

    PubMed

    Evers, Stefan; Rapoport, Alan

    2017-04-01

    Background Oxygen is recommended for the treatment of acute cluster headache attacks. However, it is not available worldwide. Methods The International Headache Society performed a survey among its national member societies on the availability and the restrictions for oxygen in the treatment of cluster headache. Results Oxygen is reimbursed in 50% of all countries responding ( n = 22). There are additional restrictions in the reimbursement of the facial mask and with respect to age. Conclusion Oxygen for the treatment of cluster headache attack is not reimbursed worldwide. Headache societies should pressure national/public health authorities to reimburse oxygen for cluster headache in all countries.

  9. Structure refinement for tantalum nitrides nanocrystals with various morphologies

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

    Liu, Lianyun; School of Science, Beijing Jiaotong University, 3 Shang Yuan Cun, Haidian District, Beijing 100044; Huang, Kai

    2012-07-15

    Graphical abstract: Tantalum nitrides nanocrystals with various phases and morphologies for the first time have been synthesized through homogenous sodium reduction under low temperature with the subsequent annealing process under high vacuum. Highlights: ► The spherical TaN, cuboidal TaN{sub 0.83} and TaN{sub 0.5} nanocrystals have been synthesized through homogenous sodium reduction under low temperature with the subsequent annealing process under high vacuum. ► The crystal structures of different tantalum nitrides were determined by Rietveld refinement on the X-ray diffraction data and the examinations of electron microcopies. ► The specific surface area of the tantalum nitrides powders was around 10 m{supmore » 2} g{sup −1}. ► Tantalum nitrides powders could be suitable for capacitor with high specific capacitance. -- Abstract: Tantalum nitrides (TaN{sub x}) nanocrystals with different phase and morphology have been synthesized through homogenous sodium reduction under low temperature with the subsequent annealing process under high vacuum. The crystal structures of tantalum nitrides were determined by Rietveld refinement based on the X-ray diffraction data. The morphologies of various tantalum nitrides nanocrystals in high quality were analyzed through the electron microcopies examinations. The spherical TaN nanoparticles, cuboidal TaN{sub 0.83} and TaN{sub 0.5} nanocrystals have been selectively prepared at different annealing temperatures. In addition, the specific surface areas of the tantalum nitrides nanocrystals measured by BET method were around 9.87–11.64 m{sup 2} g{sup −1}, indicating that such nano-sized tantalum nitrides could be suitable for capacitor with high specific capacitance.« less

  10. Scintillation Breakdowns in Chip Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2008-01-01

    Scintillations in solid tantalum capacitors are momentarily local breakdowns terminated by a self-healing or conversion to a high-resistive state of the manganese oxide cathode. This conversion effectively caps the defective area of the tantalum pentoxide dielectric and prevents short-circuit failures. Typically, this type of breakdown has no immediate catastrophic consequences and is often considered as nuisance rather than a failure. Scintillation breakdowns likely do not affect failures of parts under surge current conditions, and so-called "proofing" of tantalum chip capacitors, which is a controllable exposure of the part after soldering to voltages slightly higher than the operating voltage to verify that possible scintillations are self-healed, has been shown to improve the quality of the parts. However, no in-depth studies of the effect of scintillations on reliability of tantalum capacitors have been performed so far. KEMET is using scintillation breakdown testing as a tool for assessing process improvements and to compare quality of different manufacturing lots. Nevertheless, the relationship between failures and scintillation breakdowns is not clear, and this test is not considered as suitable for lot acceptance testing. In this work, scintillation breakdowns in different military-graded and commercial tantalum capacitors were characterized and related to the rated voltages and to life test failures. A model for assessment of times to failure, based on distributions of breakdown voltages, and accelerating factors of life testing are discussed.

  11. 21 CFR 886.3100 - Ophthalmic tantalum clip.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... blood vessels in the eye. (b) Classification. Class II (special controls). The device is exempt from the...) MEDICAL DEVICES OPHTHALMIC DEVICES Prosthetic Devices § 886.3100 Ophthalmic tantalum clip. (a) Identification. An ophthalmic tantalum clip is a malleable metallic device intended to be implanted permanently...

  12. Efficacy of Tantalum Tungsten Alloys for Diffusion Barrier Applications

    NASA Astrophysics Data System (ADS)

    Smathers, D. B.; Aimone, P. R.

    2017-12-01

    Traditionally either Niobium, Tantalum or a combination of both have been used as diffusion barriers in Nb3Sn Multi-filament wire. Vanadium has also been used successfully but the ultimate RRR of the copper is limited unless an external shell of Niobium is included. Niobium is preferred over Tantalum when alternating current losses are not an issue as the Niobium will react to form Nb3Sn. Pure Tantalum tends to deform irregularly requiring extra starting thickness to ensure good barrier qualities. Our evaluations showed Tantalum lightly alloyed with 3 wt% Tungsten is compatible with the wire drawing process while deforming as well as or better than pure Niobium. Ta3wt%W has been processed as a single barrier and as a distributed barrier to fine dimensions. In addition, the higher modulus and strength of the Tantalum Tungsten alloy improves the overall tensile properties of the wire.

  13. Degradation of Leakage Currents and Reliability Prediction for Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2016-01-01

    Two types of failures in solid tantalum capacitors, catastrophic and parametric, and their mechanisms are described. Analysis of voltage and temperature reliability acceleration factors reported in literature shows a wide spread of results and requires more investigation. In this work, leakage currents in two types of chip tantalum capacitors were monitored during highly accelerated life testing (HALT) at different temperatures and voltages. Distributions of degradation rates were approximated using a general log-linear Weibull model and yielded voltage acceleration constants B = 9.8 +/- 0.5 and 5.5. The activation energies were Ea = 1.65 eV and 1.42 eV. The model allows for conservative estimations of times to failure and was validated by long-term life test data. Parametric degradation and failures are reversible and can be annealed at high temperatures. The process is attributed to migration of charged oxygen vacancies that reduce the barrier height at the MnO2/Ta2O5 interface and increase injection of electrons from the MnO2 cathode. Analysis showed that the activation energy of the vacancies' migration is 1.1 eV.

  14. Hafnium radioisotope recovery from irradiated tantalum

    DOEpatents

    Taylor, Wayne A.; Jamriska, David J.

    2001-01-01

    Hafnium is recovered from irradiated tantalum by: (a) contacting the irradiated tantalum with at least one acid to obtain a solution of dissolved tantalum; (b) combining an aqueous solution of a calcium compound with the solution of dissolved tantalum to obtain a third combined solution; (c) precipitating hafnium, lanthanide, and insoluble calcium complexes from the third combined solution to obtain a first precipitate; (d) contacting the first precipitate of hafnium, lanthanide and calcium complexes with at least one fluoride ion complexing agent to form a fourth solution; (e) selectively adsorbing lanthanides and calcium from the fourth solution by cationic exchange; (f) separating fluoride ion complexing agent product from hafnium in the fourth solution by adding an aqueous solution of ferric chloride to obtain a second precipitate containing the hafnium and iron; (g) dissolving the second precipitate containing the hafnium and iron in acid to obtain an acid solution of hafnium and iron; (h) selectively adsorbing the iron from the acid solution of hafnium and iron by anionic exchange; (i) drying the ion exchanged hafnium solution to obtain hafnium isotopes. Additionally, if needed to remove residue remaining after the product is dried, dissolution in acid followed by cation exchange, then anion exchange, is performed.

  15. Intense photoluminescence from amorphous tantalum oxide films

    NASA Astrophysics Data System (ADS)

    Zhu, Minmin; Zhang, Zhengjun; Miao, Wei

    2006-07-01

    Tantalum oxide films were deposited on silicon substrates at a temperature of ˜450°C by heating a pure tantalum foil in a rough vacuum. The films were amorphous in structure and consisted of fully oxidized Ta2O5 and (TaOx, x <2.5) suboxides. This feature resulted in strong visible light emission from the films further oxidized in the air at temperatures of 200-300°C. The mechanism for this photoluminescence behavior of the amorphous tantalum oxide films was also investigated and discussed. This study suggests that wide-band-gap materials could act as effective visible light emitters and provides a simple route to synthesize such materials.

  16. Producing Low-Oxygen Samarium/Cobalt Magnet Alloy

    NASA Technical Reports Server (NTRS)

    Das, Dilip K.; Kumar, Kaplesh; Frost, Robert T.; Chang, C. W.

    1987-01-01

    Experiments aimed at producing SmCo5 alloy with low oxygen contamination described in report. Two methods of alloying by melting without contact with crucible walls tested. Lowest oxygen contamination, 70 parts per million achieved by dc arc melting on water-cooled, tantalum-clad copper hearth in purified quiescent argon atmosphere. Report includes photographs of equipment, photomicrographs of alloy samples, detailed descriptions of procedures tried, and tables of oxygen contamination and intrinsic coercivities of samples produced.

  17. Effects of radiation quality and oxygen on clustered DNA lesions and cell death.

    PubMed

    Stewart, Robert D; Yu, Victor K; Georgakilas, Alexandros G; Koumenis, Constantinos; Park, Joo Han; Carlson, David J

    2011-11-01

    Radiation quality and cellular oxygen concentration have a substantial impact on DNA damage, reproductive cell death and, ultimately, the potential efficacy of radiation therapy for the treatment of cancer. To better understand and quantify the effects of radiation quality and oxygen on the induction of clustered DNA lesions, we have now extended the Monte Carlo Damage Simulation (MCDS) to account for reductions in the initial lesion yield arising from enhanced chemical repair of DNA radicals under hypoxic conditions. The kinetic energy range and types of particles considered in the MCDS have also been expanded to include charged particles up to and including (56)Fe ions. The induction of individual and clustered DNA lesions for arbitrary mixtures of different types of radiation can now be directly simulated. For low-linear energy transfer (LET) radiations, cells irradiated under normoxic conditions sustain about 2.9 times as many double-strand breaks (DSBs) as cells irradiated under anoxic conditions. New experiments performed by us demonstrate similar trends in the yields of non-DSB (Fpg and Endo III) clusters in HeLa cells irradiated by γ rays under aerobic and hypoxic conditions. The good agreement among measured and predicted DSBs, Fpg and Endo III cluster yields suggests that, for the first time, it may be possible to determine nucleotide-level maps of the multitude of different types of clustered DNA lesions formed in cells under reduced oxygen conditions. As particle LET increases, the MCDS predicts that the ratio of DSBs formed under normoxic to hypoxic conditions by the same type of radiation decreases monotonically toward unity. However, the relative biological effectiveness (RBE) of higher-LET radiations compared to (60)Co γ rays (0.24 keV/μm) tends to increase with decreasing oxygen concentration. The predicted RBE of a 1 MeV proton (26.9 keV/μm) relative to (60)Co γ rays for DSB induction increases from 1.9 to 2.3 as oxygen concentration

  18. High Temperature Evaluation of Tantalum Capacitors - Test 1

    DOE Data Explorer

    Cieslewski, Grzegorz

    2014-09-28

    Tantalum capacitors can provide much higher capacitance at high-temperatures than the ceramic capacitors. This study evaluates selected tantalum capacitors at high temperatures to determine their suitability for you in geothermal field. This data set contains results of the first test where three different types of capacitors were evaluated at 260C.

  19. 2017 NEPP Tasks Update for Ceramic and Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2017-01-01

    This presentation gives an overview of current NEPP tasks on ceramic and tantalum capacitors and plans for the future. It includes tasks on leakage currents, gas generation and case deformation in wet tantalum capacitors; ESR degradation and acceleration factors in MnO2 and polymer cathode capacitors. Preliminary results on the effect of moisture on degradation of reverse currents in MnO2 tantalum capacitors are discussed. Latest results on mechanical characteristics of MLCCs and modeling of degradation of leakage currents in BME capacitors with defects are also presented.

  20. Effect of the size-selective silver clusters on lithium peroxide morphology in lithium–oxygen batteries

    DOE PAGES

    Lu, Jun; Cheng, Lei; Lau, Kah Chun; ...

    2014-09-12

    Lithium–oxygen batteries have the potential needed for long-range electric vehicles, but the charge and discharge chemistries are complex and not well understood. The active sites on cathode surfaces and their role in electrochemical reactions in aprotic lithium–oxygen cells are difficult to ascertain because the exact nature of the sites is unknown. In this paper, we report the deposition of subnanometre silver clusters of exact size and number of atoms on passivated carbon to study the discharge process in lithium–oxygen cells. The results reveal dramatically different morphologies of the electrochemically grown lithium peroxide dependent on the size of the clusters. Thismore » dependence is found to be due to the influence of the cluster size on the formation mechanism, which also affects the charge process. Finally, the results of this study suggest that precise control of subnanometre surface structure on cathodes can be used as a means to improve the performance of lithium–oxygen cells.« less

  1. 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.

  2. Fabrication of a Tantalum-Based Josephson Junction for an X-Ray Detector

    NASA Astrophysics Data System (ADS)

    Morohashi, Shin'ichi; Gotoh, Kohtaroh; Yokoyama, Naoki

    2000-06-01

    We have fabricated a tantalum-based Josephson junction for an X-ray detector. The tantalum layer was selected for the junction electrode because of its long quasiparticle lifetime, large X-ray absorption efficiency and stability against thermal cycling. We have developed a buffer layer to fabricate the tantalum layer with a body-centered cubic structure. Based on careful consideration of their superconductivity, we have selected a niobium thin layer as the buffer layer for fabricating the tantalum base electrode, and a tungsten thin layer for the tantalum counter electrode. Fabricated Nb/AlOx-Al/Ta/Nb and Nb/Ta/W/AlOx-Al/Ta/Nb Josephson junctions exhibited current-voltage characteristics with a low subgap leakage current.

  3. Extreme Response in Tension and Compression of Tantalum

    NASA Astrophysics Data System (ADS)

    Remington, Tane Perry

    This research on a model bcc metal, tantalum, has three components: the study of tensile failure; defects generated under a nanoindenter; and dislocation velocities in an extreme regime generated by pulsed lasers. The processes of dynamic failure by spalling were established in nano, poly, and mono crystalline tantalum in recovery experiments following laser compression and release. The process of spall was characterized by different techniques: optical microscopy, scanning electron microscopy, microcomputerized tomography and electron backscatter diffraction. Additionally, the pull back signal was measured by VISAR and the pressure decay was compared with HYADES simulations. There are clear differences in the microscopic fracture mechanisms, dictated by the grain sizes. In the nano and poly crystals, spalling occurred by ductile fracture favoring grain boundaries. In the monocrystals, grain boundaries are absent, and the process was of ductile failure by void initiation, growth and coalescence. The spall strength of single crystalline tantalum was higher than the poly and nano crystals. It was experimentally confirmed that spall strength in tantalum increases with strain rate. In order to generate dislocations close to the surface, single crystalline tantalum with orientations (100), (110) and (111) was nanoindented with a Berkovich tip. Atomic force microscopy showed pile-ups of dislocations around the perimeter of the nanoindentations. Sections of nanoindentations were focused ion beam cut into transmission electron microscope foils. The mechanisms of deformation under a nanoindentation in tantalum were identified and quantified. Molecular dynamics simulations were conducted and the simulated plastic deformation proceeds by the formation of nanotwins, which rapidly evolve into shear dislocation loops. Dislocation densities under the indenter were estimated experimentally (~1.2 x 1015 m-2), by MD (~7 x1015 m-2) and through an analytical calculation (2.6--19 x10

  4. Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta).

    PubMed

    Chen, Wen-Jie; Zhang, Chang-Fu; Zhang, Xian-Hui; Zhang, Yong-Fan; Huang, Xin

    2013-05-15

    Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level yield singlet and doublet ground states for the bimetallic anionic and neutral clusters, respectively. All the clusters present the six-membered ring structures with different symmetries, except that the TaW2O9(-) cluster shows a chained style with a penta-coordinated tantalum atom. Spin density analyses reveal oxygen radical species in all neutral clusters, consistent with their structural characteristics. Moreover, additional calculations are performed to study the oxidation reaction of CO molecule with the W3O9(+) cation and the isoelectronic VW2O9 cluster, and results indicate that the introduction of vanadium at tungsten site can efficiently improve the oxidation reactivity. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. ON THE GEOCHEMISTRY OF NIOBIUM AND TANTALUM IN CLAYS (in Russian)

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

    Pachadzhanov, D.N.

    1963-10-01

    With the aid of the spectral method with a preliminary enrichment in tannin, the niobium and tantalum content was determined in some humid and arid clays of the Russian platform. The investigated samples were composed of 354 specimens. The average content of niobium in humid clays is 0.0020%, of tantalum 0.00024% (the Nb/Ta ratio is 8.4) and in arid clays is respectively the content of niobium 0.00133% and the content of tantalum 0.00009% (the Nb/Ta ratio is 14.8). The average value of the content of niobium content for all studied clays is 0.00183% and of the tantalum content 0.00020%, themore » Nb/Ta ratio being 9.1. In clays an interconnection of niobium with tantalum, as well as with aluminium, titanium, zirconium, and hafnium was observed. However, on the background of this connection some separation of the named elements is noted. A tendency for the Nb/Ta ratio shift from the region of matter removal towards the center of the marine basin was observed. The study of niobium and tantalum distribution over different clay fractions showed that one part of elements is connected with zircon and titanium minerals in aleuosand fraction (0.1-- 0.01 mm). Another, approximately similar part is contained in the proper clay fraction (<0. 01 mm), the tantalum somewhat more concentrating in the aleurosand fraction and niobium in the clay fraction. (P.C.H.)« less

  6. Multi-scale Modeling of Plasticity in Tantalum.

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

    Lim, Hojun; Battaile, Corbett Chandler.; Carroll, Jay

    In this report, we present a multi-scale computational model to simulate plastic deformation of tantalum and validating experiments. In atomistic/ dislocation level, dislocation kink- pair theory is used to formulate temperature and strain rate dependent constitutive equations. The kink-pair theory is calibrated to available data from single crystal experiments to produce accurate and convenient constitutive laws. The model is then implemented into a BCC crystal plasticity finite element method (CP-FEM) model to predict temperature and strain rate dependent yield stresses of single and polycrystalline tantalum and compared with existing experimental data from the literature. Furthermore, classical continuum constitutive models describingmore » temperature and strain rate dependent flow behaviors are fit to the yield stresses obtained from the CP-FEM polycrystal predictions. The model is then used to conduct hydro- dynamic simulations of Taylor cylinder impact test and compared with experiments. In order to validate the proposed tantalum CP-FEM model with experiments, we introduce a method for quantitative comparison of CP-FEM models with various experimental techniques. To mitigate the effects of unknown subsurface microstructure, tantalum tensile specimens with a pseudo-two-dimensional grain structure and grain sizes on the order of millimeters are used. A technique combining an electron back scatter diffraction (EBSD) and high resolution digital image correlation (HR-DIC) is used to measure the texture and sub-grain strain fields upon uniaxial tensile loading at various applied strains. Deformed specimens are also analyzed with optical profilometry measurements to obtain out-of- plane strain fields. These high resolution measurements are directly compared with large-scale CP-FEM predictions. This computational method directly links fundamental dislocation physics to plastic deformations in the grain-scale and to the engineering-scale applications. Furthermore

  7. Development and Applications of Porous Tantalum Trabecular Metal Enhanced Titanium Dental Implants

    PubMed Central

    Bencharit, Sompop; Byrd, Warren C.; Altarawneh, Sandra; Hosseini, Bashir; Leong, Austin; Reside, Glenn; Morelli, Thiago; Offenbacher, Steven

    2013-01-01

    Statement of Problem Porous tantalum trabecular metal has recently been incorporated in titanium dental implants as a new form of implant surface enhancement. However, there is little information on the applications of this material in implant dentistry. Methods We, therefore review the current literature on the basic science and clinical uses of this material. Results Porous tantalum metal is used to improve the contact between osseous structure and dental implants; and therefore presumably facilitate osseointegration. Success of porous tantalum metal in orthopedic implants led to the incorporation of porous tantalum metal in the design of root-from endosseous titanium implants. The porous tantalum three-dimensional enhancement of titanium dental implant surface allows for combining bone ongrowth together with bone ingrowth, or osseoincorporation. While little is known about the biological aspect of the porous tantalum in the oral cavity, there seems to be several possible advantages of this implant design. This article reviews the biological aspects of porous tantalum enhanced titanium dental implants, in particular the effects of anatomical consideration and oral environment to implant designs. Conclusions We propose here possible clinical situations and applications for this type of dental implant. Advantages and disadvantages of the implants as well as needed future clinical studies are discussed. PMID:23527899

  8. World War II, tantalum, and the evolution of modern cranioplasty technique.

    PubMed

    Flanigan, Patrick; Kshettry, Varun R; Benzel, Edward C

    2014-04-01

    Cranioplasty is a unique procedure with a rich history. Since ancient times, a diverse array of materials from coconut shells to gold plates has been used for the repair of cranial defects. More recently, World War II greatly increased the demand for cranioplasty procedures and renewed interest in the search for a suitable synthetic material for cranioprostheses. Experimental evidence revealed that tantalum was biologically inert to acid and oxidative stresses. In fact, the observation that tantalum did not absorb acid resulted in the metal being named after Tantalus, the Greek mythological figure who was condemned to a pool of water in the Underworld that would recede when he tried to take a drink. In clinical use, malleability facilitated a single-stage cosmetic repair of cranial defects. Tantalum became the preferred cranioplasty material for more than 1000 procedures performed during World War II. In fact, its use was rapidly adopted in the civilian population. During World War II and the heyday of tantalum cranioplasty, there was a rapid evolution in prosthesis implantation and fixation techniques significantly shaping how cranioplasties are performed today. Several years after the war, acrylic emerged as the cranioplasty material of choice. It had several clear advantages over its metallic counterparts. Titanium, which was less radiopaque and had a more optimal thermal conductivity profile (less thermally conductive), eventually supplanted tantalum as the most common metallic cranioplasty material. While tantalum cranioplasty was popular for only a decade, it represented a significant breakthrough in synthetic cranioplasty. The experiences of wartime neurosurgeons with tantalum cranioplasty played a pivotal role in the evolution of modern cranioplasty techniques and ultimately led to a heightened understanding of the necessary attributes of an ideal synthetic cranioplasty material. Indeed, the history of tantalum cranioplasty serves as a model for innovative

  9. Thermal shock and erosion resistant tantalum carbide ceramic material

    NASA Technical Reports Server (NTRS)

    Honeycutt, L., III; Manning, C. R. (Inventor)

    1978-01-01

    Ceramic tantalum carbide artifacts with high thermal shock and mechanical erosion resistance are provided by incorporating tungsten-rhenium and carbon particles in a tantalum carbide matrix. The mix is sintered by hot pressing to form the ceramic article which has a high fracture strength relative to its elastic modulus and thus has an improved thermal shock and mechanical erosion resistance. The tantalum carbide is preferable less than minus 100 mesh, the carbon particles are preferable less than minus 100 mesh, and the tungsten-rhenium particles are preferable elongate, having a length to thickness ratio of at least 2/1. Tungsten-rhenium wire pieces are suitable as well as graphite particles.

  10. International strategic minerals inventory summary report; niobium (columbium) and tantalum

    USGS Publications Warehouse

    Crockett, R.N.; Sutphin, D.M.

    1993-01-01

    Major world resources of niobium and tantalum are described in this summary report of information in the International Strategic Minerals Inventory (ISMI). ISMI is a cooperative data-collection effort of earth-science and mineral-resource agencies in Australia, Canada, the Federal Republic of Germany, the Republic of South Africa, the United Kingdom, and the United States of America. Part I of this report presents an overview of the resources and potential supply of niobium and tantalum based on inventory information; Part II contains tables of both geologic and mineral-resource information and includes production data collected by ISMI participants. Niobium is used principally as an alloying element in special steels and superalloys, and tantalum is used mainly in electronics. Minerals in the columbite-tantalite series are principal ore minerals of niobium and tantalum. Pyrochlore is a principal source of niobium. These minerals are found in carbonatite, certain rocks in alkaline igneous complexes, pegmatite, and placer deposits. ISMI estimates show that there are over 7 million metric tons of niobium and almost 0.5 million metric tons of tantalum in known deposits, outside of China and the former Soviet Union, for which reliable estimates have been made. Brazilian deposits, followed by Canadian deposits, contain by far the largest source of niobium. Tantalum production is spread widely among several countries, and Brazil and Canada are the most significant of these producers. Brazil's position is further strengthened by potential byproduct columbite from tin mining. Present economically exploitable resources of niobium appear to be sufficient for the near future, but Brazil will continue to be the predominant world supplier of ferrocolumbium. Tantalum, a byproduct of tin production, has been captive to the fluctuations of that market, but resources in pegmatite in Canada and Australia make it likely that future increases in the present modest demand will be met.

  11. Tantalum coatings for inertial confinement fusion dry wall designs

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

    Taylor, L.H.; Green, L.

    1996-12-31

    The coating on a dry first wall inertial confinement fusion reactor must survive the target explosion and be ductile, inexpensive, and compatible with the materials in the target, i.e. have a high atomic number Z. Calculations indicate that tantalum is the best choice for the coating material. As a test of this design 1 mm tantalum coatings were plasma sprayed onto ferrite steel tubes. They were then subjected to 100 heating-cooling cycles which simulated the stressful thermal cycling which would be encountered during five years of plant startups and shutdowns. The coatings were undamaged and continued to bond well tomore » the steel. Furthermore, chemical reactions should not degrade tantalum coatings.« less

  12. Constitutive behavior of tantalum and tantalum-tungsten alloys

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

    Chen, S.R.; Gray, G.T. III

    1996-10-01

    The effects of strain rate, temperature, and tungsten alloying on the yield stress and the strain-hardening behavior of tantalum were investigated. The yield and flow stresses of unalloyed Ta and tantalum-tungsten alloys were found to exhibit very high rate sensitivities, while the hardening rates in Ta and Ta-W alloys were found to be insensitive to strain rate and temperature at lower temperatures or at higher strain rates. This behavior is consistent with the observation that overcoming the intrinsic Peierls stress is shown to be the rate-controlling mechanism in these materials at low temperatures. The dependence of yield stress on temperaturemore » and strain rate was found to decrease, while the strain-hardening rate increased with tungsten alloying content. The mechanical threshold stress (MTS) model was adopted to model the stress-strain behavior of unalloyed Ta and the Ta-W alloys. Parameters for the constitutive relations for Ta and the Ta-W alloys were derived for the MTS model, the Johnson-Cook (JC), and the Zerilli-Armstrong (ZA) models. The results of this study substantiate the applicability of these models for describing the high strain-rate deformation of Ta and Ta-W alloys. The JC and ZA models, however, due to their use of a power strain-hardening law, were found to yield constitutive relations for Ta and Ta-W alloys that are strongly dependent on the range of strains for which the models were optimized.« less

  13. Mineral-deposit model for lithium-cesium-tantalum pegmatites

    USGS Publications Warehouse

    Bradley, Dwight C.; McCauley, Andrew D.; Stillings, Lisa L.

    2017-06-20

    Lithium-cesium-tantalum (LCT) pegmatites comprise a compositionally defined subset of granitic pegmatites. The major minerals are quartz, potassium feldspar, albite, and muscovite; typical accessory minerals include biotite, garnet, tourmaline, and apatite. The principal lithium ore minerals are spodumene, petalite, and lepidolite; cesium mostly comes from pollucite; and tantalum mostly comes from columbite-tantalite. Tin ore as cassiterite and beryllium ore as beryl also occur in LCT pegmatites, as do a number of gemstones and high-value museum specimens of rare minerals. Individual crystals in LCT pegmatites can be enormous: the largest spodumene was 14 meters long, the largest beryl was 18 meters long, and the largest potassium feldspar was 49 meters long.Lithium-cesium-tantalum pegmatites account for about one-fourth of the world’s lithium production, most of the tantalum production, and all of the cesium production. Giant deposits include Tanco in Canada, Greenbushes in Australia, and Bikita in Zimbabwe. The largest lithium pegmatite in the United States, at King’s Mountain, North Carolina, is no longer being mined although large reserves of lithium remain. Depending on size and attitude of the pegmatite, a variety of mining techniques are used, including artisanal surface mining, open-pit surface mining, small underground workings, and large underground operations using room-and-pillar design. In favorable circumstances, what would otherwise be gangue minerals (quartz, potassium feldspar, albite, and muscovite) can be mined along with lithium and (or) tantalum as coproducts.Most LCT pegmatites are hosted in metamorphosed supracrustal rocks in the upper greenschist to lower amphibolite facies. Lithium-cesium-tantalum pegmatite intrusions generally are emplaced late during orogeny, with emplacement being controlled by pre-existing structures. Typically, they crop out near evolved, peraluminous granites and leucogranites from which they are inferred to be

  14. Oxidation state and interfacial effects on oxygen vacancies in tantalum pentoxide

    DOE PAGES

    Bondi, Robert J.; Marinella, Matthew J.

    2015-02-28

    First-principles density-functional theory (DFT) calculations are used to study the atomistic structure, structural energetics, and electron density near the O monovacancy (V O n; n=0,1+,2+) in both bulk, amorphous tantalum pentoxide (a-Ta 2O 5) and also at vacuum and metallic Ta interfaces. We calculate multivariate vacancy formation energies to evaluate stability as a function of oxidation state, distance from interface plane, and Fermi energy. V O n of all oxidation states preferentially segregate at both Ta and vacuum interfaces, where the metallic interface exhibits global formation energy minima. In a-Ta 2O 5, V O 0 are characterized by structural contractionmore » and electron density localization, while V O 2+ promote structural expansion and are depleted of electron density. In contrast, interfacial V O 0 and V O 2+ show nearly indistinguishable ionic and electronic signatures indicative of a reduced V O center. Interfacial V O 2+ extract electron density from metallic Ta indicating V O 2+ is spontaneously reduced at the expense of the metal. This oxidation/reduction behavior suggests careful selection and processing of both oxide layer and metal electrodes for engineering memristor device operation.« less

  15. Kramers degeneracy and relaxation in vanadium, niobium and tantalum clusters

    NASA Astrophysics Data System (ADS)

    Diaz-Bachs, A.; Katsnelson, M. I.; Kirilyuk, A.

    2018-04-01

    In this work we use magnetic deflection of V, Nb, and Ta atomic clusters to measure their magnetic moments. While only a few of the clusters show weak magnetism, all odd-numbered clusters deflect due to the presence of a single unpaired electron. Surprisingly, for the majority of V and Nb clusters an atomic-like behavior is found, which is a direct indication of the absence of spin–lattice interaction. This is in agreement with Kramers degeneracy theorem for systems with a half-integer spin. This purely quantum phenomenon is surprisingly observed for large systems of more than 20 atoms, and also indicates various quantum relaxation processes, via Raman two-phonon and Orbach high-spin mechanisms. In heavier, Ta clusters, the relaxation is always present, probably due to larger masses and thus lower phonon energies, as well as increased spin–orbit coupling.

  16. Normobaric and hyperbaric oxygen therapy for the treatment and prevention of migraine and cluster headache.

    PubMed

    Bennett, Michael H; French, Christopher; Schnabel, Alexander; Wasiak, Jason; Kranke, Peter; Weibel, Stephanie

    2015-12-28

    Migraine and cluster headaches are severe and disabling. Migraine affects up to 18% of women, while cluster headaches are much less common (0.2% of the population). A number of acute and prophylactic therapies are available. Hyperbaric oxygen therapy (HBOT) is the therapeutic administration of 100% oxygen at environmental pressures greater than one atmosphere, while normobaric oxygen therapy (NBOT) is oxygen administered at one atmosphere. This is an updated version of the original Cochrane review published in Issue 3, 2008 under the title 'Normobaric and hyperbaric oxygen for migraine and cluster headache'. To examine the efficacy and safety of normobaric oxygen therapy (NBOT) and hyperbaric oxygen therapy (HBOT) in the treatment and prevention of migraine and cluster headache. We updated searches of the following databases up to 15 June 2015: CENTRAL (the Cochrane Library), MEDLINE, EMBASE, and CINAHL. For the original review we searched the following databases up to May 2008: CENTRAL, MEDLINE, EMBASE, CINAHL, DORCTIHM, and reference lists from relevant articles. We handsearched relevant journals and contacted researchers to identify trials. Randomised controlled trials comparing HBOT or NBOT with one another, other active therapies, placebo (sham) interventions, or no treatment in participants with migraine or cluster headache. Three review authors independently extracted data and assessed the quality of the evidence using the GRADE approach. In this update, we included 11 trials with 209 participants. Five trials (103 participants) compared HBOT versus sham therapy for acute migraine, three trials compared NBOT to sham therapy or ergotamine tartrate for cluster headache (145 participants), two trials evaluated HBOT for cluster headache (29 participants), and one trial (56 participants) compared NBOT to sham for a mixed group of headache. The risk of bias varied considerably across these trials but in general trial quality was poor to moderate. One trial may not

  17. 40 CFR 421.110 - Applicability: Description of the primary columbium-tantalum subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROTECTION AGENCY (CONTINUED) EFFLUENT GUIDELINES AND STANDARDS NONFERROUS METALS MANUFACTURING POINT SOURCE... the production of columbium or tantalum by primary columbium-tantalum facilities. [49 FR 8817, Mar. 8...

  18. Stability and migration of large oxygen clusters in UO(2+x): density functional theory calculations.

    PubMed

    Andersson, D A; Espinosa-Faller, F J; Uberuaga, B P; Conradson, S D

    2012-06-21

    Using ab initio molecular dynamics simulations and nudged elastic band calculations we examine the finite temperature stability, transition pathways, and migration mechanisms of large oxygen clusters in UO(2+x). Here we specifically consider the recently proposed split quad-interstitial and cuboctahedral oxygen clusters. It is shown that isolated cuboctahedral clusters may transform into more stable configurations that are closely linked to the split quad-interstitial. The split quad-interstitial is stable with respect to single interstitials occupying the empty octahedral holes of the UO(2) lattice. In order to better understand discrepancies between theory and experiments, the simulated atomic pair distribution functions for the split quad-interstitial structures are analyzed with respect to the distribution function for U(4)O(9) previously obtained from neutron diffraction data. Our nudged elastic band calculations suggest that the split quad-interstitial may migrate by translating one of its constituent di-interstitial clusters via a barrier that is lower than the corresponding barrier for individual interstitials, but higher than the barrier for the most stable di-interstitial cluster.

  19. Topical Report Tantalum – 2.5% Tungsten Machinability Testing

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

    L. J. Lazarus

    2009-09-02

    Protection Association (NFPA). NFPA 484, Standard for Combustible Metals, Chapter 9 Tantalum and Annex E, supplemental Information on Tantalum require cutting oil be used when machining tantalum because it burns at such a high temperature that it breaks down the water in a water-based metalworking fluid (MWF). The NFPA guide devotes approximately 20 pages to this material. The Kansas City Plant (KCP) uses Fuchs Lubricants Ecocut Base 44 LVC as a MWF. This is a highly chlorinated oil with a high flash point (above 200° F). The chlorine is very helpful in preventing BUE (Built Up Edge) that occurs frequentlymore » with this very gummy material. The Ecocut is really a MWF additive that Fuchs uses to add chlorinated fats to other non-chlorinated MWF.« less

  20. Advanced Wet Tantalum Capacitors: Design, Specifications and Performance

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2016-01-01

    Insertion of new types of commercial, high volumetric efficiency wet tantalum capacitors in space systems requires reassessment of the existing quality assurance approaches that have been developed for capacitors manufactured to MIL-PRF-39006 requirements. The specifics of wet electrolytic capacitors is that leakage currents flowing through electrolyte can cause gas generation resulting in building up of internal gas pressure and rupture of the case. The risk associated with excessive leakage currents and increased pressure is greater for high value advanced wet tantalum capacitors, but it has not been properly evaluated yet. This presentation gives a review of specifics of the design, performance, and potential reliability risks associated with advanced wet tantalum capacitors. Problems related to setting adequate requirements for DPA, leakage currents, hermeticity, stability at low and high temperatures, ripple currents for parts operating in vacuum, and random vibration testing are discussed. Recommendations for screening and qualification to reduce risks of failures have been suggested.

  1. Advanced Wet Tantalum Capacitors: Design, Specifications and Performance

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2017-01-01

    Insertion of new types of commercial, high volumetric efficiency wet tantalum capacitors in space systems requires reassessment of the existing quality assurance approaches that have been developed for capacitors manufactured to MIL-PRF-39006 requirements. The specifics of wet electrolytic capacitors is that leakage currents flowing through electrolyte can cause gas generation resulting in building up of internal gas pressure and rupture of the case. The risk associated with excessive leakage currents and increased pressure is greater for high value advanced wet tantalum capacitors, but it has not been properly evaluated yet. This presentation gives a review of specifics of the design, performance, and potential reliability risks associated with advanced wet tantalum capacitors. Problems related to setting adequate requirements for DPA, leakage currents, hermeticity, stability at low and high temperatures, ripple currents for parts operating in vacuum, and random vibration testing are discussed. Recommendations for screening and qualification to reduce risks of failures have been suggested.

  2. Tribological performance of polycrystalline tantalum-carbide-incorporated diamond films on silicon substrates

    NASA Astrophysics Data System (ADS)

    Ullah, Mahtab; Rana, Anwar Manzoor; Ahmed, E.; Malik, Abdul Sattar; Shah, Z. A.; Ahmad, Naseeb; Mehtab, Ujala; Raza, Rizwan

    2018-05-01

    Polycrystalline tantalum-carbide-incorporated diamond coatings have been made on unpolished side of Si (100) wafer by hot filament chemical vapor deposition process. Morphology of the coatings has been found to vary from (111) triangular-facetted to predominantly (111) square-faceted by increasing the concentration of tantalum carbide. The results have been compared to those of a diamond reference coating with no tantalum content. An increase in roughness has been observed with the increase of tantalum carbide (TaC) due to change in morphology of the diamond films. It is noticed that roughness of the coatings increases as grains become more square-faceted. It is found that diamond coatings involving tantalum carbide are not as resistant as diamond films with no TaC content and the coefficient of friction for such coatings with microcrystalline grains can be manipulated to 0·33 under high vacuum of 10-7 Torr. Such a low friction coefficient value enhances tribological behavior of unpolished Si substrates and can possibly be used in sliding applications.

  3. Anomalous softening of yield strength in tantalum at high pressures

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

    Jing, Qiumin, E-mail: j-qm@163.com; Wu, Qiang; Xu, Ji-an

    2015-02-07

    The pressure dependence of the yield strength of tantalum was investigated experimentally up to 101 GPa at room temperature using a diamond anvil cell. A yield strength softening is observed between 52 and 84 GPa, whereas a normal trend is observed below 52 GPa and above 84 GPa. The onset pressure of the softening is in agreement with previous results obtained by the pressure gradient method and shock wave experiments. This unusual strength softening in tantalum is not related with structural transformation, preferred orientation, or material damage. Our measurements indicate that microscopic deviatoric strain is the major reason for the observed strength softening inmore » tantalum.« less

  4. High efficiency tantalum-based ceramic composite structures

    NASA Technical Reports Server (NTRS)

    Stewart, David A. (Inventor); Leiser, Daniel B. (Inventor); DiFiore, Robert R. (Inventor); Katvala, Victor W. (Inventor)

    2010-01-01

    Tantalum-based ceramics are suitable for use in thermal protection systems. These composite structures have high efficiency surfaces (low catalytic efficiency and high emittance), thereby reducing heat flux to a spacecraft during planetary re-entry. These ceramics contain tantalum disilicide, molybdenum disilicide and borosilicate glass. The components are milled, along with a processing aid, then applied to a surface of a porous substrate, such as a fibrous silica or carbon substrate. Following application, the coating is then sintered on the substrate. The composite structure is substantially impervious to hot gas penetration and capable of surviving high heat fluxes at temperatures approaching 3000.degree. F. and above.

  5. A niobium oxide-tantalum oxide selector-memristor self-aligned nanostack

    NASA Astrophysics Data System (ADS)

    Diaz Leon, Juan J.; Norris, Kate J.; Yang, J. Joshua; Sevic, John F.; Kobayashi, Nobuhiko P.

    2017-03-01

    The integration of nonlinear current-voltage selectors and bi-stable memristors is a paramount step for reliable operation of crossbar arrays. In this paper, the self-aligned assembly of a single nanometer-scale device that contains both a selector and a memristor is presented. The two components (i.e., selector and memristor) are vertically assembled via a self-aligned fabrication process combined with electroforming. In designing the device, niobium oxide and tantalum oxide are chosen as materials for selector and memristor, respectively. The formation of niobium oxide is visualized by exploiting the self-limiting reaction between niobium and tantalum oxide; crystalline niobium (di)oxide forms at the interface between metallic niobium and tantalum oxide via electrothermal heating, resulting in a niobium oxide selector self-aligned to a tantalum oxide memristor. A steady-state finite element analysis is used to assess the electrothermal heating expected to occur in the device. Current-voltage measurements and structural/chemical analyses conducted for the virgin device, the electroforming process, and the functional selector-memristor device are presented. The demonstration of a self-aligned, monolithically integrated selector-memristor device would pave a practical pathway to various circuits based on memristors attainable at manufacturing scales.

  6. Analysis of Weibull Grading Test for Solid Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2010-01-01

    Weibull grading test is a powerful technique that allows selection and reliability rating of solid tantalum capacitors for military and space applications. However, inaccuracies in the existing method and non-adequate acceleration factors can result in significant, up to three orders of magnitude, errors in the calculated failure rate of capacitors. This paper analyzes deficiencies of the existing technique and recommends more accurate method of calculations. A physical model presenting failures of tantalum capacitors as time-dependent-dielectric-breakdown is used to determine voltage and temperature acceleration factors and select adequate Weibull grading test conditions. This, model is verified by highly accelerated life testing (HALT) at different temperature and voltage conditions for three types of solid chip tantalum capacitors. It is shown that parameters of the model and acceleration factors can be calculated using a general log-linear relationship for the characteristic life with two stress levels.

  7. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

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

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.

    Quantum chemical calculations were employed to model the interactions of the [(NH 4 +) 4(HSO 4 -) 4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH 4 +) 4(SOmore » 4 -) 4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

  8. Growth of Ammonium Bisulfate Clusters by Adsorption of Oxygenated Organic Molecules

    DOE PAGES

    DePalma, Joseph W.; Wang, Jian; Wexler, Anthony S.; ...

    2015-10-21

    Quantum chemical calculations were employed to model the interactions of the [(NH 4 +) 4(HSO 4 -) 4] ammonium bisulfate cluster with one or more molecular products of monoterpene oxidation. A strong interaction was found between the bisulfate ion of the cluster and a carboxylic acid, aldehyde or ketone functionality of the organic molecule. Free energies of adsorption for carboxylic acids were in the -70 to -73 kJ/mol range, while those for aldehydes and ketones were in the -46 to -50 kJ/mol range. These values suggest that a small ambient ammonium bisulfate cluster, such as the [(NH 4 +) 4(SOmore » 4 -) 4] cluster, is able to adsorb an oxygenated organic molecule. Although adsorption of the first molecule is highly favorable, adsorption of subsequent molecules is not, suggesting that sustained uptake of organic molecules does not occur, and thus is not a pathway for continuing growth of the cluster. This result is consistent with ambient measurements showing that particles below ~1 nm grow slowly, while those above 1 nm grow at an increasing rate presumably due to a lower surface energy barrier enabling the uptake of organic molecules. This work provides insight into the molecular level interactions which affect sustained cluster growth by uptake of organic molecules.« less

  9. The Tri-lab Tantalum Strength Consortium

    NASA Astrophysics Data System (ADS)

    Flicker, Dawn G.; Arsenlis, Thomas A.; Austin, Ryan; Barton, Nathan R.; Benage, John F.; Bronkhorst, Curt A.; Brown, Justin L.; Brown, Staci L.; Buttler, William T.; Shen, Shuh-Rong; Dattelbaum, Dana M.; Fensin, Sayu J.; Gray, George T., III; Lane, J. Matthew D.; Lim, Hojun; Luscher, D. J.; Mattsson, Thomas R.; McNabb, Dennis P.; Remington, Bruce A.; Park, Hye-Sook; Prisbrey, Shon T.; Prime, Michael B.; Scharff, Robert J.; Schraad, Mark W.; Sun, Amy C.

    2017-06-01

    A Tri-lab consortium of experimentalists and theorists at SNL, LLNL, and LANL is joining forces to better understand tantalum strength across an unprecedented range of loading conditions. The team is collecting and comparing tantalum strength data from Hopkinson bar, Taylor cylinder, guns, Z, Omega and the NIF. These experiments, all using Ta from a single lot, span pressures from tenths to hundreds of GPa and strain rates from 103 to 107. New experiments are underway to provide more overlap between the platforms. The experiments are being simulated with a variety of models in order to determine which processes are important under which conditions. The presentation will show results to date. Sandia is a multi-program laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.

  10. Simultaneous determination of tantalum and hafnium in silicates by neutron activation analysis

    USGS Publications Warehouse

    Greenland, L.P.

    1968-01-01

    A neutron activation procedure suitable for the routine determination of tantalum and hafnium in silicates is described. The irradiated sample is fused with sodium peroxide and leached, and the insoluble hydroxides are dissolved in dilute hydrofluoric acid-hydrochloric acid. After LaF3 and AgCl scavenges, tantalum and hafnium are separated by anion exchange. Tantalum is obtained radiochemically pure; 233Pa and 95Zr contaminants in the hafnium fraction are resolved by ??-ray spectrometry. The chemical yield of the procedure is detemined after counting by re-irradiation. Values for the 8 U.S. Geological Survey standard rocks are reported. ?? 1968.

  11. Synthesis of Coral-Like Tantalum Oxide Films via Anodization in Mixed Organic-Inorganic Electrolytes

    PubMed Central

    Yu, Hongbin; Zhu, Suiyi; Yang, Xia; Wang, Xinhong; Sun, Hongwei; Huo, Mingxin

    2013-01-01

    We report a simple method to fabricate nano-porous tantalum oxide films via anodization with Ta foils as the anode at room temperature. A mixture of ethylene glycol, phosphoric acid, NH4F and H2O was used as the electrolyte where the nano-porous tantalum oxide could be synthesized by anodizing a tantalum foil for 1 h at 20 V in a two–electrode configuration. The as-prepared porous film exhibited a continuous, uniform and coral-like morphology. The diameters of pores ranged from 30 nm to 50 nm. The pores interlaced each other and the depth was about 150 nm. After calcination, the as-synthesized amorphous tantalum oxide could be crystallized to the orthorhombic crystal system. As observed in photocatalytic experiments, the coral-like tantalum oxide exhibited a higher photocatalytic activity for the degradation of phenol than that with a compact surface morphology, and the elimination rate of phenol increased by 66.7%. PMID:23799106

  12. Biological Response of Human Bone Marrow-Derived Mesenchymal Stem Cells to Commercial Tantalum Coatings with Microscale and Nanoscale Surface Topographies

    NASA Astrophysics Data System (ADS)

    Skoog, Shelby A.; Kumar, Girish; Goering, Peter L.; Williams, Brian; Stiglich, Jack; Narayan, Roger J.

    2016-06-01

    Tantalum is a promising orthopaedic implant coating material due to its robust mechanical properties, corrosion resistance, and excellent biocompatibility. Previous studies have demonstrated improved biocompatibility and tissue integration of surface-treated tantalum coatings compared to untreated tantalum. Surface modification of tantalum coatings with biologically inspired microscale and nanoscale features may be used to evoke optimal tissue responses. The goal of this study was to evaluate commercial tantalum coatings with nanoscale, sub-microscale, and microscale surface topographies for orthopaedic and dental applications using human bone marrow-derived mesenchymal stem cells (hBMSCs). Tantalum coatings with different microscale and nanoscale surface topographies were fabricated using a diffusion process or chemical vapor deposition. Biological evaluation of the tantalum coatings using hBMSCs showed that tantalum coatings promote cellular adhesion and growth. Furthermore, hBMSC adhesion to the tantalum coatings was dependent on surface feature characteristics, with enhanced cell adhesion on sub-micrometer- and micrometer-sized surface topographies compared to hybrid nano-/microstructures. Nanostructured and microstructured tantalum coatings should be further evaluated to optimize the surface coating features to promote osteogenesis and enhance osseointegration of tantalum-based orthopaedic implants.

  13. The Evaluation of Hydroxyapatite (HA) Coated and Uncoated Porous Tantalum for Biomedical Material Applications

    NASA Astrophysics Data System (ADS)

    Safuan, Nadia; Sukmana, Irza; Kadir, Mohammed Rafiq Abdul; Noviana, Deni

    2014-04-01

    Porous tantalum has been used as an orthopedic implant for bone defects as it has a good corrosion resistance and fatigue behaviour properties. However, there are some reports on the rejection of porous Ta after the implantation. Those clinical cases refer to the less bioactivity of metallic-based materials. This study aims to evaluate hydroxyapatite coated and uncoated porous Tantalum in order to improve the biocompatibility of porous tantalum implant and osseointegration. Porous tantalum was used as metallic-base substrate and hydroxyapatite coating has been done using plasma-spraying technique. Scanning Electron Microscopy (SEM) and Field Emission Scanning Electron Microscopy (FESEM) techniques were utilizes to investigate the coating characteristics while Confocal Raman Microscopy to investigate the interface and image. The effect of coating to the corrosion behaviour was assessed by employing potentiodynamic polarization tests in simulated body fluid at 37±1 °C. Based on SEM and FESEM results, the morphologies as well the weight element consists in the uncoated and hydroxyapatite coated porous tantalum were revealed. The results indicated that the decrease in corrosion current density for HA coated porous Ta compared to the uncoated porous Ta. This study concluded that by coating porous tantalum with HA supports to decrease the corrosion rate of pure porous.

  14. NIOBIUM-TANTALUM SEPARATION

    DOEpatents

    Wilhelm, H.A.; Foos, R.A.

    1959-01-27

    The usual method for the separation of tantalum and niobium consists of a selective solvent extraction from an aqueous hydrofluoric acid solution of the metals. A difficulty encountered in this process is the fact that the corrosion problems associated with hydrofluoric acid are serious. It has been found that the corrosion caused by the hydrofluoric acid may be substantially reduced by adding to the acidic solution an amine, such as phenyl diethanolamine or aniline, and adjusting pH value to between 4 and 6.

  15. Tantalum modified ferritic iron base alloys

    NASA Technical Reports Server (NTRS)

    Oldrieve, R. E.; Blankenship, C. P. (Inventor)

    1977-01-01

    Strong ferritic alloys of the Fe-CR-Al type containing 0.4% to 2% tantalum were developed. These alloys have improved fabricability without sacrificing high temperature strength and oxidation resistance in the 800 C (1475 F) to 1040 C (1900 F) range.

  16. Effect of Compressive Stresses on Leakage Currents in Microchip Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2012-01-01

    Microchip tantalum capacitors are manufactured using new technologies that allow for production of small size capacitors (down to EIA case size 0402) with volumetric efficiency much greater than for regular chip capacitors. Due to a small size of the parts and leadless design they might be more sensitive to mechanical stresses that develop after soldering onto printed wiring boards (PWB) compared to standard chip capacitors. In this work, the effect of compressive stresses on leakage currents in capacitors has been investigated in the range of stresses up to 200 MPa. Significant, up to three orders of magnitude, variations of currents were observed after the stress exceeds a certain critical level that varied from 10 MPa to 180 MPa for capacitors used in this study. A stress-induced generation of electron traps in tantalum pentoxide dielectric is suggested to explain reversible variations of leakage currents in tantalum capacitors. Thermo-mechanical characteristics of microchip capacitors have been studied to estimate the level of stresses caused by assembly onto PWB and assess the risk of stress-related degradation and failures. Keywords: tantalum capacitors, leakage current, soldering, reliability, mechanical stress.

  17. The preparation of tantalum powder using a MR-EMR combination process

    NASA Astrophysics Data System (ADS)

    Yoon, Jae Sik; Kim, Byung Il

    2007-04-01

    In the conventional metallothermic reduction (MR) process used to obtain tantalum powder in batch-type operation, it is difficult to control the morphology and location of the tantalum deposits. In contrast, an electronically mediated reaction (EMR) process is capable of overcoming this difficulty. It has the advantage of being a continuous process, but has the disadvantage of a poor reduction yield. A process known as the MR-EMR combination process is able to overcome the shortcomings of the MR and EMR processes. In this study, an MR-EMR combination process is applied to the production of tantalum powder via sodium reduction of K2TaF7. In the MR-EMR combination process, the total charge passed through an external circuit and the average particle size (FSSS) increase as the reduction temperature increases. In addition, the proportion of fine particles (-325 mesh) decreases as the reduction temperature increasess. The tantalum yield improved from 65 to 74% as the reduction temperature increased. Taking into account the charge, impurities, morphology, particle size and yield, a reduction temperature of 1123 K was found to be optimum for the MR-EMR combination process.

  18. Reliability of High-Voltage Tantalum Capacitors. Parts 3 and 4)

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2010-01-01

    Weibull grading test is a powerful technique that allows selection and reliability rating of solid tantalum capacitors for military and space applications. However, inaccuracies in the existing method and non-adequate acceleration factors can result in significant, up to three orders of magnitude, errors in the calculated failure rate of capacitors. This paper analyzes deficiencies of the existing technique and recommends more accurate method of calculations. A physical model presenting failures of tantalum capacitors as time-dependent-dielectric-breakdown is used to determine voltage and temperature acceleration factors and select adequate Weibull grading test conditions. This model is verified by highly accelerated life testing (HALT) at different temperature and voltage conditions for three types of solid chip tantalum capacitors. It is shown that parameters of the model and acceleration factors can be calculated using a general log-linear relationship for the characteristic life with two stress levels.

  19. Surface nanotexturing of tantalum by laser ablation in water

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

    Barmina, E V; Simakin, Aleksandr V; Shafeev, Georgii A

    2009-01-31

    Surface nanotexturing of tantalum by ablation with short laser pulses in water has been studied experimentally using three ablation sources: a neodymium laser with a pulse duration of 350 ps, an excimer laser (248 nm) with a pulse duration of 5 ps and a Ti:sapphire laser with a pulse duration of 180 fs. The morphology of the nanotextured surfaces has been examined using a nanoprofilometer and field emission scanning electron microscope. The results demonstrate that the average size of the hillocks produced on the target surface depends on the laser energy density and is {approx}200 nm at an energy densitymore » approaching the laser-melting threshold of tantalum and a pulse duration of 350 ps. Their surface density reaches 10{sup 6} cm{sup -2}. At a pulse duration of 5 ps, the average hillock size is 60-70 nm. Nanotexturing is accompanied by changes in the absorption spectrum of the tantalum surface in the UV and visible spectral regions. The possible mechanisms of surface nanotexturing and potential applications of this effect are discussed. (nanostructures)« less

  20. Semimicrodetermination of combined tantalum and niobium with selenous acid

    USGS Publications Warehouse

    Grimaldi, F.S.; Schnepfe, M.

    1959-01-01

    Tantalum and niobium are separated and determined gravimetrically by precipitation with selenous acid from highly acidic solutions in the absence of complexing agents. Hydrogen peroxide is used in the preparation of the solution and later catalytically destroyed during digestion of the precipitate. From 0.2 to 30 mg., separately or in mixtures, of niobium or tantalum pentoxide can be separated from mixtures containing 100 mg. each of the oxides of scandium, yttrium, cerium, vanadium, molybdenum, iron, aluminum, tin, lead, and bismuth with a single precipitation; and from 30 mg. of titanium dioxide, and 50 mg. each of the oxides of antimony and thorium, when present separately, with three precipitations. At least 50 mg. of uranium(VI) oxide can be separated with a single precipitation when present alone; otherwise, three precipitations may be needed. Zirconium does not interfere when the tantalum and niobium contents of the sample are small, but in general, zirconium as well as tungsten interfere. The method is applied to the determination of the earth acids in tantaloniobate ores.

  1. Tantalum protective coatings for fusion reactor applications

    NASA Astrophysics Data System (ADS)

    Brossa, Francesco; Piatti, Giovanni; Bardy, Michel

    Tantalum has a very low sputtering yield, high melting point, low vapour pressure and good mechanical properties at low and high temperatures, so it is a very interesting candidate for the first wall and blanket structural components. Tantalum coatings overcome the problems of fabrication and joining bulk Ta, thus reducing also dead weight and cost. Ta coatings were produced by chemical vapour deposition and plasma spraying on four conventional structural materials: Al, Cu, AISI 316 L and Inconel 600. The conditions which improve adherence have been studied. The composition of the films was determined by chemical means and by X-ray analysis. Metallographie examination was employed to define the morphological structure of the deposits. The adherence of the coatings was determined by subjecting the samples to bend tests and to thermal shocks.

  2. Effects of severe stressing on tantalum capacitors

    NASA Technical Reports Server (NTRS)

    Shakar, J. F.; Fairfield, E. H.

    1981-01-01

    The ultimate capabilities of an all tantalum capacitor were determined and evaluated. The evaluation included: 175 C life; 100 cycle thermal shock; 70 g random vibration; 3000 g shock; and 90 C ase ripple current.

  3. Micro/Nano Structural Tantalum Coating for Enhanced Osteogenic Differentiation of Human Bone Marrow Stem Cells

    PubMed Central

    Ding, Ding; Xie, Youtao; Li, Kai; Huang, Liping; Zheng, Xuebin

    2018-01-01

    Recently, tantalum has been attracting much attention for its anticorrosion resistance and biocompatibility, and it has been widely used in surface modification for implant applications. To improve its osteogenic differentiation of human bone marrow stem cells (hBMSCs), a micro/nano structure has been fabricated on the tantalum coating surface through the combination of anodic oxidation and plasma spraying method. The morphology, composition, and microstructure of the modified coating were comprehensively studied by employing scanning electron microscopy (SEM), X-ray diffraction (XRD) as well as transmission electron microscopy (TEM). The effects of hierarchical structures as well as micro-porous structure of tantalum coating on the behavior for human bone marrow stem cells (hBMSCs) were evaluated and compared at both cellular and molecular levels in vitro. The experimental results show that a hierarchical micro/nano structure with Ta2O5 nanotubes spread onto a micro-scale tantalum coating has been fabricated successfully, which is confirmed to promote cell adhesion and spreading. Besides, the hierarchical micro/nano tantalum coating can provide 1.5~2.1 times improvement in gene expression, compared with the micro-porous tantalum coating. It demonstrates that it can effectively enhance the proliferation and differentiation of hBMSCs in vitro. PMID:29614022

  4. Micro/Nano Structural Tantalum Coating for Enhanced Osteogenic Differentiation of Human Bone Marrow Stem Cells.

    PubMed

    Ding, Ding; Xie, Youtao; Li, Kai; Huang, Liping; Zheng, Xuebin

    2018-04-03

    Recently, tantalum has been attracting much attention for its anticorrosion resistance and biocompatibility, and it has been widely used in surface modification for implant applications. To improve its osteogenic differentiation of human bone marrow stem cells (hBMSCs), a micro/nano structure has been fabricated on the tantalum coating surface through the combination of anodic oxidation and plasma spraying method. The morphology, composition, and microstructure of the modified coating were comprehensively studied by employing scanning electron microscopy (SEM), X-ray diffraction (XRD) as well as transmission electron microscopy (TEM). The effects of hierarchical structures as well as micro-porous structure of tantalum coating on the behavior for human bone marrow stem cells (hBMSCs) were evaluated and compared at both cellular and molecular levels in vitro. The experimental results show that a hierarchical micro/nano structure with Ta₂O₅ nanotubes spread onto a micro-scale tantalum coating has been fabricated successfully, which is confirmed to promote cell adhesion and spreading. Besides, the hierarchical micro/nano tantalum coating can provide 1.5~2.1 times improvement in gene expression, compared with the micro-porous tantalum coating. It demonstrates that it can effectively enhance the proliferation and differentiation of hBMSCs in vitro.

  5. Random Vibration Testing of Advanced Wet Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2015-01-01

    Advanced wet tantalum capacitors allow for improved performance of power supply systems along with substantial reduction of size and weight of the systems that is especially beneficial for space electronics. Due to launch-related stresses, acceptance testing of all space systems includes random vibration test (RVT). However, many types of advanced wet tantalum capacitors cannot pass consistently RVT at conditions specified in MIL-PRF-39006, which impedes their use in space projects. This requires a closer look at the existing requirements, modes and mechanisms of failures, specifics of test conditions, and acceptance criteria. In this work, different lots of advanced wet tantalum capacitors from four manufacturers have been tested at step stress random vibration conditions while their currents were monitored before, during, and after the testing. It has been shown that the robustness of the parts and their reliability are mostly due to effective self-healing processes and limited current spiking or minor scintillations caused by RVT do not increase the risk of failures during operation. A simple model for scintillations events has been used to simulate current spiking during RVT and optimize test conditions. The significance of scintillations and possible effects of gas generation have been discussed and test acceptance criteria for limited current spiking have been suggested.

  6. A niobium and tantalum co-doped perovskite cathode for solid oxide fuel cells operating below 500 °C

    PubMed Central

    Li, Mengran; Zhao, Mingwen; Li, Feng; Zhou, Wei; Peterson, Vanessa K.; Xu, Xiaoyong; Shao, Zongping; Gentle, Ian; Zhu, Zhonghua

    2017-01-01

    The slow activity of cathode materials is one of the most significant barriers to realizing the operation of solid oxide fuel cells below 500 °C. Here we report a niobium and tantalum co-substituted perovskite SrCo0.8Nb0.1Ta0.1O3−δ as a cathode, which exhibits high electroactivity. This cathode has an area-specific polarization resistance as low as ∼0.16 and ∼0.68 Ω cm2 in a symmetrical cell and peak power densities of 1.2 and 0.7 W cm−2 in a Gd0.1Ce0.9O1.95-based anode-supported fuel cell at 500 and 450 °C, respectively. The high performance is attributed to an optimal balance of oxygen vacancies, ionic mobility and surface electron transfer as promoted by the synergistic effects of the niobium and tantalum. This work also points to an effective strategy in the design of cathodes for low-temperature solid oxide fuel cells. PMID:28045088

  7. Guidelines for the selection and application of tantalum electrolytic capacitors in highly reliable equipment

    NASA Technical Reports Server (NTRS)

    Holladay, A. M.

    1978-01-01

    Guidelines are given for the selection and application of three types of tantalum electrolytic capacitors in current use in the design of electrical and electronic circuits for space flight missions. In addition, the guidelines supplement requirements of existing military specifications used in the procurement of capacitors. A need exists for these guidelines to assist designers in preventing some of the recurring, serious problems experienced with tantalum electrolytic capacitors in the recent past. The three types of capacitors covered by these guidelines are; solid, wet foil, and tantalum cased wet slug.

  8. Electronic transitions of tantalum monofluoride

    NASA Astrophysics Data System (ADS)

    Ng, K. F.; Zou, Wenli; Liu, Wenjian; Cheung, A. S.-C.

    2017-03-01

    The electronic transition spectrum of the tantalum monofluoride (TaF) molecule in the spectral region between 448 and 560 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. The TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Twenty-two vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transitions. The X3Σ-(0+) state has been identified to be the ground state and the determined equilibrium bond length, re, and vibrational frequency, ωe, are 1.8184 Å and 700.1 cm-1, respectively. The low-lying Λ-S states and Ω sub-states of TaF were also theoretically studied at the MRCISD+Q level of theory with spin-orbit coupling. The Ω = 0+ and 2 sub-states from the -3Σ and 3Φ state have been found to be the ground and the first excited states, respectively, which agrees well with our experimental determinations. This work represents the first experimental investigation of the molecular structure of the TaF molecule.

  9. Probing C-O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

    NASA Astrophysics Data System (ADS)

    Lyon, Jonathan T.; Gruene, Philipp; Fielicke, André; Meijer, Gerard; Rayner, David M.

    2009-11-01

    The binding of carbon monoxide to iron, ruthenium, rhenium, and tungsten clusters is studied by means of infrared multiple photon dissociation spectroscopy. The CO stretching mode is used to probe the interaction of the CO molecule with the metal clusters and thereby the activation of the C-O bond. CO is found to adsorb molecularly to atop positions on iron clusters. On ruthenium and rhenium clusters it also binds molecularly. In the case of ruthenium, binding is predominantly to atop sites, however higher coordinated CO binding is also observed for both metals and becomes prevalent for rhenium clusters containing more than nine atoms. Tungsten clusters exhibit a clear size dependence for molecular versus dissociative CO binding. This behavior denotes the crossover to the purely dissociative CO binding on the earlier transition metals such as tantalum.

  10. Performance and Reliability of Solid Tantalum Capacitors at Cryogenic Conditions

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2006-01-01

    Performance of different types of solid tantalum capacitors was evaluated at room and low temperatures, down to 15 K. The effect of temperature on frequency dependencies of capacitance, effective series resistances (ESR), leakage currents, and breakdown voltages has been investigated and analyzed. To assess thermo-mechanical robustness of the parts, several groups of loose capacitors and those soldered on FR4 boards were subjected to multiple (up to 500) temperature cycles between room temperature and 77 K. Experiments and mathematical modeling have shown that degradation in tantalum capacitors at low temperatures is mostly due to increasing resistance of the manganese cathode layer, resulting in substantial decrease of the roll-off frequency. Absorption currents follow a power law, I approximately t(sup -m), with the exponent m varying from 0.8 to 1.1. These currents do not change significantly at cryogenic conditions and the value of the exponent remains the same down to 15 K. Variations of leakage currents with voltage can be described by Pool-Frenkel and Schottky mechanisms of conductivity, with the Schottky mechanism prevailing at cryogenic conditions. Breakdown voltages of tantalum capacitors increase and the probability of scintillations decreases at cryogenic temperatures. However, breakdown voltages measured during surge current testing decrease at liquid nitrogen (LN) compared to room-temperature conditions. Results of temperature cycling suggest that tantalum capacitors are capable of withstanding multiple exposures to cryogenic conditions, but the probability of failures varies for different part types.

  11. EUV emission spectra in collisions of highly charged tantalum ions with nitrogen and oxygen molecules

    NASA Astrophysics Data System (ADS)

    Tanuma, Hajime; Numadate, Naoki; Uchikura, Yoshiyuki; Shimada, Kento; Akutsu, Takuto; Long, Elaine; O'Sullivan, Gerry

    2017-10-01

    We have performed ion beam collision experiments using multiply charged tantalum ions and observed EUV (extreme ultra-violet) emission spectra in collisions of ions with molecular targets, N2 and O2. Broad UTAs (un-resolved transition arrays) from multiply charged Ta ions were observed, and the mean wavelengths of the UTAs shifted and became shorter at higher charge statea of Ta ions. These UTAs may be attributed to the 4f-5d and 4f-5g transitions. Not only the UTA emission from incident ions, but also the sharp emission lines from multiply charged fragment atomic ions were observed. Production of temporary highly charged molecular ions, their kinetic energy and fragmentation processes have been investigated with coincident detection technique. However, the observation of emission from the fragments might be for the first time. The formation mechanisms of the multiply charged fragment atomic ions from target molecules are discussed.

  12. Tantalum-based thin film coatings for wear resistant arthroprostheses.

    PubMed

    Balagna, C; Faga, M G; Spriano, S

    2011-10-01

    Cobalt-chromium-molybdenum alloys with high carbon content (HC-CoCrMo) are widely used as materials for arthroprosthesis, in particular in metal-on-metal (MoM) hip joints. In spite of their good wear and corrosion resistance, production of metallic wear particles and metal ion release will occur on a large time-scale. An enhancement of the metal ion level in the patient's blood and urine is often reported in clinical data. Hypersensitivity, inflammatory response and cell necrosis can occur as consequence. So implants on young patients and women on childbearing age are not so widespread. The aim of this research is the realization of a thin film coating in order to improve the biocompatibility of Co-based alloys and to reduce debris production, ion release and citotoxicity. The innovative process consists of a thermal treatment in molten salts, in order to obtain a tantalum enriched thin film coating. Tantalum is chosen because it is considered a biocompatible metal with high corrosion resistance and low ion release. Three HC-CoCrMo alloys, produced by different manufacturing processes, are tested as substrates. The coating is a thin film of TaC or it can be composed by a multilayer of two tantalum carbides and metallic tantalum, depending on the temperature of the treatment and on the carbon content of the substrate. The thin films as well the substrates are characterized from the structural, chemical and morphological point of view. Moreover mechanical behaviour of treated and untreated materials is analyzed by means of nanohardness, scratch and ball-on-disc wear tests. The coating increases the mechanical and tribological properties of HC-CoCrMo.

  13. A preliminary deposit model for lithium-cesium-tantalum (LCT) pegmatites

    USGS Publications Warehouse

    Bradley, Dwight; McCauley, Andrew

    2013-01-01

    This report is part of an effort by the U.S. Geological Survey to update existing mineral deposit models and to develop new ones. We emphasize practical aspects of pegmatite geology that might directly or indirectly help in exploration for lithium-cesium-tantalum (LCT) pegmatites, or for assessing regions for pegmatite-related mineral resource potential. These deposits are an important link in the world’s supply chain of rare and strategic elements, accounting for about one-third of world lithium production, most of the tantalum, and all of the cesium.

  14. Deformation of Cases in High Capacitance Value Wet Tantalum Capacitors under Environmental Stresses

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2016-01-01

    Internal gas pressure in hermetic wet tantalum capacitors is created by air, electrolyte vapor, and gas generated by electrochemical reactions at the electrodes. This pressure increases substantially with temperature and time of operation due to excessive leakage currents. Deformation of the case occurs when the internal pressure exceeds pressure of the environments and can raise significantly when a part operates in space. Contrary to the cylinder case wet tantalum capacitors that have external sealing by welding and internal sealing provided by the Teflon bushing and crimping of the case, no reliable internal sealing exists in the button case capacitors. Single seal design capacitors are used for high capacitance value wet tantalum capacitors manufactured per DLA L&M drawings #04003, 04005, and 10011, and require additional analysis to assure their reliable application in space systems. In this work, leakage currents and case deformation of button case capacitors were measured during different environmental test conditions. Recommendations for derating, screening and qualification testing are given. This work is a continuation of a series of NEPP reports related to quality and reliability of wet tantalum capacitors.

  15. Superconducting characteristics in purified tantalum-foils

    NASA Astrophysics Data System (ADS)

    Hu, Qinghua; Wang, Zhihe

    2018-07-01

    We have conducted extensive investigations on the electrical transport and magnetization on a purified tantalum foil with extremely sharp resistive transition (transition width ΔTc < 0.02 K) at 0 T and residual resistivity ratio ρ290K/ρ5K= 16.75. Many effects, such as anisotropic field-induced resistive broadening and second peak of the magnetization-hysteresis loop, are observed in the sample. The maximum upper critical field determined by criteria of R/Rn = 0.9 is about 1.08 T rather weak compared to that in cuprate and/or iron-based superconductors. Although the value of upper critical field Hc2(0) and the field dependence of effective pinning energy U show that the flux pinning potential is weaker, the critical current density Jc(2 K, 0 T) = 1.145 × 105 A/cm2 and the effect of second peak indicate that there should be higher collective vortex pinning potential in the tantalum foil. The carriers are dominated by holes with the density n = 6.6 × 1022/cm3.

  16. Catalytic Hydroamination of Alkynes and Norbornene with Neutral and Cationic Tantalum Imido Complexes

    PubMed Central

    Anderson, Laura L.; Arnold, John; Bergman, Robert G.

    2005-01-01

    Several tantalum imido complexes have been synthesized and shown to efficiently catalyze the hydroamination of internal and terminal alkynes. An unusual hydroamination/hydroarylation reaction of norbornene catalyzed by a highly electrophilic cationic tantalum imido complex is also reported. Factors affecting catalyst activity and selectivity are discussed along with mechanistic insights gained from stoichiometric reactions. PMID:15255680

  17. Characterization of Tantalum Polymer Capacitors

    NASA Technical Reports Server (NTRS)

    Spence, Penelope

    2012-01-01

    Overview Reviewed data Caution must be taken when accelerating test conditions Data not useful to establish an acceleration model Introduction of new failure mechanism skewing results Evidence of Anti-Wear-Out De-doping of polymer Decreased capacitance Increased ESR Not dielectric breakdown Needs further investigation Further investigation into tantalum polymer capacitor technology Promising acceleration model for Manufacturer A Possibility for use in high-reliability space applications with suitable voltage derating.

  18. Physically-based strength model of tantalum incorporating effects of temperature, strain rate and pressure

    DOE PAGES

    Lim, Hojun; Battaile, Corbett C.; Brown, Justin L.; ...

    2016-06-14

    In this work, we develop a tantalum strength model that incorporates e ects of temperature, strain rate and pressure. Dislocation kink-pair theory is used to incorporate temperature and strain rate e ects while the pressure dependent yield is obtained through the pressure dependent shear modulus. Material constants used in the model are parameterized from tantalum single crystal tests and polycrystalline ramp compression experiments. It is shown that the proposed strength model agrees well with the temperature and strain rate dependent yield obtained from polycrystalline tantalum experiments. Furthermore, the model accurately reproduces the pressure dependent yield stresses up to 250 GPa.more » The proposed strength model is then used to conduct simulations of a Taylor cylinder impact test and validated with experiments. This approach provides a physically-based multi-scale strength model that is able to predict the plastic deformation of polycrystalline tantalum through a wide range of temperature, strain and pressure regimes.« less

  19. Vacuum pyrolysis characteristics and parameter optimization of recycling organic materials from waste tantalum capacitors.

    PubMed

    Chen, Zhenyang; Niu, Bo; Zhang, Lingen; Xu, Zhenming

    2018-01-15

    Recycling rare metal tantalum from waste tantalum capacitors (WTCs) is significant to alleviate the shortage of tantalum resource. However, environmental problems will be caused if the organic materials from WTCs are improperly disposed. This study presented a promising vacuum pyrolysis technology to recycle the organic materials from WTCs. The organics removal rate could reach 94.32wt% according to TG results. The optimal parameters were determined as 425°C, 50Pa and 30min on the basis of response surface methodology (RSM). The oil yield and residual rate was 18.09wt% and 74.94wt%, respectively. All pyrolysis products can be recycled through a reasonable route. Besides, to deeply understand the pyrolysis process, the pyrolysis mechanism was also proposed based on the product and free radical theory. This paper provides an efficient process for recycling the organic material from WTCs, which can facilitate the following tantalum recovery. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Exploring the possibility to store the mixed oxygen-hydrogen cluster in clathrate hydrate in molar ratio 1:2 (O2+2H2).

    PubMed

    Qin, Yan; Du, Qi-Shi; Xie, Neng-Zhong; Li, Jian-Xiu; Huang, Ri-Bo

    2017-05-01

    An interesting possibility is explored: storing the mixture of oxygen and hydrogen in clathrate hydrate in molar ratio 1:2. The interaction energies between oxygen, hydrogen, and clathrate hydrate are calculated using high level quantum chemical methods. The useful conclusion points from this study are summarized as follows. (1) The interaction energies of oxygen-hydrogen mixed cluster are larger than the energies of pure hydrogen molecular cluster. (2) The affinity of oxygen molecules with water molecules is larger than that of the hydrogen molecules with water molecules. (3) The dimension of O 2 -2H 2 interaction structure is smaller than the dimension of CO 2 -2H 2 interaction structure. (4) The escaping energy of oxygen molecules from the hydrate cell is larger than that of the hydrogen molecules. (5) The high affinity of the oxygen molecules with both the water molecules and the hydrogen molecules may promote the stability of oxygen-hydrogen mixture in the clathrate hydrate. Therefore it is possible to store the mixed (O 2 +2H 2 ) cluster in clathrate hydrate. Copyright © 2017 Elsevier Inc. All rights reserved.

  1. Corrosion resistance of porous binary tantalum and titanium carbides of various composition

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

    Artyunina, N.P.; Komratov, G.N.; Bolonova, E.A.

    1993-12-20

    Resistance of porous binary tantalum and titanium carbides in solutions of mineral acids and their mixtures, of several organic acids, and of ammonium and potassium hydroxide was studied. It has been shown that as the content of tantalum in a material increases its resistance in solutions of oxidizing acids is improved, but it is reduced in solutions of sulfuric and hydrofluoric acids and also in solutions of potassium hydroxide.

  2. Physiological oxygen prevents frequent silencing of the DLK1-DIO3 cluster during human embryonic stem cells culture.

    PubMed

    Xie, Pingyuan; Sun, Yi; Ouyang, Qi; Hu, Liang; Tan, Yueqiu; Zhou, Xiaoying; Xiong, Bo; Zhang, Qianjun; Yuan, Ding; Pan, Yi; Liu, Tiancheng; Liang, Ping; Lu, Guangxiu; Lin, Ge

    2014-02-01

    Genetic and epigenetic alterations are observed in long-term culture (>30 passages) of human embryonic stem cells (hESCs); however, little information is available in early cultures. Through a large-scale gene expression analysis between initial-passage hESCs (ihESCs, <10 passages) and early-passage hESCs (ehESCs, 20-30 passages) of 12 hESC lines, we found that the DLK1-DIO3 gene cluster was normally expressed and showed normal methylation pattern in ihESC, but was frequently silenced after 20 passages. Both the DLK1-DIO3 active status in ihESCs and the inactive status in ehESCs were inheritable during differentiation. Silencing of the DLK1-DIO3 cluster did not seem to compromise the multilineage differentiation ability of hESCs, but was associated with reduced DNA damage-induced apoptosis in ehESCs and their differentiated hepatocyte-like cell derivatives, possibly through attenuation of the expression and phosphorylation of p53. Furthermore, we demonstrated that 5% oxygen, instead of the commonly used 20% oxygen, is required for preserving the expression of the DLK1-DIO3 cluster. Overall, the data suggest that active expression of the DLK1-DIO3 cluster represents a new biomarker for epigenetic stability of hESCs and indicates the importance of using a proper physiological oxygen level during the derivation and culture of hESCs. © AlphaMed Press.

  3. [Short-term curative effects of Tantalum rod treatment in early avascular necrosis].

    PubMed

    Ye, Fu-Sheng; Ni, Zhe-Ji; Chu, Xiao-Bing; He, Bang-Jian; Li, Ju; Tong, Pei-Jian

    2013-08-01

    To explore the recent clinical curative effect of Tantalum rod in treating the early avascular necrosis. From January 2008 to November 2008, the 25 patients (39 hips) with early avascular necrosis accepted tantalum rod placement and included 9 males (11 hips) and 16 females (28 hips) with an average age of 37 years old ranging from 18 to 74 years old. Four patients (6 hips) caused by Alcoholic, 6 patients (8 hips) by hormone, 2 cases (2 hips) by traumatic, 13 cases (23 hips) by idiopathic. Steinberg preoperative stage involved 7 hips in period I, 24 hips in period II, 8 hips in period III. Curative effect analysis included preoperative and postoperative Harris score, radiographic changes and hip replacement for follow-up to accept the end of the femoral head survival rate. All patients were followed up for 6 to 47 months (averaged 37.4 months). All 12 hips imaging appeard progress,including tantalum rod exit in 1 hip, hip hemiarthroplasty collapse in 3 hips, the area increased to avascular necrosis in 8 hips. Six hips accepted total hip replacement, including imaging progress in 5 hips (41.7%, 5/12), no imaging progress in 1 hip (3.7%,1/27). All hips' Kaplan-Meier survival curves showed 6-month survival rate was (97.4 +/- 2.5)% after tantalum stick insertion, 1-year survival rate was (94.7 +/- 3.6), and 2-year survival rate was (88.6 +/- 5.4)%, 3-year survival rate was (72.5 +/- 11.2). It is effective for treatment of avascular necrosis of femoral head in Steinberg I and II by Tantalum rod, and it can effectively relieve femoral head replacement time.

  4. The effects of argon ion bombardment on the corrosion resistance of tantalum

    NASA Astrophysics Data System (ADS)

    Ramezani, A. H.; Sari, A. H.; Shokouhy, A.

    2017-02-01

    Application of ion beam has been widely used as a surface modification method to improve surface properties. This paper investigates the effect of argon ion implantation on surface structure as well as resistance against tantalum corrosion. In this experiment, argon ions with energy of 30 keV and in doses of 1 × 1017-10 × 1017 ions/cm2 were used. The surface bombardment with inert gases mainly produces modified topography and morphology of the surface. Atomic Force Microscopy was also used to patterned the roughness variations prior to and after the implantation phase. Additionally, the corrosion investigation apparatus wear was applied to compare resistance against tantalum corrosion both before and after ion implantation. The results show that argon ion implantation has a substantial impact on increasing resistance against tantalum corrosion. After the corrosion test, scanning electron microscopy (SEM) analyzed the samples' surface morphologies. In addition, the elemental composition is characterized by energy-dispersive X-ray (EDX) analysis. The purpose of this paper was to obtain the perfect condition for the formation of tantalum corrosion resistance. In order to evaluate the effect of the ion implantation on the corrosion behavior, potentiodynamic tests were performed. The results show that the corrosion resistance of the samples strongly depends on the implantation doses.

  5. An exploration in mineral supply chain mapping using tantalum as an example

    USGS Publications Warehouse

    Soto-Viruet, Yadira; Menzie, W. David; Papp, John F.; Yager, Thomas R.

    2013-01-01

    This report uses the supply chain of tantalum (Ta) to investigate the complexity of mineral and metal supply chains in general and show how they can be mapped. A supply chain is made up of all the manufacturers, suppliers, information networks, and so forth, that provide the materials and parts that go into making up a final product. The mineral portion of the supply chain begins with mineral material in the ground (the ore deposit); extends through a series of processes that include mining, beneficiation, processing (smelting and refining), semimanufacture, and manufacture; and continues through transformation of the mineral ore into concentrates, refined mineral commodities, intermediate forms (such as metals and alloys), component parts, and, finally, complex products. This study analyses the supply chain of tantalum beginning with minerals in the ground to many of the final goods that contain tantalum.

  6. STUDIES ON ANALYTICAL METHODS FOR TRACE ELEMENTS IN METALS BY USING RADIOACTIVE ISOTOPE. III. DETERMINATION OF TANTALUM BY MEANS OF ISOTOPE DILUTION METHOD

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

    Amano, H.

    1959-10-01

    The determination of tantalum by the isotope dilution method in the presence of niobium was investigated by the use of the radioisotope Ta/sup 185/. Tantalum was separated from niobium as tantalum-tannin precipitate under the optimum conditions of a pH of 1.9 to 2.5 and a tantalum/niobium ratio of up to 1/ 50. If niobium was present in amounts 100 times or more that of tantalum, reprecipitation was needed. The reciprocal of the specific activity of tanthlum pentoxide precipitate was in a linear relation to the change in the amount of tantalum added. The recommended method gave an accurate result inmore » the determination of tantalum in steal. (auth)« less

  7. Effect of low-oxygen-concentration layer on iron gettering capability of carbon-cluster ion-implanted Si wafer for CMOS image sensors

    NASA Astrophysics Data System (ADS)

    Onaka-Masada, Ayumi; Nakai, Toshiro; Okuyama, Ryosuke; Okuda, Hidehiko; Kadono, Takeshi; Hirose, Ryo; Koga, Yoshihiro; Kurita, Kazunari; Sueoka, Koji

    2018-02-01

    The effect of oxygen (O) concentration on the Fe gettering capability in a carbon-cluster (C3H5) ion-implanted region was investigated by comparing a Czochralski (CZ)-grown silicon substrate and an epitaxial growth layer. A high Fe gettering efficiency in a carbon-cluster ion-implanted epitaxial growth layer, which has a low oxygen region, was observed by deep-level transient spectroscopy (DLTS) and secondary ion mass spectroscopy (SIMS). It was demonstrated that the amount of gettered Fe in the epitaxial growth layer is approximately two times higher than that in the CZ-grown silicon substrate. Furthermore, by measuring the cathodeluminescence, the number of intrinsic point defects induced by carbon-cluster ion implantation was found to differ between the CZ-grown silicon substrate and the epitaxial growth layer. It is suggested that Fe gettering by carbon-cluster ion implantation comes through point defect clusters, and that O in the carbon-cluster ion-implanted region affects the formation of gettering sinks for Fe.

  8. Thermocouples of tantalum and rhenium alloys for more stable vacuum-high temperature performance

    NASA Technical Reports Server (NTRS)

    Morris, J. F. (Inventor)

    1977-01-01

    Thermocouples of the present invention provide stability and performance reliability in systems involving high temperatures and vacuums by employing a bimetallic thermocouple sensor wherein each metal of the sensor is selected from a group of metals comprising tantalum and rhenium and alloys containing only those two metals. The tantalum, rhenium thermocouple sensor alloys provide bare metal thermocouple sensors having advantageous vapor pressure compatibilities and performance characteristics. The compatibility and physical characteristics of the thermocouple sensor alloys of the present invention result in improved emf, temperature properties and thermocouple hot junction performance. The thermocouples formed of the tantalum, rhenium alloys exhibit reliability and performance stability in systems involving high temperatures and vacuums and are adaptable to space propulsion and power systems and nuclear environments.

  9. Oxygen-tolerant [NiFe]-hydrogenases: the individual and collective importance of supernumerary cysteines at the proximal Fe-S cluster.

    PubMed

    Lukey, Michael J; Roessler, Maxie M; Parkin, Alison; Evans, Rhiannon M; Davies, Rosalind A; Lenz, Oliver; Friedrich, Baerbel; Sargent, Frank; Armstrong, Fraser A

    2011-10-26

    An important clue to the mechanism for O(2) tolerance of certain [NiFe]-hydrogenases is the conserved presence of a modified environment around the iron-sulfur cluster that is proximal to the active site. The O(2)-tolerant enzymes contain two cysteines, located at opposite ends of this cluster, which are glycines in their O(2)-sensitive counterparts. The strong correlation highlights special importance for electron-transfer activity in the protection mechanism used to combat O(2). Site-directed mutagenesis has been carried out on Escherichia coli hydrogenase-1 to substitute these cysteines (C19 and C120) individually and collectively for glycines, and the effects of each replacement have been determined using protein film electrochemistry and electron paramagnetic resonance (EPR) spectroscopy. The "split" iron-sulfur cluster EPR signal thus far observed when oxygen-tolerant [NiFe]-hydrogenases are subjected to oxidizing potentials is found not to provide any simple, reliable correlation with oxygen tolerance. Oxygen tolerance is largely conferred by a single cysteine (C19), replacement of which by glycine removes the ability to function even in 1% O(2).

  10. Tantalum capacitor behavior under fast transient overvoltages. [circuit protection against lightning

    NASA Technical Reports Server (NTRS)

    Zill, J. A.; Castle, K. D.

    1974-01-01

    Tantalum capacitors were tested to determine failure time when subjected to short-duration, high-voltage surges caused by lightning strikes. Lightning is of concern to NASA because of possible damage to critical spacecraft circuits. The test was designed to determine the minimum time for tantalum capacitor failure and the amount of overvoltage a capacitor could survive, without permanent damage, in 100 microseconds. All tested exhibited good recovery from the transient one-shot pulses with no failure at any voltage, forward or reverse, in less than 25 microseconds.

  11. SU-E-J-201: Position Verification in Breast Cancer Radiotherapy Using Tantalum Clips in the Lumpectomy Cavity

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

    Santvoort, J van; Van der Drift, M; Kuipers, J

    2014-06-01

    Purpose: To find out whether tantalum surgical clips can be used for online position verification in treatment of the lumpectomy cavity (LC) in breast cancer patients. Tantalum is a high density metal that could be visible on Electronic Portal Images (EPIs) and be an affordable alternative to gold markers. Clips are considered more representative for the LC position than nearby bony structures. Methods: In twelve patients the surgeon had placed 2 to 5 tantalum clips in the LC. The AP and lateral fields used for portal imaging, were adapted. In doing so, both bony structures and tantalum clips were visiblemore » on EPIs. The following analyses were performed:1. Image degradation, with respect to delineating the CTV, of the axial CT slices by artefacts because of the tantalum clips was evaluated by a radiation oncologist;2. The visibility of the tantalum clips on the EPIs was evaluated by four radiation therapists (RTTs);3. Bony anatomy and tantalum clip matches were performed on the same images independently by two observers. Results: 1. Delineation of the CTV by the radiation oncologist was not hampered by CT image artefacts because of the clips.2. The mean score for visibility of the clips on the EPIs, analysed by the four RTTs, was 5.6 on a scale of 10 (range 3.9 – 8.0).3. In total 12 patients with 16 fractions each were analysed. The differences between clip match and bone match are significant with a mean vector length of 5.2 mm (SD 1.9 mm) for the difference. Conclusion: Results of matches on tantalum clips as compared to matches on bony structures differ substantially. Therefore clip matches can result in smaller CTV to PTV margins than bone matches. Visibility of the clips on EPIs is sufficient, so they can be an alternative to gold markers.« less

  12. The application of porous tantalum cylinder to the repair of comminuted bone defects: a study of rabbit firearm injuries

    PubMed Central

    Ren, Bo; Zhai, Zhenbo; Guo, Kai; Liu, Yanpu; Hou, Weihuan; Zhu, Qingsheng; Zhu, Jinyu

    2015-01-01

    The aim of this study is to investigate the effect of porous tantalum material in repair tibial defects caused by firearm injuries in a rabbit model. A multifunctional biological impact machine was used to establish a rabbit tibial defect model of firearm injury. Porous tantalum rods were processed into a hollow cylinder. Kirschner wires were used for intramedullary fixation. We compared the differences of the bone ingrowth of the porous tantalum material by gross observations, X-rays and histological evaluations. The radiographic observations revealed that fibrous tissue covered the material surface after 4 weeks, and periosteal reactions and new bone callus extending materials appeared after 8 weeks. After 16 weeks, the calluses of the firearm injury group were completely wrapped around a porous tantalum material. The group with the highest Lane-Sandhu X-rays cores was the firearm injury and tantalum implant group, and the blank control group exhibited the lowest scores. The histological evaluations revealed that the presence of new bone around the biomaterial had grown into the porous tantalum. By the 16th week, the areas of bone tissue of the firearm injury group was significant higher than that of non-firearm injury group (P<0.05). The comminuted fractures treated with tantalum cylinders exhibited greater bone ingrowth in the firearm injury group. In conditions of firearm injuries, the porous tantalum biomaterial exhibited bone ingrowth that was beneficial to the treatment of bone defects. PMID:26131078

  13. Characterization of Oxygen Defect Clusters in UO2+ x Using Neutron Scattering and PDF Analysis.

    PubMed

    Ma, Yue; Garcia, Philippe; Lechelle, Jacques; Miard, Audrey; Desgranges, Lionel; Baldinozzi, Gianguido; Simeone, David; Fischer, Henry E

    2018-06-18

    In hyper-stoichiometric uranium oxide, both neutron diffraction work and, more recently, theoretical analyses report the existence of clusters such as the 2:2:2 cluster, comprising two anion vacancies and two types of anion interstitials. However, little is known about whether there exists a region of low deviation-from-stoichiometry in which defects remain isolated, or indeed whether at high deviation-from-stoichiometry defect clusters prevail that contain more excess oxygen atoms than the di-interstitial cluster. In this study, we report pair distribution function (PDF) analyses of UO 2 and UO 2+ x ( x ≈ 0.007 and x ≈ 0.16) samples obtained from high-temperature in situ neutron scattering experiments. PDF refinement for the lower deviation from stoichiometry sample suggests the system is too dilute to differentiate between isolated defects and di-interstitial clusters. For the UO 2.16 sample, several defect structures are tested, and it is found that the data are best represented assuming the presence of center-occupied cuboctahedra.

  14. Transition of dislocation glide to shear transformation in shocked tantalum

    DOE PAGES

    Hsiung, Luke L.; Campbell, Geoffrey H.

    2017-02-28

    A TEM study of pure tantalum and tantalum-tungsten alloys explosively shocked at a peak pressure of 30 GPa (strain rate: ~1 x 10 4 sec -1) is presented. While no ω (hexagonal) phase was found in shock-recovered pure Ta and Ta-5W that contain mainly a low-energy cellular dislocation structure, shock-induced ω phase was found to form in Ta-10W that contains evenly distributed dislocations with a stored dislocation density higher than 1 x 10 12 cm -2. The TEM results clearly reveal that shock-induced α (bcc) → ω (hexagonal) shear transformation occurs when dynamic recovery reactions which lead the formation low-energymore » cellular dislocation structure become largely suppressed in Ta-10W shocked under dynamic (i.e., high strain-rate and high-pressure) conditions. A novel dislocation-based mechanism is proposed to rationalize the transition of dislocation glide to twinning and/or shear transformation in shock-deformed tantalum. Lastly, twinning and/or shear transformation take place as an alternative deformation mechanism to accommodate high-strain-rate straining when the shear stress required for dislocation multiplication exceeds the threshold shear stresses for twinning and/or shear transformation.« less

  15. Effect of Reverse Bias Stress on Leakage Currents and Breakdown Voltages of Solid Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2011-01-01

    The majority of solid tantalum capacitors are produced by high-temperature sintering of a fine tantalum powder around a tantalum wire followed by electrolytic anodization that forms a thin amorphous Ta2O5 dielectric layer and pyrolysis of manganese nitrite on the oxide to create a conductive manganese dioxide electrode. A contact to tantalum wire is used as anode terminal and to the manganese layer as a cathode terminal of the device. This process results in formation of an asymmetric Ta -- Ta2O5 -- MnO2 capacitor that has different characteristics at forward (positive bias applied to tantalum) and reverse (positive bias applied to manganese cathode) voltages. Reverse bias currents might be several orders of magnitude larger than forward leakage currents so I-V characteristics of tantalum capacitors resemble characteristics of semiconductor rectifiers. Asymmetric I-V characteristics of Ta -- anodic Ta2O5 systems have been observed at different top electrode materials including metals, electrolytes, conductive polymers, and manganese oxide thus indicating that this phenomenon is likely related to the specifics of the Ta -- Ta2O5 interface. There have been multiple attempts to explain rectifying characteristics of capacitors employing anodic tantalum pentoxide dielectrics. A brief review of works related to reverse bias (RB) behavior of tantalum capacitors shows that the mechanism of conduction in Ta -- Ta2O5 systems is still not clear and more testing and analysis is necessary to understand the processes involved. If tantalum capacitors behave just as rectifiers, then the assessment of the safe reverse bias operating conditions would be a relatively simple task. Unfortunately, these parts can degrade with time under reverse bias significantly, and this further complicates analysis of the I-V characteristics and establishing safe operating areas of the parts. On other hand, time dependence of reverse currents might provide additional information for investigation of

  16. Deposition and characterization of magnetron sputtered bcc tantalum

    NASA Astrophysics Data System (ADS)

    Patel, Anamika

    The goal of this thesis was to provide scientific and technical research results for developing and characterizing tantalum (Ta) coatings on steel substrates deposited by DC magnetron sputtering. Deposition of tantalum on steel is of special interest for the protection it offers to surfaces, e.g. the surfaces of gun barrels against the erosive wear of hot propellant gases and the mechanical damage caused by the motion of launching projectiles. Electro-plated chromium is presently most commonly used for this purpose; however, it is considered to be carcinogenic in its hexavalent form. Tantalum is being investigated as non-toxic alternative to chromium and also because of its superior protective properties in these extreme environments. DC magnetron sputtering was chosen for this investigation of tantalum coatings on steel substrates because it is a versatile industrial proven process for deposition of metals. Sputter deposited Ta films can have two crystallographic structures: (1) body center cubic (bcc) phase, characterized by high toughness and high ductility and (2) a tetragonal beta phase characterized by brittleness and a tendency to fail under stress. It was found in this work that the bcc Ta coatings on steel can be obtained reliably by either of two methods: (1) depositing Ta on a submicron, stoichiometric TaN seed layer reactively sputtered on unheated steel and (2) depositing Ta directly on steel heated above a critical temperature. For argon sputtering gas this critical temperature was found to be 400°C at a pressure of 5 mtorr. With the heavier krypton gas, this critical temperature is reduced to 350°C. X-ray diffraction (XRD) was used to investigate the structure of tantalum and nitride films, and the composition of the nitride films was measured by nuclear reaction analyses (NRA), which were used to study in detail the enhancement of the bcc phase of Ta on steel. The scratch adhesion tests performed with a diamond hemispherical tip of radius 200 mum

  17. Heat Treatment of Tantalum and Niobium Powders Prepared by Magnesium-Thermic Reduction

    NASA Astrophysics Data System (ADS)

    Orlov, V. M.; Prokhorova, T. Yu.

    2017-11-01

    Changes in the specific surface area and porous structure of tantalum and niobium powders, which were prepared by magnesium-thermic reduction of Ta2O5, Mg4Ta2O9, and Mg4Nb2O9 oxide compounds and subjected to heat treatments at temperatures of 600-1500°C, have been studied. It is noted that, owing to the mesoporous structure of the magnesium-thermic powders, the decrease in the surface area during heat treatment, first of all, is related to a decrease in the amount of pores less than 10 nm in size. The heat treatment of a reacting mass is shown to allow us to correct the specific surface area of the powder without any increase in the oxygen content in it. Data on the effect of heat treatment conditions on the specific charge of capacitor anodes are reported.

  18. Mineral resource of the month: tantalum

    USGS Publications Warehouse

    Cunningham, Larry D.

    2004-01-01

    Tantalum is a metal that is critical to the United States because of its defense-related applications in aircraft, missiles and radio communications. It is ductile, easily fabricated, highly resistant to corrosion by acids, a good conductor of heat and electricity, and has a high melting point. Tantalum’s first commercial usage was as filament material in incandescent electric lamps in the early 1900s.

  19. Tantalum coating of porous carbon scaffold supplemented with autologous bone marrow stromal stem cells for bone regeneration in vitro and in vivo.

    PubMed

    Wei, Xiaowei; Zhao, Dewei; Wang, Benjie; Wang, Wei; Kang, Kai; Xie, Hui; Liu, Baoyi; Zhang, Xiuzhi; Zhang, Jinsong; Yang, Zhenming

    2016-03-01

    Porous tantalum metal with low elastic modulus is similar to cancellous bone. Reticulated vitreous carbon (RVC) can provide three-dimensional pore structure and serves as the ideal scaffold of tantalum coating. In this study, the biocompatibility of domestic porous tantalum was first successfully tested with bone marrow stromal stem cells (BMSCs) in vitro and for bone tissue repair in vivo. We evaluated cytotoxicity of RVC scaffold and tantalum coating using BMSCs. The morphology, adhesion, and proliferation of BMSCs were observed via laser scanning confocal microscope and scanning electron microscopy. In addition, porous tantalum rods with or without autologous BMSCs were implanted on hind legs in dogs, respectively. The osteogenic potential was observed by hard tissue slice examination. At three weeks and six weeks following implantation, new osteoblasts and new bone were observed at the tantalum-host bone interface and pores. At 12 weeks postporous tantalum with autologous BMSCs implantation, regenerated trabecular equivalent to mature bone was found in the pore of tantalum rods. Our results suggested that domestic porous tantalum had excellent biocompatibility and could promote new bone formation in vivo. Meanwhile, the osteogenesis of porous tantalum associated with autologous BMSCs was more excellent than only tantalum implantation. Future clinical studies are warranted to verify the clinical efficacy of combined implantation of this domestic porous tantalum associated with autologous BMSCs implantation and compare their efficacy with conventional autologous bone grafting carrying blood vessel in patients needing bone repairing. © 2016 by the Society for Experimental Biology and Medicine.

  20. Tantalum coating of porous carbon scaffold supplemented with autologous bone marrow stromal stem cells for bone regeneration in vitro and in vivo

    PubMed Central

    Wei, Xiaowei; Wang, Benjie; Wang, Wei; Kang, Kai; Xie, Hui; Liu, Baoyi; Zhang, Xiuzhi; Zhang, Jinsong; Yang, Zhenming

    2016-01-01

    Porous tantalum metal with low elastic modulus is similar to cancellous bone. Reticulated vitreous carbon (RVC) can provide three-dimensional pore structure and serves as the ideal scaffold of tantalum coating. In this study, the biocompatibility of domestic porous tantalum was first successfully tested with bone marrow stromal stem cells (BMSCs) in vitro and for bone tissue repair in vivo. We evaluated cytotoxicity of RVC scaffold and tantalum coating using BMSCs. The morphology, adhesion, and proliferation of BMSCs were observed via laser scanning confocal microscope and scanning electron microscopy. In addition, porous tantalum rods with or without autologous BMSCs were implanted on hind legs in dogs, respectively. The osteogenic potential was observed by hard tissue slice examination. At three weeks and six weeks following implantation, new osteoblasts and new bone were observed at the tantalum–host bone interface and pores. At 12 weeks postporous tantalum with autologous BMSCs implantation, regenerated trabecular equivalent to mature bone was found in the pore of tantalum rods. Our results suggested that domestic porous tantalum had excellent biocompatibility and could promote new bone formation in vivo. Meanwhile, the osteogenesis of porous tantalum associated with autologous BMSCs was more excellent than only tantalum implantation. Future clinical studies are warranted to verify the clinical efficacy of combined implantation of this domestic porous tantalum associated with autologous BMSCs implantation and compare their efficacy with conventional autologous bone grafting carrying blood vessel in patients needing bone repairing. PMID:26843518

  1. Antimicrobial activity of tantalum oxide coatings decorated with Ag nanoparticles

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

    Cao, Huiliang, E-mail: hlc@mail.sic.ac.cn; Meng, Fanhao; Liu, Xuanyong, E-mail: xyliu@mail.sic.ac.cn

    Silver plasma immersion ion implantation was used to decorate silver nanoparticles (Ag NPs) on tantalum oxide (TO) coatings. The coatings acted against bacterial cells (Staphylococcus epidermidis) in the dark by disrupting their integrity. The action was independent of silver release and likely driven by the electron storage capability of the Schottky barriers established at the interfaces between Ag NPs and the TO support. Moreover, no apparent side effect on the adhesion and differentiation of rat bone mesenchymal stem cells was detected when using Ag NPs-modified TO coatings. These results demonstrate that decoration of tantalum oxide using Ag NPs could bemore » a promising procedure for improving the antibacterial properties for orthopedic and dental implants.« less

  2. Application of pyrolysis to recycling organics from waste tantalum capacitors.

    PubMed

    Niu, Bo; Chen, Zhenyang; Xu, Zhenming

    2017-08-05

    Tantalum capacitors (TCs) are widely used in electronic appliances. The rapid replacement of electronic products results in generating large amounts of waste TCs (WTCs). WTCs, rich in valuable tantalum, are considered as high quality tantalum resources for recycling. However, environmental pollution will be caused if the organics of WTCs were not properly disposed. Therefore, effectively recycling the organics of WTCs is significant for recovering the valuable parts. This study proposed an argon (Ar) pyrolysis process to recycle the organics from WTCs. The organic decomposition kinetic was first analyzed by thermogravimetry. The results showed that the organics were decomposed in two major steps and the average activation energy was calculated to 234kJ/mol. Then, the suitable pyrolysis parameters were determined as 550°C, 30min and 100ml/min. The organics were effectively decomposed and converted to oils (mainly contained phenol homologs and benzene homologs) and gases (some hydrocarbon). These pyrolysis products could be reutilized as energy sources. Moreover, based on the products and bond energy theory, the pyrolysis mechanisms of the organics were also discussed. Finally, a reasonable technological process for products utilization was presented. This study contributes to the efficient recycling the organics before valuable material recovery from WTCs. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Achieving surface chemical and morphologic alterations on tantalum by plasma electrolytic oxidation.

    PubMed

    Goularte, Marcelo Augusto Pinto Cardoso; Barbosa, Gustavo Frainer; da Cruz, Nilson Cristino; Hirakata, Luciana Mayumi

    2016-12-01

    Search for materials that may either replace titanium dental implants or constitute an alternative as a new dental implant material has been widely studied. As well, the search for optimum biocompatible metal surfaces remains crucial. So, the aim of this work is to develop an oxidized surface layer on tantalum using plasma electrolytic oxidation (PEO) similar to those existing on oral implants been marketed today. Cleaned tantalum samples were divided into group 1 (control) and groups 2, 3, and 4 (treated by PEO for 1, 3, and 5 min, respectively). An electrolytic solution diluted in 1-L deionized water was used for the anodizing process. Then, samples were washed with anhydrous ethyl alcohol and dried in the open air. For complete anodic treatment disposal, the samples were immersed in acetone altogether, taken to the ultrasonic tank for 10 min, washed again in distilled water, and finally air-dried. For the scanning electron microscopy (SEM) analysis, all samples were previously coated with gold; the salt deposition analysis was conducted with an energy-dispersive X-ray spectroscopy (EDS) system integrated with the SEM unit. SEM images confirmed the changes on tantalum strips surface according to different exposure times while EDS analysis confirmed increased salt deposition as exposure time to the anodizing process also increased. PEO was able to produce both surface alteration and salt deposition on tantalum strips similar to those existing on oral implants been marketed today.

  4. Synthesis and characterization of polystyrene embolization particles doped with tantalum oxide nanoparticles for X-ray contrast.

    PubMed

    Morrison, Rachel; Thompson, James; Bird, Luke; Hill, Mark A; Townley, Helen

    2015-08-01

    Radiopaque and fluorescent embolic particles have been synthesized and characterised to match the size of vasculature found in tumours to ensure effective occlusion of the vessels. A literature search showed that the majority of vessels surrounding a tumour were less than 50 µm and therefore polydispersed polystyrene particles with a peak size of 50 µm have been synthesised. The embolic particles contain 5-8 nm amorphous tantalum oxide nanoparticles which provide X-ray contrast. Embolic particles containing up to 9.4 wt% tantalum oxide were prepared and showed significant contrast compared to the undoped polystyrene particles. The X-ray contrast of the embolic particles was shown to be linear (R(2) = 0.9) with respect to the concentration of incorporated tantalum nanoparticles. A model was developed which showed that seventy-five 50 µm embolic particles containing 10% tantalum oxide could provide the same contrast as 5 cm of bone. Therefore, the synthesized particles would provide sufficient X-ray contrast to enable visualisation within a tumour.

  5. Crystalline phase-stability of tantalum pentoxide

    NASA Astrophysics Data System (ADS)

    Walton, Santiago; Padilha, Antonio; Dalpian, Gustavo; Guillén, Jorge; Dalpian's Research Group Collaboration; Grupo de Estado Solido Collaboration; Gritad Collaboration

    2013-03-01

    Memristive devices are attractive candidates to provide a paradigm change in memory devices fabrication. These new devices would be faster, denser and less power consuming than those available today. However, the mechanism of memristance is not yet well understood. It is believed that a voltage/current-driven phase transition occurs in the material, which leads to significant changes in the device's conductivity. In the particular case of tantalum-oxide-based devices the relevant crystalline phases are still a matter of debate. Some of these phases are not even completely known and there is no agreement about which model best explains the crystallographic results. In this work we have performed ab-initio DFT based calculations to study the structural properties of different phases (and models) of Ta2O5 - the structure which is believed to exist inside Tantalum Oxide based devices. The equations of state for this material were constructed through first principles total energy calculations and we have also calculated the phonon frequencies at Γ. These results show that the most stable phase of this oxide (B-Ta2O5) is in fact composed of octahedral, instead of pentagonal (as L-Ta2O5) or hexagonal (as δ-Ta2O5) bipyramids. Fapesp, CNPq, Capes,CODI-UdeA

  6. A unique iron-sulfur cluster is crucial for oxygen tolerance of a [NiFe]-hydrogenase.

    PubMed

    Goris, Tobias; Wait, Annemarie F; Saggu, Miguel; Fritsch, Johannes; Heidary, Nina; Stein, Matthias; Zebger, Ingo; Lendzian, Friedhelm; Armstrong, Fraser A; Friedrich, Bärbel; Lenz, Oliver

    2011-05-01

    Hydrogenases are essential for H(2) cycling in microbial metabolism and serve as valuable blueprints for H(2)-based biotechnological applications. However, most hydrogenases are extremely oxygen sensitive and prone to inactivation by even traces of O(2). The O(2)-tolerant membrane-bound [NiFe]-hydrogenase of Ralstonia eutropha H16 is one of the few examples that can perform H(2) uptake in the presence of ambient O(2). Here we show that O(2) tolerance is crucially related to a modification of the internal electron-transfer chain. The iron-sulfur cluster proximal to the active site is surrounded by six instead of four conserved coordinating cysteines. Removal of the two additional cysteines alters the electronic structure of the proximal iron-sulfur cluster and renders the catalytic activity sensitive to O(2) as shown by physiological, biochemical, spectroscopic and electrochemical studies. The data indicate that the mechanism of O(2) tolerance relies on the reductive removal of oxygenic species guided by the unique architecture of the electron relay rather than a restricted access of O(2) to the active site.

  7. Evaluation of the 3D Finite Element Method Using a Tantalum Rod for Osteonecrosis of the Femoral Head

    PubMed Central

    Shi, Jingsheng; Chen, Jie; Wu, Jianguo; Chen, Feiyan; Huang, Gangyong; Wang, Zhan; Zhao, Guanglei; Wei, Yibing; Wang, Siqun

    2014-01-01

    Background The aim of this study was to contrast the collapse values of the postoperative weight-bearing areas of different tantalum rod implant positions, fibula implantation, and core decompression model and to investigate the advantages and disadvantages of tantalum rod implantation in different ranges of osteonecrosis in comparison with other methods. Material/Methods The 3D finite element method was used to establish the 3D finite element model of normal upper femur, 3D finite element model after tantalum rod implantation into different positions of the upper femur in different osteonecrosis ranges, and other 3D finite element models for simulating fibula implant and core decompression. Results The collapse values in the weight-bearing area of the femoral head of the tantalum rod implant model inside the osteonecrosis area, implant model in the middle of the osteonecrosis area, fibula implant model, and shortening implant model exhibited no statistically significant differences (p>0.05) when the osteonecrosis range was small (60°). The stress values on the artificial bone surface for the tantalum rod implant model inside the osteonecrosis area and the shortening implant model exhibited statistical significance (p<0.01). Conclusions Tantalum rod implantation into the osteonecrosis area can reduce the collapse values in the weight-bearing area when osteonecrosis of the femoral head (ONFH) was in a certain range, thereby obtaining better clinical effects. When ONFH was in a large range (120°), the tantalum rod implantation inside the osteonecrosis area, shortening implant or fibula implant can reduce the collapse values of the femoral head, as assessed by other methods. PMID:25479830

  8. The effect of tantalum and carbon on the structure/properties of a single crystal nickel-base superalloy. M.S. Thesis. Final Report

    NASA Technical Reports Server (NTRS)

    Nguyen, H. C.

    1984-01-01

    The microstructure, phase chemistry, and creep and hot tensile properties were studied as a function of tantalum and carbon levels in Mar-M247 type single crystal alloys. Microstructural studies showed that several types of carbides (MC, M23C6 and M5C) are present in the normal carbon (0.10 wt % C) alloys after heat treatment. In general, the composition of the MC carbides changes from titanium rich to tantalum rich as the tantalum level in the alloy increases. Small M23C6 carbides are present in all alloys. Tungsten rich M6C carbides are also observed in the alloy containing no tantalum. No carbides are present in the low carbon (0.01 wt % C) alloy series. The morphology of gamma prime is observed to be sensitive to heat treatment and tantalum level in the alloy. Cuboidal gamma prime is present in all the as cast structures. After heat treatment, the gamma prime precipitates tend to have a more spheroidal like morphology, and this tendency increases as the tantalum level decreases. On prolonged aging, the gamma prime reverts back to a cuboidal morphology or under stress at high temperatures, forms a rafted structure. The weight fraction and lattice parameter of the spheroidal gamma prime increases with increasing tantalum content. Changes in the phase chemistry of the gamma prime matrix and gamma prime have also been analyzed using phase extraction techniques. The partitioning ratio decreases for tungsten and aluminum and increases for tantalum as the tantalum content increases for both alloy series; no significant changes occur in the partitioning ratios of the other alloying elements. A reduction in secondary creep rate and an increase in rupture time result from increasing the tantalum content and decreasing the carbon level.

  9. Conflict minerals from the Democratic Republic of the Congo: global tantalum processing plants, a critical part of the tantalum supply chain

    USGS Publications Warehouse

    Papp, John F.

    2014-01-01

    Post-beneficiation processing plants (generally called smelters and refineries) for 3TG mineral ores and concentrates were identified by company and industry association representatives as being the link in the 3TG mineral supply chain through which these minerals can be traced to their source of origin (mine). The determination of the source of origin is critical to the development of a complete and transparent conflict-free mineral supply chain. Tungsten processing plants were the subject of the first fact sheet in this series published by USGS NMIC in August 2014. Background information about historical conditions and multinational stakeholders’ voluntary due diligence guidance for minerals from conflict-affected and high-risk areas is presented in the tungsten fact sheet. This fact sheet, the second in a series about 3TG minerals, focuses on the tantalum supply chain by listing selected processors that produced tantalum materials commercially worldwide during 2013–14. It does not provide any information regarding the sources of material processed in these facilities.

  10. A novel tantalum-based sol-gel packed microextraction syringe for highly specific enrichment of phosphopeptides in MALDI-MS applications.

    PubMed

    Çelikbıçak, Ömür; Atakay, Mehmet; Güler, Ülkü; Salih, Bekir

    2013-08-07

    A new tantalum-based sol-gel material was synthesized using a unique sol-gel synthesis pathway by PEG incorporation into the sol-gel structure without performing a calcination step. This improved its chemical and physical properties for the high capacity and selective enrichment of phosphopeptides from protein digests in complex biological media. The specificity of the tantalum-based sol-gel material for phosphopeptides was evaluated and compared with tantalum(V) oxide (Ta2O5) in different phosphopeptide enrichment applications. The tantalum-based sol-gel and tantalum(V) oxide were characterized in detail using FT-IR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM), and also using a surface area and pore size analyzer. In the characterization studies, the surface morphology, pore volume, crystallinity of the materials and PEG incorporation into the sol-gel structure to produce a more hydrophilic material were successfully demonstrated. The X-ray diffractograms of the two different materials were compared and it was noted that the broad signals of the tantalum-based sol-gel clearly represented the amorphous structure of the sol-gel material, which was more likely to create enough surface area and to provide more accessible tantalum atoms for phosphopeptides to be easily adsorbed when compared with the neat and more crystalline structure of Ta2O5. Therefore, the phosphopeptide enrichment performance of the tantalum-based sol-gels was found to be remarkably higher than the more crystalline Ta2O5 in our studies. Phosphopeptides at femtomole levels could be selectively enriched using the tantalum-based sol-gel and detected with a higher signal-to-noise ratio by matrix-assisted laser desorption/ionization-mass spectrometer (MALDI-MS). Moreover, phosphopeptides in a tryptic digest of non-fat bovine milk as a complex real-world biological sample were retained with higher yield using a tantalum-based sol-gel. Additionally, the sol-gel material

  11. Effect of Temperature Cycling and Exposure to Extreme Temperatures on Reliability of Solid Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2007-01-01

    In this work, results of multiple temperature cycling (TC) (up to 1,000 cycles) of different types of solid tantalum capacitors are analyzed and reported. Deformation of chip tantalum during temperature variations simulating reflow soldering conditions was measured to evaluate the possibility of the pop-corning effect in the parts. To simulate the effect of short-time exposures to solder reflow temperatures on the reliability of tantalum capacitors, several part types were subjected to multiple cycles (up to 100) between room temperature and 240 C with periodical measurements of electrical characteristics of the parts. Mechanisms of degradation caused by temperature cycling and exposure to high temperatures, and the requirements of MIL-PRF-55365 for assessment of the resistance of the parts to soldering heat are discussed.

  12. CONTRIBUTION TO THE GEOCHEMISTRY OF TANTALUM AND NIOBIUM IN THE HYDROTHERMAL-PNEUMATHOLYTIC PROCESS (in Russian)

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

    Beus, A.A.; Sitnin, A.A.

    1961-01-01

    S>Data obtained as a result of geochemical investigations show that tantalum and niobium are typical elements of high-temperature postmagmatic processes (early albitization, greysening) connected with granites. The separation of tantalum and niobium in the hydrothermal-pneumatholytic process (greysening stage), which leads to the concentration of tantalum in albitized and greysenized granites (40 to 100 times compared to the average content in granites) is connected with the different mobility and stability of their acido- complex compounds (in particular fluor- and oxyfluorcomplexes), the existence of which in greysening solutions is suggested. A natural analogy in the behavior of both elements in the processesmore » of postmagmatic metasomatose in granites and granitic pegmatites is suggested. (tr-auth)« less

  13. Early/Late Heterobimetallic Tantalum/Rhodium Species Assembled Through a Novel Bifunctional NHC-OH Ligand.

    PubMed

    Srivastava, Ravi; Moneuse, Raphaël; Petit, Julien; Pavard, Paul-Alexis; Dardun, Vincent; Rivat, Madleen; Schiltz, Pauline; Solari, Marius; Jeanneau, Erwann; Veyre, Laurent; Thieuleux, Chloé; Quadrelli, Elsje Alessandra; Camp, Clément

    2018-03-20

    The straightforward synthesis of a new unsymmetrical hydroxy-tethered N-heterocyclic carbene (NHC) ligand, HL, is presented. The free ligand exhibits an unusual OH-carbene hydrogen-bonding interaction. This OH-carbene motif was used to yield 1) the first tantalum complex displaying both a Fischer- and Schrock-type carbene ligand and 2) a unique NHC-based early/late heterobimetallic complex. More specifically, the protonolysis chemistry between the ligand's hydroxy group and imido-alkyl or alkylidene-alkyl tantalum precursor complexes yielded the rare monometallic tantalum-NHC complexes [Ta(XtBu)(L)(CH 2 tBu) 2 ] (X=N, CH), in which the alkoxy-carbene ligand acts as a chelate. In contrast, HL only binds to rhodium through the NHC unit in [Rh(HL)(cod)Cl] (cod=cycloocta-1,5-diene), the hydroxy pendant arm remaining unbound. This bifunctional ligand scaffold successfully promoted the assembly of rhodium/tantalum heterobimetallic complexes upon either 1) the insertion of [Rh(cod)Cl] 2 into the Ta-NHC bond in [Ta(NtBu)(L)(CH 2 tBu) 2 ] or 2) protonolysis between the free hydroxy group in [Rh(HL)(cod)Cl] and one alkyl group in [Ta(NtBu)(CH 2 tBu) 3 ]. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Hot pressing of nanocrystalline tantalum using high frequency induction heating and pulse plasma sintering

    NASA Astrophysics Data System (ADS)

    Jakubowicz, J.; Adamek, G.; Sopata, M.; Koper, J. K.; Siwak, P.

    2017-12-01

    The paper presents the results of nanocrystalline powder tantalum consolidation using hot pressing. The authors used two different heating techniques during hot pressing: high-frequency induction heating (HFIH) and pulse plasma sintering (PPS). A comparison of the structure, microstructure, mechanical properties and corrosion resistance of the bulk nanocrystalline tantalum obtained in both techniques was performed. The nanocrystalline powder was made to start from the microcrystalline one using the high-energy ball milling process. The nanocrystalline powder was hot-pressed at 1000 °C, whereas, for comparison, the microcrystalline powder was hot pressed up to 1500 °C for proper consolidation. The authors found that during hot pressing, the powder partially reacts with the graphite die covered by boron nitride, which facilitated punches and powder displacement in the die during densification. Tantalum carbide and boride in the nanocrystalline material was found, which can improve the mechanical properties. The hardness of the HFIH and PPS nanocrystalline tantalum was as high as 625 and 615 HV, respectively. The microstructure was more uniform in the PPS nanomaterial. The corrosion resistance in both cases deteriorated, in comparison to the microcrystalline material, while the PPS material corrosion resistance was slightly better than that of the HFIH one.

  15. The effect of tantalum on the structure/properties of two polycrystalline nickel-base superalloys: B-1900 + Hf MAR-M247. M.S. Thesis, Final Report

    NASA Technical Reports Server (NTRS)

    Janowski, G. M.

    1985-01-01

    The microstructure, phase compositions, and phase fractions were studied in conventionally cast B-1900 + Hf and both conventionally cast and directionally solidified MAR-M247 as a function of tantalum concentration. The hot tensile and creep rupture properties of the solutionized and aged MAR-M247-type alloys were also determined as a function of tantalum level. The effects of tantalum on the microstructure and phase compositions of B-1900 + Hf and MAR-M247 (conventionally cast and directionally solidified) were found to be very similar. The addition of tantalum to the as cast and heat treated alloys was shown to cause the partial replacement of the Hf in the MC carbides by Ta, although the degree of replacement was decreased by the solutionizing and aging heat treatment. The gamma prime and minor phase fractions (primarily MC type carbides) both increased approximately linearly with tantalum concentration. The gamma prime phase compositions were relatively insensitive to tantalum variations with the exception of the tantalum and/or hafnium levels. Bulk tantalum additions increased the tantalum, chromium, and cobalt levels of the gamma phase in both alloy series. The increase in the concentrations of the latter two elements in the gamma phase was a result of the decrease in the gamma phase fraction with increasing bulk tantalum concentration and constant gamma/gamma prime partitioning ratio. Tantalum additions increased the yield stress and ultimate tensile strength of the directionally solidified MAR-M247 type alloys and had no significant effect on ductility.

  16. Primary human osteoblasts grow into porous tantalum and maintain an osteoblastic phenotype.

    PubMed

    Welldon, Katie J; Atkins, Gerald J; Howie, Donald W; Findlay, David M

    2008-03-01

    Porous tantalum (Ta) has found application in orthopedics, although the interaction of human osteoblasts (HOB) with this material has not been reported. The aim of this study was to investigate the interaction of primary HOB with porous tantalum, using 5-mm thick discs of porous tantalum. Comparison was made with discs of solid tantalum and tissue culture plastic. Confocal microscopy was used to investigate the attachment and growth of cells on porous Ta, and showed that HOB attached successfully to the metal "trabeculae," underwent extensive cell division, and penetrated into the Ta pores. The maturation of HOB on porous Ta was determined in terms of cell expression of the osteoblast phenotypic markers, STRO-1, and alkaline phosphatase. Despite some donor-dependent variation in STRO-1/AlkPhos expression, growth of cells grown on porous Ta either promoted, or did not impede, the maturation of HOB. In addition, the expression of key osteoblastic genes was investigated after 14 days of culture. The relative levels of mRNA encoding osteocalcin, osteopontin and receptor activator of NFkappaB ligand (RANKL) was not different between porous or solid Ta or plastic, although these genes were expressed differently by cells of different donors. However, bone sialoprotein and type I collagen mRNA species showed a decreased expression on porous Ta compared with expression on plastic. No substrate-dependent differences were seen in the extent of in vitro mineralization by HOB. These results indicate that porous Ta is a good substrate for the attachment, growth, and differentiated function of HOB. (c) 2007 Wiley Periodicals, Inc.

  17. Performance and Reliability of Electrowetting-on-Dielectric (EWOD) Systems Based on Tantalum Oxide.

    PubMed

    Mibus, Marcel; Zangari, Giovanni

    2017-12-06

    The electrowetting-on-dielectric behavior of Cytop/Tantalum oxide (TaOx) bilayers is studied by measuring their response vs applied voltage and under prolonged periodic cycling, below and above the threshold voltage V T corresponding to the breakdown field for the oxide. TaOx exhibits symmetric solid state I-V characteristics, with electronic conduction dominated by Schottky, Poole-Frenkel emission; conduction is attributed to oxygen vacancies (6 × 10 16 cm -3 ), resulting in large currents at low bias. Electrolyte/Metal Oxide/Metal I-V characteristics show oxide degradation at (<5 V) cathodic bias; anodic bias in contrast results in stable characteristics until reaching the anodization voltage, where the oxide thickens, leading eventually to breakdown and oxygen production at the electrode. Electrowetting angle vs applied voltage undergoes three different stages: a parabolic variation of contact angle (CA) with applied voltage, CA saturation, and rebound of the CA to higher values due to degradation of the polymer layer. The contact angle remained stable for several hundred cycles if the applied voltage was less than V T ; degradation in contrast is fast when the voltage is above V T . Degradation of the electrowetting response with time is linked to charge accumulation in the polymer, which inhibits the rebound of the CA when voltage is being applied.

  18. SODIUM AND OXYGEN ABUNDANCES IN THE OPEN CLUSTER NGC 6791 FROM APOGEE H-BAND SPECTROSCOPY

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

    Cunha, Katia; Souto, Diogo; Smith, Verne V.

    2015-01-10

    The open cluster NGC 6791 is among the oldest, most massive, and metal-rich open clusters in the Galaxy. High-resolution H-band spectra from the Apache Point Observatory Galactic Evolution Experiment (APOGEE) of 11 red giants in NGC 6791 are analyzed for their chemical abundances of iron, oxygen, and sodium. The abundances of these three elements are found to be homogeneous (with abundance dispersions at the level of ∼0.05-0.07 dex) in these cluster red giants, which span much of the red-giant branch (T {sub eff} ∼ 3500-4600 K), and include two red clump giants. From the infrared spectra, this cluster is confirmed to be amongmore » the most metal-rich clusters in the Galaxy (([Fe/H]) = 0.34 ± 0.06) and is found to have a roughly solar value of [O/Fe] and slightly enhanced [Na/Fe]. Our non-LTE calculations for the studied Na I lines in the APOGEE spectral region (16373.86 Å and 16388.85 Å) indicate only small departures from LTE (≤0.04 dex) for the parameter range and metallicity of the studied stars. The previously reported double population of cluster members with different Na abundances is not found among the studied sample.« less

  19. Leakage Currents and Gas Generation in Advanced Wet Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2015-01-01

    Currently, military grade, established reliability wet tantalum capacitors are among the most reliable parts used for space applications. This has been achieved over the years by extensive testing and improvements in design and materials. However, a rapid insertion of new types of advanced, high volumetric efficiency capacitors in space systems without proper testing and analysis of degradation mechanisms might increase risks of failures. The specifics of leakage currents in wet electrolytic capacitors is that the conduction process is associated with electrolysis of electrolyte and gas generation resulting in building up of internal gas pressure in the parts. The risk associated with excessive leakage currents and increased pressure is greater for high value advanced wet tantalum capacitors, but it has not been properly evaluated yet. In this work, in Part I, leakages currents in various types of tantalum capacitors have been analyzed in a wide range of voltages, temperatures, and time under bias. Gas generation and the level of internal pressure have been calculated in Part II for different case sizes and different hermeticity leak rates to assess maximal allowable leakage currents. Effects related to electrolyte penetration to the glass seal area have been studied and the possibility of failures analyzed in Part III. Recommendations for screening and qualification to reduce risks of failures have been suggested.

  20. Theoretical analysis of oxygen diffusion at startup in an alkali metal heat pipe with gettered alloy walls

    NASA Technical Reports Server (NTRS)

    Tower, L. K.

    1973-01-01

    The diffusion of oxygen into, or out of, a gettered alloy exposed to oxygenated alkali liquid metal coolant, a situation arising in some high temperature heat transfer systems, was analyzed. The relation between the diffusion process and the thermochemistry of oxygen in the alloy and in the alkali metal was developed by making several simplifying assumptions. The treatment is therefore theoretical in nature. However, a practical example pertaining to the startup of a heat pipe with walls of T-111, a tantalum alloy, and lithium working fluid illustrates the use of the figures contained in the analysis.

  1. Effect of Mechanical Stresses on Characteristics of Chip Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2007-01-01

    The effect of compressive mechanical stresses on chip solid tantalum capacitors is investigated by monitoring characteristics of different part types under axial and hydrostatic stresses. Depending on part types, an exponential increase of leakage currents was observed when stresses exceeded 10 MPa to 40 MPa. For the first time, reversible variations of leakage currents (up to two orders of magnitude) with stress have been demonstrated. Mechanical stresses did not cause significant changes of AC characteristics of the capacitors, whereas breakdown voltages measured during the surge current testing decreased substantially indicating an increased probability of failures of stressed capacitors in low impedance applications. Variations of leakage currents are explained by a combination of two mechanisms: stress-induced scintillations and stress-induced generation of electron traps in the tantalum pentoxide dielectric.

  2. Heat of combustion of tantalum-tungsten oxide thermite composites

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

    Cervantes, Octavio G.; Department of Chemical Engineering and Materials Science, University of California, Davis, CA 95616; Kuntz, Joshua D.

    2010-12-15

    The heat of combustion of two distinctly synthesized stoichiometric tantalum-tungsten oxide energetic composites was investigated by bomb calorimetry. One composite was synthesized using a sol-gel (SG) derived method in which micrometric-scale tantalum is immobilized in a tungsten oxide three-dimensional nanostructured network structure. The second energetic composite was made from the mixing of micrometric-scale tantalum and commercially available (CA) nanometric tungsten oxide powders. The energetic composites were consolidated using the spark plasma sintering (SPS) technique under a 300 MPa pressure and at temperatures of 25, 400, and 500 C. For samples consolidated at 25 C, the density of the CA compositemore » is 61.65 {+-} 1.07% in comparison to 56.41 {+-} 1.19% for the SG derived composite. In contrast, the resulting densities of the SG composite are higher than the CA composite for samples consolidated at 400 and 500 C. The theoretical maximum density for the SG composite consolidated to 400 and 500 C are 81.30 {+-} 0.58% and 84.42 {+-} 0.62%, respectively. The theoretical maximum density of the CA composite consolidated to 400 and 500 C are 74.54 {+-} 0.80% and 77.90 {+-} 0.79%, respectively. X-ray diffraction analyses showed an increase of pre-reaction of the constituents with an increase in the consolidation temperature. The increase in pre-reaction results in lower stored energy content for samples consolidated to 400 and 500 C in comparison to samples consolidated at 25 C. (author)« less

  3. Use of a Tantalum Liner to Reduce Bore Erosion and Increase Muzzle Velocity in Two-Stage Light Gas Guns

    NASA Technical Reports Server (NTRS)

    Bogdanoff, David W.

    2015-01-01

    Muzzle velocities and gun erosion predicted by earlier numerical simulations of two stage light gas guns with steel gun tubes were in good agreement with experimental values. In a subsequent study, simulations of high performance shots were repeated with rhenium (Re) gun tubes. Large increases in muzzle velocity (2 - 4 km/sec) were predicted for Re tubes. In addition, the hydrogen-produced gun tube erosion was, in general, predicted to be zero with Re tubes. Tantalum (Ta) has some mechanical properties superior to those of Re. Tantalum has a lower modulus of elasticity than Re for better force transmission from the refractory metal liner to an underlying thick wall steel tube. Tantalum also has greater ductility than Re for better survivability during severe stress/strain cycles. Also, tantalum has been used as a coating or liner in military powder guns with encouraging results. Tantalum has, however, somewhat inferior thermal properties to those of rhenium, with a lower melting point and lower density and thermal conductivity. The present study was undertaken to see to what degree the muzzle velocity gains of rhenium gun tubes (over steel tubes) could be achieved with tantalum gun tubes. Nine high performance shots were modeled with a new version of our CFD gun code for steel, rhenium and tantalum gun tubes. For all except the highest velocity shot, the results with Ta tubes were nearly identical with those for Re tubes. Even for the highest velocity shot, the muzzle velocity gain over a steel tube using Ta was 82% of the gain obtained using Re. Thus, the somewhat inferior thermal properties of Ta (when compared to those of Re) translate into only very slightly poorer overall muzzle velocity performance. When this fact is combined with the superior mechanical properties of Ta and the encouraging performance of Ta liners/coatings in military powder guns, tantalum is to be preferred over Re as a liner/coating material for two stage light gas guns to increase muzzle

  4. Evaluation of Ferrite Chip Beads as Surge Current Limiters in Circuits with Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2014-01-01

    Limiting resistors are currently required to be connected in series with tantalum capacitors to reduce the risk of surge current failures. However, application of limiting resistors decreases substantially the efficiency of the power supply systems. An ideal surge current limiting device should have a negligible resistance for DC currents and high resistance at frequencies corresponding to transients in tantalum capacitors. This work evaluates the possibility of using chip ferrite beads (FB) as such devices. Twelve types of small size FBs from three manufacturers were used to evaluate their robustness under soldering stresses and at high surge current spikes associated with transients in tantalum capacitors. Results show that FBs are capable to withstand current pulses that are substantially greater than the specified current limits. However, due to a sharp decrease of impedance with current, FBs do not reduce surge currents to the required level that can be achieved with regular resistors.

  5. Tantalum-containing catalyst useful for producing alcohols from synthesis gas

    DOEpatents

    Kinkade, Nancy E.

    1991-01-01

    A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

  6. Tantalum-containing catalyst useful for producing alcohols from synthesis gas

    DOEpatents

    Kinkade, Nancy E.

    1992-01-01

    A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

  7. Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen

    DOE PAGES

    Qian, Linping; Wang, Zhen; Beletskiy, Evgeny V.; ...

    2017-03-28

    Here, the ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml –1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s –1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participationmore » in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.« less

  8. Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen

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

    Qian, Linping; Wang, Zhen; Beletskiy, Evgeny V.

    Here, the ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml –1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s –1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participationmore » in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.« less

  9. Inferring Strength of Tantalum from Hydrodynamic Instability Recovery Experiments

    NASA Astrophysics Data System (ADS)

    Sternberger, Z.; Maddox, B.; Opachich, Y.; Wehrenberg, C.; Kraus, R.; Remington, B.; Randall, G.; Farrell, M.; Ravichandran, G.

    2018-05-01

    Hydrodynamic instability experiments allow access to material properties at extreme conditions, where strain rates exceed 105 s-1 and pressures reach 100 GPa. Current hydrodynamic instability experimental methods require in-flight radiography to image the instability growth at high pressure and high strain rate, limiting the facilities where these experiments can be performed. An alternate approach, recovering the sample after loading, allows measurement of the instability growth with profilometry. Tantalum samples were manufactured with different 2D and 3D initial perturbation patterns and dynamically compressed by a blast wave generated by laser ablation. The samples were recovered from peak pressures between 30 and 120 GPa and strain rates on the order of 107 s-1, providing a record of the growth of the perturbations due to hydrodynamic instability. These records are useful validation points for hydrocode simulations using models of material strength at high strain rate. Recovered tantalum samples were analyzed, providing an estimate of the strength of the material at high pressure and strain rate.

  10. Upgrading tantalum and niobium oxides content in Bangka tin slag with double leaching

    NASA Astrophysics Data System (ADS)

    Soedarsono, J. W.; Permana, S.; Hutauruk, J. K.; Adhyputra, R.; Rustandi, A.; Maksum, A.; Widana, K. S.; Trinopiawan, K.; Anggraini, M.

    2018-03-01

    Tantalum has become one of the 14 types of critical materials where the level of its availability is assumed as the midterm critical metal. Benefits of the element tantalum in the electronics field increased the deficit balance of supply / demand, as more variations of electronic products developed. The tantalum experts calculated the level of availability until 2020. Base on the previous studies, tin slag is a secondary source of tantalum and niobium. This study uses tin slag from Bangka, Indonesia, abbreviated, Bangka Tin Slag (BTS). BTS was roasted, water quenched and sieved, abbreviated BTS-RQS.BTS was roasted, water quenched and sieved, abbreviated BTS-RQS.BTS-RQS was roasted at a temperature 700□C given sample code BTS-R700QS, while roasted at 800°C given sample code BTS-R800QS.A variable leaching experiment on BTS-R700QS was solvent concentration variable and on BTS-R800QS was time variable. The entire residue was characterized by X-Ray Fluorescence (XRF), and the optimum results are on the BTS-R800QS leaching into 5 M NaOH for 20 min followed by 5M HCl for 50 min, with content of Ta2O5 and Nb2O51.56% and 1.11%, respectively. The result of XRF measurement showed was the increasing of TNO content due to the increasing solvent concentration and time of acid leaching. The discussion of thermodynamics this study used was HSC Chemistry 6 as a supporting data.

  11. Evaluation of Polymer Hermetically Sealed Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2014-01-01

    Polymer cathode tantalum capacitors have lower ESR (equivalent series resistance) compared to other types of tantalum capacitors and for this reason have gained popularity in the electronics design community. Their use allows improved performance of power supply systems along with substantial reduction of size and weight of the components used. However, these parts have poor thermal stability and can degrade in humid environments. Polymer hermetically sealed (PHS) capacitors avoid problems related to environmental degradation of molded case parts and can potentially replace current wet and solid hermetically sealed capacitors. In this work, PHS capacitors manufactured per DLA LAM DWG#13030 are evaluated for space applications. Several lots of capacitors manufactured over period from 2010 to 2014 were tested for the consistency of performance, electrical and thermal characteristics, highly accelerated life testing, and robustness under reverse bias and random vibration conditions. Special attention was given to analysis of leakage currents and the effect of long-term high temperature storage on capacitors in as is condition and after hermeticity loss. The results show that PHS capacitors might be especially effective for low-temperature applications or for system requiring a cold start-up. Additional screening and qualification testing have been recommended to assure the necessary quality of capacitors for space projects.

  12. Migration of defect clusters and xenon-vacancy clusters in uranium dioxide

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

    Chen, Dong; Gao, Fei; Deng, Huiqiu

    2014-07-01

    The possible transition states, minimum energy paths and migration mechanisms of defect clusters and xenon-vacancy defect clusters in uranium dioxide have been investigated using the dimer and the nudged elastic-band methods. The nearby O atom can easily hop into the oxygen vacancy position by overcoming a small energy barrier, which is much lower than that for the migration of a uranium vacancy. A simulation for a vacancy cluster consisting of two oxygen vacancies reveals that the energy barrier of the divacancy migration tends to decrease with increasing the separation distance of divacancy. For an oxygen interstitial, the migration barrier formore » the hopping mechanism is almost three times larger than that for the exchange mechanism. Xe moving between two interstitial sites is unlikely a dominant migration mechanism considering the higher energy barrier. A net migration process of a Xe-vacancy pair containing an oxygen vacancy and a xenon interstitial is identified by the NEB method. We expect the oxygen vacancy-assisted migration mechanism to possibly lead to a long distance migration of the Xe interstitials in UO2. The migration of defect clusters involving Xe substitution indicates that Xe atom migrating away from the uranium vacancy site is difficult.« less

  13. Tantalum-containing catalyst useful for producing alcohols from synthesis gas

    DOEpatents

    Kinkade, N.E.

    1992-04-07

    A catalyst is described which is useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols. The catalyst consists essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

  14. Frequency spectrum of tantalum at temperatures of 293-2300 K

    NASA Astrophysics Data System (ADS)

    Semenov, V. A.; Kozlov, Zh. A.; Krachun, L.; Mateescu, G.; Morozov, V. M.; Oprea, A. I.; Oprea, K.; Puchkov, A. V.

    2010-05-01

    The temperature dependence of the frequency spectrum of tantalum in the temperature range from room temperature to 2300 K has been studied for the first time using inelastic slow-neutron scattering. The inelastic slow-neutron scattering spectra have been measured at different temperatures on a DIN-2PI time-of-flight spectrometer installed at the IBR-2 nuclear reactor (Joint Institute for Nuclear Research, Dubna, Russia) with the use of a TS3000K high-temperature thermostat. From the measured spectra, the frequency spectra of the tantalum crystal lattice have been determined at temperatures of 293, 1584, and 2300 K by the iteration method. As the temperature increases, the frequency spectrum, on the whole, is softened and the specific features manifested themselves at room temperature are smoothed. The variations observed have been explained by the increase in the role of the effects of vibration anharmonism at high temperatures.

  15. Atomization from a tantalum surface in graphite furnace atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Gregoire, D. C.; Chakrabarti, C. L.

    The mechanism of atom formation of U, V, Mo, Ni, Mn, Cu and Mg atomized from pyrolytic graphite and tantalum metal surfaces has been studied. The mechanism of atom formation for U from a graphite tube atomizer is reported for the first time. The peak absorbance for U and Cu is increased by factors of 59.7 and 2.0, respectively, whereas that of V, Mo and Ni is reduced by several orders of magnitude when they are atomized from a tantalum metal surface. The peak absorbance of Mn and Mg is not appreciably affected by the material of the atomization surface. Interaction of Mn and Mg with the graphite surface and formation of their refractory carbides was found to be negligible. Uranium forms a refractory carbide when heated from a graphite surface.

  16. 2014 NEPP Tasks Update for Ceramic and Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2014-01-01

    Presentation describes recent development in research on MnO2, wet, and polymer tantalum capacitors. Low-voltage failures in multilayer ceramic capacitors and techniques to reveal precious metal electrode (PME) and base metal electrode (BME) capacitors with cracks are discussed. A voltage breakdown technique is suggested to select high quality low-voltage BME ceramic capacitors.

  17. Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

    PubMed

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2011-10-12

    Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

  18. Alkyl group effects on CO insertion into coordinatively unsaturated early-transition-metal alkyls. Preparations and the first structural characterizations of tantalum enolate-O and tantalum. eta. sup 2 -acyl complexes

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

    Meyer, T.Y.; Garner, L.R.; Baenziger, N.C.

    1990-10-03

    Low-pressure carbonylation of the mono(peralkylcyclopentadienyl)tantalum(V) alkyls ({eta}-C{sub 5}Me{sub 4}R)TaR{prime}Cl{sub 3} (R = Me, Et; R{prime} = CH{sub 2}C{sub 6}H{sub 4}-p-Me, CH{sub 2}CMe{sub 3}) yields either the O-bound enolate or the {eta}{sup 2}-acyl as shown by ir/NMR spectroscopy and x-ray diffractometry. The p-tolyl enolate ({eta}-C{sub 5}Me{sub 5})Ta(OCH{double bond}CHC{sub 6}H{sub 4}-p-Me)Cl{sub 3}, derived directly from carbonylation of the tantalum 4-methylbenzyl precursor, is shown to possess a cis configuration in solution and in the solid state. Key structural features from a single-crystal x-ray diffraction study of the tetrahydrofuran-ligated enolate complex are reported. The mechanism of formation of the enolate from carbonylation of themore » 4-methylbenzyl complex is discussed. The previously reported acyl ({eta}-C{sub 5}Me{sub 4}R)Ta(C(O)CH{sub 2}CMe{sub 3})Cl{sub 3} has been reexamined and found to possess a symmetric, strongly distorted {eta}{sup 2}-acyl coordination by solution {sup 1}H NMR spectroscopy and solid-state x-ray diffractometry. The molecular structures of ({eta}-C{sub 5}Me{sub 5})Ta(OCH{double bond}CHC{sub 6}H{sub 4}-p-Me)Cl{sub 3} and ({eta}-C{sub 5}Me{sub 5})Ta(C(O)CH{sub 2}CMe{sub 3})Cl{sub 3}, which are reported here, are the first structural determinations of a tantalum enolate and of a tantalum {eta}{sup 2}-acyl. 41 refs., 2 figs., 8 tabs.« less

  19. Defect engineering of the oxygen-vacancy clusters formation in electron irradiated silicon by isovalent doping: An infrared perspective

    NASA Astrophysics Data System (ADS)

    Londos, C. A.; Sgourou, E. N.; Chroneos, A.

    2012-12-01

    Infrared spectroscopy was used to study the production and evolution of oxygen-vacancy (VOn for n = 1, 2, 3 and VmO for m = 1, 2, 3) clusters, in electron-irradiated Czochralski silicon (Cz-Si) samples, doped with isovalent dopants. It was determined that the production of the VO pair is enhanced in Ge-doped Si but is suppressed in Sn and Pb-doped Si. The phenomenon is discussed in terms of the competition between isovalent dopants and oxygen atoms in capturing vacancies in the course of irradiation. In the case of Ge, only transient GeV pairs form, leading finally to an increase of the VO production. Conversely, for Sn and Pb the corresponding pairs with vacancies are stable, having an opposite impact on the formation of VO pairs. Regarding V2O and V3O clusters, our measurements indicate that Ge doping enhances their formation, although Sn and Pb dopants suppress it. Similar arguments as those for the VO pair could be put forward, based on the effect of isovalent impurities on the availability of vacancies. Additionally, it was found that the conversion ratio of VO to VO2 decreases as the covalent radius of the isovalent dopant increases. These results are discussed in terms of the local strains introduced by the isovalent dopants in the Si lattice. These local strains affect the balance of the intrinsic defects created as a result of irradiation, as well as the balance between the two main reactions (VO + Oi → VO2 and VO + SiI → Oi) participating in the VO annealing, leading finally to a decrease of the VO2 production. The larger the covalent radius of the isovalent dopant (rGe < rSn < rPb), the larger the introduced strains in the lattice and then the less the VO2 formation in accordance with our experimental results. Interestingly, an opposite trend was observed for the conversion ratio of VO2 to VO3. The phenomenon is attributed to the enhanced diffusivity of oxygen impurity as a result of the presence of isovalent dopants, leading to an enhanced formation

  20. Study of surge current effects on solid tantalum capacitors

    NASA Technical Reports Server (NTRS)

    1980-01-01

    Results are presented of a 2,000 hour cycled life test program conducted to determine the effect of short term surge current screening on approximately 47 micron f/volt solid tantalum capacitors. The format provides average values and standard deviations of the parameters, capacitance, dissipation factor, and equivalent series resistance at 120 Hz, 1KHz, abd 40 KHz.

  1. Hydrogen bonding interaction of small acetaldehyde clusters studied with core-electron excitation spectroscopy in the oxygen K-edge region

    NASA Astrophysics Data System (ADS)

    Tabayashi, K.; Chohda, M.; Yamanaka, T.; Tsutsumi, Y.; Takahashi, O.; Yoshida, H.; Taniguchi, M.

    2010-06-01

    In order to examine inner-shell electron excitation spectra of molecular clusters with strong multipole interactions, excitation spectra and time-of-flight (TOF) fragment-mass spectra of small acetaldehyde (AA) clusters have been studied under the beam conditions. The TOF spectra at the oxygen K-edge region showed an intense growth of the protonated clusters, MnH+ (M=CH3CHO) in the cluster beams. "cluster-specific" excitation spectra could be generated by monitoring partial-ion-yields of the protonated clusters. The most intense band of O1s→π*CO was found to shift to a higher energy by 0.15 eV relative to the monomer band upon clusterization. X-ray absorption spectra (XAS) were also calculated for the representative dimer configurations using a computer modelling program based on the density functional theory. The XAS prediction for the most stable (non-planar) configuration was found to give a close comparison with the cluster-band shift observed. The band shift was interpreted as being due to the HOMO-LUMO interaction within the complex where a contribution of vibrationally blue-shifting hydrogen bonding could be identified.

  2. Diffusion-Cooled Tantalum Hot-Electron Bolometer Mixers

    NASA Technical Reports Server (NTRS)

    Skalare, Anders; McGrath, William; Bumble, Bruce; LeDuc, Henry

    2004-01-01

    A batch of experimental diffusion-cooled hot-electron bolometers (HEBs), suitable for use as mixers having input frequencies in the terahertz range and output frequencies up to about a gigahertz, exploit the superconducting/normal-conducting transition in a thin strip of tantalum. The design and operation of these HEB mixers are based on mostly the same principles as those of a prior HEB mixer that exploited the superconducting/normal- conducting transition in a thin strip of niobium and that was described elsewhere.

  3. Electron-ion temperature equilibration in warm dense tantalum

    DOE PAGES

    Doppner, T; LePape, S.; Ma, T.; ...

    2014-11-05

    We present measurements of electron-ion temperature equilibration in proton-heated tantalum, under warm dense matter conditions. Our results agree with theoretical predictions for metals calculated using input data from ab initio simulations. Furthermore, the fast relaxation observed in the experiment contrasts with much longer equilibration times found in proton heated carbon, indicating that the energy flow pathways in warm dense matter are far from being fully understood.

  4. Response and representation of ductile damage under varying shock loading conditions in tantalum

    DOE PAGES

    Bronkhorst, C. A.; Gray, III, G. T.; Addessio, F. L.; ...

    2016-02-25

    The response of polycrystalline metals, which possess adequate mechanisms for plastic deformation under extreme loading conditions, is often accompanied by the formation of pores within the structure of the material. This large deformation process is broadly identified as progressive with nucleation, growth, coalescence, and failure the physical path taken over very short periods of time. These are well known to be complex processes strongly influenced by microstructure, loading path, and the loading profile, which remains a significant challenge to represent and predict numerically. In the current study, the influence of loading path on the damage evolution in high-purity tantalum ismore » presented. Tantalum samples were shock loaded to three different peak shock stresses using both symmetric impact, and two different composite flyer plate configurations such that upon unloading the three samples displayed nearly identical “pull-back” signals as measured via rear-surface velocimetry. While the “pull-back” signals observed were found to be similar in magnitude, the sample loaded to the highest peak stress nucleated a connected field of ductile fracture which resulted in complete separation, while the two lower peak stresses resulted in incipient damage. The damage evolution in the “soft” recovered tantalum samples was quantified using optical metallography, electron-back-scatter diffraction, and tomography. These experiments are examined numerically through the use of a model for shock-induced porosity evolution during damage. The model is shown to describe the response of the tantalum reasonably well under strongly loaded conditions but less well in the nucleation dominated regime. As a result, numerical results are also presented as a function of computational mesh density and discussed in the context of improved representation of the influence of material structure upon macro-scale models of ductile damage.« less

  5. Effect of dielectric stoichiometry and interface chemical state on band alignment between tantalum oxide and platinum

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

    Lebedinskii, Yu. Yu.; National Research Nuclear University MEPhI; Chernikova, A. G.

    2015-10-05

    The tantalum oxide–platinum interface electronic properties determined by X-ray photoelectron spectroscopy are found to depend on the dielectric stoichiometry and platinum chemical state. We demonstrate the slow charging of the tantalum oxide in cases of Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt interfaces under the X-ray irradiation. This behavior is proposed to be related to the charge accumulation at oxygen vacancies induced traps. Based on the proposed methodology, we define the intrinsic conductive band offset (CBO) ∼1.3 eV (both for Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt) and CBO after the full saturation of the traps charging ∼0.5 eV, while the lastmore » one defines the energy position of charged traps below the bottom of conduction band. We demonstrate also the pining at the both Ta{sub 2}O{sub 5}/Pt and Ta{sub 2}O{sub 5−y}/Pt interfaces even in the “intrinsic” state, apparently induced by the presence of additional interfacial states. No shifts of Ta4f line and band alignment in over stoichiometric Ta{sub 2}O{sub 5+x}/Pt structure during X-ray irradiation, as well as the absence of pinning, resulting in increase of CBO up to 2.3 eV are found. This behavior is related to the PtO{sub 2} interfacing layer formation at Ta{sub 2}O{sub 5+x}/Pt, blocking the charging of the surface states and associated dipole formation.« less

  6. The structure, bond strength and apatite-inducing ability of micro-arc oxidized tantalum and their response to annealing

    NASA Astrophysics Data System (ADS)

    Wang, Cuicui; Wang, Feng; Han, Yong

    2016-01-01

    In this study, the tantalum oxide coatings were formed on pure tantalum (Ta) by micro-arc oxidation (MAO) in electrolytic solutions of calcium acetate and β-glycerophosphate disodium, and the effect of the applied voltage on the microstructure and bond strength of the MAO coatings was systematically investigated. The effect of annealing treatment on the microstructure, bond strength and apatite-inducing ability of the MAO coatings formed at 350 and 450 V was also studied. The study revealed that during the preparation of tantalum oxide coatings on Ta substrate by MAO, the applied voltage considerably affected the phase components, morphologies and bond strength of the coatings, but had little effect on surface chemical species. After annealing treatment, newly formed CaTa4O11 phase mainly contributed to the much more stronger apatite-inducing ability of the annealed tantalum oxide coatings than those that were not annealed. The better apatite-inducing ability of the MAO coatings formed at 450 V compared to those formed at 350 V was attributed to the less amorphous phase and more crystalline phase as well as more Ca and P contained in the MAO coatings with increasing the applied voltage.

  7. XPS investigation of depth profiling induced chemistry

    NASA Astrophysics Data System (ADS)

    Pratt, Quinn; Skinner, Charles; Koel, Bruce; Chen, Zhu

    2017-10-01

    Surface analysis is an important tool for understanding plasma-material interactions. Depth profiles are typically generated by etching with a monatomic argon ion beam, however this can induce unintended chemical changes in the sample. Tantalum pentoxide, a sputtering standard, and PEDOT:PSS, a polymer that was used to mimic the response of amorphous carbon-hydrogen co-deposits, were studied. We compare depth profiles generated with monatomic and gas cluster argon ion beams (GCIB) using X-ray photoelectron spectroscopy (XPS) to quantify chemical changes. In both samples, monatomic ion bombardment led to beam-induced chemical changes. Tantalum pentoxide exhibited preferential sputtering of oxygen and the polymer experienced significant bond modification. Depth profiling with clusters is shown to mitigate these effects. We present sputtering rates for Ta2O5 and PEDOT:PSS as a function of incident energy and flux. Support was provided through DOE Contract Number DE-AC02-09CH11466.

  8. Design, Development, manufacture and qualification of wet-slug all-tantalum capacitors

    NASA Technical Reports Server (NTRS)

    Maher, R. H.

    1977-01-01

    Specifications and qualification tests data are presented for over eleven hundred T3 case all-tantalum capacitors encompassing four ratings. The finalized product has all the advantages of the silver cased wet and is capable of withstanding some reverse potential ac ripple current.

  9. Physics of Shock Compression and Release: NEMD Simulations of Tantalum and Silicon

    NASA Astrophysics Data System (ADS)

    Hahn, Eric; Meyers, Marc; Zhao, Shiteng; Remington, Bruce; Bringa, Eduardo; Germann, Tim; Ravelo, Ramon; Hammerberg, James

    2015-06-01

    Shock compression and release allow us to evaluate physical deformation and damage mechanisms occurring in extreme environments. SPaSM and LAMMPS molecular dynamics codes were employed to simulate single and polycrystalline tantalum and silicon at strain rates above 108 s-1. Visualization and analysis was accomplished using OVITO, Crystal Analysis Tool, and a redesigned orientation imaging function implemented into SPaSM. A comparison between interatomic potentials for both Si and Ta (as pertaining to shock conditions) is conducted and the influence on phase transformation and plastic relaxation is discussed. Partial dislocations, shear induced disordering, and metastable phase changes are observed in compressed silicon. For tantalum, the role of grain boundary and twin intersections are evaluated for their role in ductile spallation. Finally, the temperature dependent response of both Ta and Si is investigated.

  10. Calcium EXAFS Establishes the Mn-Ca Cluster in the Oxygen-Evolving Complex of Photosystem II†

    PubMed Central

    Cinco, Roehl M.; Holman, Karen L. McFarlane; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

    2014-01-01

    The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 Å, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is ~ 3.5 Å distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster. PMID:12390018

  11. Intraoperative Localization of Tantalum Markers for Proton Beam Radiation of Choroidal Melanoma by an Opto-Electronic Navigation System: A Novel Technique

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

    Amstutz, Christoph A., E-mail: christoph.amstutz@usz.ch; Bechrakis, Nikolaos E.; Foerster, Michael H.

    2012-03-15

    Purpose: External beam proton radiation therapy has been used since 1975 to treat choroidal melanoma. For tumor location determination during proton radiation treatment, surgical tantalum clips are registered with image data. This report introduces the intraoperative application of an opto-electronic navigation system to determine with high precision the position of the tantalum markers and their spatial relationship to the tumor and anatomical landmarks. The application of the technique in the first 4 patients is described. Methods and Materials: A navigated reference base was attached noninvasively to the eye, and a navigated pointer device was used to record the spatial positionmore » of the tantalum markers, the tumor, and anatomical landmarks. Measurement accuracy was assessed on ex vivo porcine eye specimen by repetitive recording of the tantalum marker positions. The method was applied intraoperatively on 4 patients undergoing routine tantalum clip surgery. The spatial position information delivered by the navigation system was compared to the geometric data generated by the EYEPLAN software. Results: In the ex vivo experiments, the maximum repetition error was 0.34 mm. For the intraoperative application, the root mean square error of paired-points matching of the marker positions from the navigation system and from the EYEPLAN software was 0.701-1.25 mm. Conclusions: Navigation systems are a feasible tool for accurate localization of tantalum markers and anatomic landmarks. They can provide additional geometric information, and therefore have the potential to increase the reliability and accuracy of external beam proton radiation therapy for choroidal melanoma.« less

  12. Novel hierarchical tantalum oxide-PDMS hybrid coating for medical implants: One pot synthesis, characterization and modulation of fibroblast proliferation.

    PubMed

    Tran, Phong A; Fox, Kate; Tran, Nhiem

    2017-01-01

    Surface properties such as morphology, roughness and charge density have a strong influence on the interaction of biomaterials and cells. Hierarchical materials with a combination of micron/submicron and nanoscale features for coating of medical implants could therefore have significant potential to modulate cellular responses and eventually improve the performance of the implants. In this study, we report a simple, one pot wet chemistry preparation of a hybrid coating system with hierarchical surface structures consisting of polydimethylsiloxane (PDMS) and tantalum oxide. Medical grade, amine functional PDMS was mixed with tantalum ethoxide which subsequently formed Ta 2 O 5 in situ through hydrolysis and condensation during coating process. The coatings were characterized by SEM, EDS, XPS, confocal scanning microscopy, contact angle measurement and in vitro cell culture. Varying PDMS and tantalum ethoxide ratios resulted in coatings of different surface textures ranging from smooth to submicro- and nano-structured. Strikingly, hierarchical surfaces containing both microscale (1-1.5μm) and nanoscale (86-163nm) particles were found on coatings synthesized with 20% and 40% (v/v) tantalum ethoxide. The coatings were similar in term of hydrophobicity but showed different surface roughness and chemical composition. Importantly, higher cell proliferation was observed on hybrid surface with hierarchical structures compared to pure PDMS or pure tantalum oxide. The coating process is simple, versatile, carried out under ambient condition and requires no special equipment. Copyright © 2016 Elsevier Inc. All rights reserved.

  13. Observations on Si-based micro-clusters embedded in TaN thin film deposited by co-sputtering with oxygen contamination

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

    Lee, Young Mi; Jung, Min-Sang; Choi, Duck-Kyun, E-mail: duck@hanyang.ac.kr, E-mail: mcjung@oist.jp

    2015-08-15

    Using scanning electron microscopy (SEM) and high-resolution x-ray photoelectron spectroscopy with the synchrotron radiation we investigated Si-based micro-clusters embedded in TaSiN thin films having oxygen contamination. TaSiN thin films were deposited by co-sputtering on fixed or rotated substrates and with various power conditions of TaN and Si targets. Three types of embedded micro-clusters with the chemical states of pure Si, SiO{sub x}-capped Si, and SiO{sub 2}-capped Si were observed and analyzed using SEM and Si 2p and Ta 4f core-level spectra were derived. Their different resistivities are presumably due to the different chemical states and densities of Si-based micro-clusters.

  14. Patterning of magnetic thin films and multilayers using nanostructured tantalum gettering templates.

    PubMed

    Qiu, Wenlan; Chang, Long; Lee, Dahye; Dannangoda, Chamath; Martirosyan, Karen; Litvinov, Dmitri

    2015-03-25

    This work demonstrates that a nonmagnetic thin film of cobalt oxide (CoO) sandwiched between Ta seed and capping layers can be effectively reduced to a magnetic cobalt thin film by annealing at 200 °C, whereas CoO does not exhibit ferromagnetic properties at room temperature and is stable at up to ∼400 °C. The CoO reduction is attributed to the thermodynamically driven gettering of oxygen by tantalum, similar to the exothermic reduction-oxidation reaction observed in thermite systems. Similarly, annealing at 200 °C of a nonmagnetic [CoO/Pd]N multilayer thin film sandwiched between Ta seed and Ta capping layers results in the conversion into a magnetic [Co/Pd]N multilayer, a material with perpendicular magnetic anisotropy that is of interest for magnetic data storage applications. A nanopatterning approach is introduced where [CoO/Pd]N multilayers is locally reduced into [Co/Pd]N multilayers to achieve perpendicular magnetic anisotropy nanostructured array. This technique can potentially be adapted to nanoscale patterning of other systems for which thermodynamically favorable combination of oxide and gettering layers can be identified.

  15. Effect of Surge Current Testing on Reliability of Solid Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2008-01-01

    Tantalum capacitors manufactured per military specifications are established reliability components and have less than 0.001% of failures per 1000 hours for grades D or S, thus positioning these parts among electronic components with the highest reliability characteristics. Still, failures of tantalum capacitors do happen and when it occurs it might have catastrophic consequences for the system. To reduce this risk, further development of a screening and qualification system with special attention to the possible deficiencies in the existing procedures is necessary. The purpose of this work is evaluation of the effect of surge current stress testing on reliability of the parts at both steady-state and multiple surge current stress conditions. In order to reveal possible degradation and precipitate more failures, various part types were tested and stressed in the range of voltage and temperature conditions exceeding the specified limits. A model to estimate the probability of post-surge current testing-screening failures and measures to improve the effectiveness of the screening process has been suggested.

  16. In-operando synchronous time-multiplexed O K-edge x-ray absorption spectromicroscopy of functioning tantalum oxide memristors

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

    Kumar, Suhas; Department of Electrical Engineering, Stanford University, Stanford, California 94305; Graves, Catherine E.

    2015-07-21

    Memristors are receiving keen interest because of their potential varied applications and promising large-scale information storage capabilities. Tantalum oxide is a memristive material that has shown promise for high-performance nonvolatile computer memory. The microphysics has been elusive because of the small scale and subtle physical changes that accompany conductance switching. In this study, we probed the atomic composition, local chemistry, and electronic structure of functioning tantalum oxide memristors through spatially mapped O K-edge x-ray absorption. We developed a time-multiplexed spectromicroscopy technique to enhance the weak and possibly localized oxide modifications with spatial and spectral resolutions of <30 nm and 70 meV, respectively.more » During the initial stages of conductance switching of a micrometer sized crosspoint device, the spectral changes were uniform within the spatial resolution of our technique. When the device was further driven with millions of high voltage-pulse cycles, we observed lateral motion and separation of ∼100 nm-scale agglomerates of both oxygen interstitials and vacancies. We also demonstrate a unique capability of this technique by identifying the relaxation behavior in the material during electrical stimuli by identifying electric field driven changes with varying pulse widths. In addition, we show that changes to the material can be localized to a spatial region by modifying its topography or uniformity, as against spatially uniform changes observed here during memristive switching. The goal of this report is to introduce the capability of time-multiplexed x-ray spectromicroscopy in studying weak-signal transitions in inhomogeneous media through the example of the operation and temporal evolution of a memristor.« less

  17. Effect of silicon, tantalum, and tungsten doping and polarization on bioactivity of hydroxyapatite

    NASA Astrophysics Data System (ADS)

    Dhal, Jharana

    Hydroxyapatite (HAp) ceramics has important applications as bone graft because of the structural and compositional similarities with bone tissue. However, inferior osteogenic capacity to bone and poor mechanical properties have been identified to be major disadvantages of synthetic HAp compared to the living bone tissue. The objective of the current study is to evaluate the effect of doping with higher valent cations (Tungsten, tantalum, and silicon) and polarization or combination of both on change in property of doped HAp and subsequent impact its bioactivity. In vitro study with human osteoblast cells was used to investigate the influences of doping and polarization on bone cell-materials interactions. The bioactivity of doped HAp was compared with pure HAp. Effect of doping and polarization on the change in HAp was investigated by monitoring change in mineral phases, stored charge, and activation energy of HAp. Activation energy of depolarization was used to explain the possible mechanism of polarization in doped samples. Bioactivity of HAp increased when doped with tantalum and tungsten. Polarization further increased the bioactivity of tungsten- and tantalum-doped samples. Increase in bioactivity on polarized and doped samples was attributed to increase in surface energy and increase in surface wettability. Whereas, an increase in bioactivity on doped unpolarized surface was attributed to change in microstructure. Polarized charge calculated from TSDC indicates that polarized charge decreases on tantalum- and tungsten-doped HAp. The decrease in polarized charge was attributed to the presence of significant amount of different phases that may hinder the ionic motion in doped samples. However, for silicon-doped HAp, TSDC study showed no difference in the mechanism of polarization between doped and undoped samples. Increase in silicon doping decreased the grain size though mechanism is not affected by grain size. Total stored charge decreased with increase in

  18. Evaluation of wet tantalum capacitors after exposure to extended periods of ripple current, volume 1

    NASA Technical Reports Server (NTRS)

    Watson, G. W.; Lasharr, J. C.; Shumaker, M. J.

    1974-01-01

    The application of tantalum capacitors in the Viking Lander includes both dc voltage and ripple current electrical stress, high temperature during nonoperating times (sterilization), and high vibration and shock loads. The capacitors must survive these severe environments without any degradation if reliable performance is to be achieved. A test program was established to evaluate both wet-slug tantalum and wet-foil capacitors under conditions accurately duplicating actual Viking applications. Test results of the electrical performance characteristics during extended periods of ripple current, the characteristics of the internal silver migration as a function for extended periods of ripple current, and the existence of any memory characteristics are presented.

  19. Evaluation of wet tantalum capacitors after exposure to extended periods of ripple current, volume 2

    NASA Technical Reports Server (NTRS)

    Ward, C. M.

    1975-01-01

    The application of tantalum capacitors in the Viking Lander includes dc voltage and ripple current electrical stress, high temperature during nonoperating times (sterilization), and high vibration and shock loads. The capacitors must survive these severe environments without any degradation if reliable performance is to be achieved. A test program was established to evaluate both wet-slug tantalum and wet-foil capacitors under conditions accurately duplicating actual Viking applications. Test results of the electrical performance characteristics during extended periods of ripple current, the characteristics of the internal silver migration as a function of extended periods of ripple current, and the existence of any memory characteristics are presented.

  20. Niobium (columbium) and tantalum resources of Brazil

    USGS Publications Warehouse

    White, Max Gregg

    1975-01-01

    Most of the niobium resources of Brazil occur as pyrochlore in carbonatites within syenitic intrusives of Late Cretaceous to early Tertiary age in western Minas Gerais and southeastern Goils. Minor amounts of it are produced together with tantalum from columbite-tantalite concentrates from pegmatites and placers adjacent to them, in the Sao Joao del Rei district in south-central Minas Gerais. All the niobium and tantalum produced in Brazil is exported. The only pyrochlore mined is from the Barreiro carbonatite deposit near Araxa in Minas Gerais where concentrates and ferroniobium are produced. Exploration work for pyrochlore and other mineral resources are being undertaken on other carbonatites, particularly at Catalao I in southeast Goias and at Tapira and Serra Negra in western Minas Gerais. Annual production and export from the Barreiro deposit are about 8,000 metric tons of pyrochlore concentrate containing about 60 percent Nb205 and about 2,700 metric tons of ferroniobium with 63 percent Nb2O5. The annual production capacity of the Barreiro plant is 18,000 tons of concentrate and 4,000 tons of ferroniobium. Ore reserves of the Barreiro deposit in all categories are 380 million tons with percent Nb2O5. Annual production of tantalite-columbite from the Sao Joao del Rei district, most of which is exported to the United States, is about 290 tons, of which about 79 percent is tantalite and about percent is columbite. Reserves of tantalite-columbite in the Sao Joao del Rei district are about 43,000 tons of proved and 73,000 tons of probable ore.

  1. Photospheric carbon and oxygen abundances of F-G type stars in the Pleiades cluster*

    NASA Astrophysics Data System (ADS)

    Takeda, Yoichi; Hashimoto, Osamu; Honda, Satoshi

    2017-02-01

    In order to investigate the carbon-to-oxygen ratio of the young open cluster M 45 (Pleiades), the C and O abundances of 32 selected F-G type dwarfs (in the effective temperature range of Teff ˜ 5800-7600 K and projected rotational velocity range of vesin i ˜ 10-110 km s-1) belonging to this cluster were determined by applying the synthetic spectrum-fitting technique to C i 5380 and O i 6156-8 lines. The non-local thermodynamical equilibrium corrections for these C i and O i lines were found to be practically negligible (less than a few hundredths dex).The resulting C and O abundances (along with the Fe abundance) turned out nearly uniform without any systematic dependence upon Teff or vesin i. We found, however, in spite of almost solar Fe abundance ([Fe/H] ˜ 0), carbon turned out to be slightly subsolar ([C/H] ˜ -0.1) while that of oxygen was slightly supersolar ([O/H] ˜ +0.1). This leads to a conclusion that the [C/O] ratio was moderately subsolar (˜ -0.2) in the primordial gas from which these Pleiades stars were formed ˜ 120-130 Myr ago. Interestingly, similarly young B-type stars are reported to show just the same result ([C/O] ˜ -0.2), while rather aged (˜ 1-10 Gyr) field F-G stars of near-solar metallicity yield almost the solar value ([C/O] ˜ 0) on average. Such a difference in the C/O ratio between two star groups of distinctly different ages may be explained as a consequence of the orbit migration mechanism which Galactic stars may undergo over a long time.

  2. Development of high temperature materials for solid propellant rocket nozzle applications. [tantalum carbides-tungsten fiber composites

    NASA Technical Reports Server (NTRS)

    Manning, C. R., Jr.; Honeycutt, L., III

    1974-01-01

    Evaluation of tantalum carbide-tungsten fiber composites has been completed as far as weight percent carbon additions and weight percent additions of tungsten fiber. Extensive studies were undertaken concerning Young's Modulus and fracture strength of this material. Also, in-depth analysis of the embrittling effects of the extra carbon additions on the tungsten fibers has been completed. The complete fabrication procedure for the tantalum carbide-tungsten fiber composites with extra carbon additions is given. Microprobe and metallographic studies showed the effect of extra carbon on the tungsten fibers, and evaluation of the thermal shock parameter fracture strength/Young's Modulus is included.

  3. Use of steel and tantalum apparatus for molten Cd-Mg-Zn alloys

    NASA Technical Reports Server (NTRS)

    Bennett, G. A.; Burris, L., Jr.; Kyle, M. L.; Nelson, P. A.

    1966-01-01

    Steel and tantalum apparatus contains various ternary alloys of cadmium, zinc, and magnesium used in pyrochemical processes for the recovery of uranium-base reactor fuels. These materials exhibit good corrosion resistance at the high temperatures necessary for fuel separation in liquid metal-molten salt solvents.

  4. Synthesis, Consolidation and Characterization of Sol-gel Derived Tantalum-Tungsten Oxide Thermite Composites

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

    Cervantes, O

    2010-06-01

    Energetic composite powders consisting of sol-gel (SG) derived nanostructured tungsten oxide were produced with various amounts of micrometer-scale tantalum fuel metal. Such energetic composite powders were ignition-tested and results show that the powders are not sensitive to friction, spark and/or impact ignition. Initial consolidation experiments, using the High Pressure Spark Plasma Sintering (HPSPS) technique, on the SG derived nanostructured tungsten oxide produced samples with higher relative density than can be achieved with commercially available tungsten oxide. The SG derived nanostructured tungsten oxide with immobilized tantalum fuel metal (Ta - WO3) energetic composite was consolidated to a density of 9.17 g·cm-3more » or 93% relative density. In addition, those samples were consolidated without significant pre-reaction of the constituents, thus retaining their stored chemical energy.« less

  5. Effect of Preconditioning and Soldering on Failures of Chip Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2014-01-01

    Soldering of molded case tantalum capacitors can result in damage to Ta205 dielectric and first turn-on failures due to thermo-mechanical stresses caused by CTE mismatch between materials used in the capacitors. It is also known that presence of moisture might cause damage to plastic cases due to the pop-corning effect. However, there are only scarce literature data on the effect of moisture content on the probability of post-soldering electrical failures. In this work, that is based on a case history, different groups of similar types of CWR tantalum capacitors from two lots were prepared for soldering by bake, moisture saturation, and longterm storage at room conditions. Results of the testing showed that both factors: initial quality of the lot, and preconditioning affect the probability of failures. Baking before soldering was shown to be effective to prevent failures even in lots susceptible to pop-corning damage. Mechanism of failures is discussed and recommendations for pre-soldering bake are suggested based on analysis of moisture characteristics of materials used in the capacitors' design.

  6. NEPP Evaluation of Automotive Grade Tantalum Chip Capacitors

    NASA Technical Reports Server (NTRS)

    Sampson, Mike; Brusse, Jay

    2018-01-01

    Automotive grade tantalum (Ta) chip capacitors are available at lower cost with smaller physical size and higher volumetric efficiency compared to military/space grade capacitors. Designers of high reliability aerospace and military systems would like to take advantage of these attributes while maintaining the high standards for long-term reliable operation they are accustomed to when selecting military-qualified established reliability tantalum chip capacitors (e.g., MIL-PRF-55365). The objective for this evaluation was to assess the long-term performance of off-the-shelf automotive grade Ta chip capacitors (i.e., manufacturer self-qualified per AEC Q-200). Two (2) lots of case size D manganese dioxide (MnO2) cathode Ta chip capacitors from 1 manufacturer were evaluated. The evaluation consisted of construction analysis, basic electrical parameter characterization, extended long-term (2000 hours) life testing and some accelerated stress testing. Tests and acceptance criteria were based upon manufacturer datasheets and the Automotive Electronics Council's AEC Q-200 qualification specification for passive electronic components. As-received a few capacitors were marginally above the specified tolerance for capacitance and ESR. X-ray inspection found that the anodes for some devices may not be properly aligned within the molded encapsulation leaving less than 1 mil thickness of the encapsulation. This evaluation found that the long-term life performance of automotive grade Ta chip capacitors is generally within specification limits suggesting these capacitors may be suitable for some space applications.

  7. Antibacterial properties and cytocompatibility of tantalum oxide coatings with different silver content

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

    Huang, Heng-Li; Chang, Yin-Yu, E-mail: yinyu@mail2000.com.tw; Chen, Hung-Jui

    Tantalum (Ta) oxides and their coatings have been proved to increase their applications in the biomedical fields by improving osseointegration and wear resistance. In this study, Ta oxide coatings containing different proportions of Ag are deposited on SS304 materials. A twin-gun magnetron sputtering system is used to deposit the tantalum oxide-Ag coating. In this study, Staphylococcus aureus, which exhibits physiological commensalism on the human skin, nares, and mucosal and oral areas, is chosen as the model for in vitro antibacterial analyses via a fluorescence staining method using Syto9. The cytocompatibility and adhesive morphology of human skin fibroblast cells (CCD-966SK) onmore » the coatings are also determined by using the microculture tetrazolium assay. This study shows that Ta{sub 2}O{sub 5} and Ta{sub 2}O{sub 5}-Ag coatings with 12.5 at. % of Ag exhibit improved antibacterial effects against S. aureus and have good skin fibroblast cell cellular biocompatibility.« less

  8. Analysis of shockless dynamic compression data on solids to multi-megabar pressures: Application to tantalum

    DOE PAGES

    Davis, Jean -Paul; Brown, Justin L.; Knudson, Marcus D.; ...

    2014-11-26

    In this research, magnetically-driven, planar shockless-compression experiments to multi-megabar pressures were performed on tantalum samples using a stripline target geometry. Free-surface velocity waveforms were measured in 15 cases; nine of these in a dual-sample configuration with two samples of different thicknesses on opposing electrodes, and six in a single-sample configuration with a bare electrode opposite the sample. Details are given on the application of inverse Lagrangian analysis (ILA) to these data, including potential sources of error. The most significant source of systematic error, particularly for single-sample experiments, was found to arise from the pulse-shape dependent free-surface reflected wave interactions withmore » the deviatoric-stress response of tantalum. This could cause local, possibly temporary, unloading of material from a ramp compressed state, and thus multi-value response in wave speed that invalidates the free-surface to in-material velocity mapping step of ILA. By averaging all 15 data sets, a final result for the principal quasi-isentrope of tantalum in stress-strain was obtained to a peak longitudinal stress of 330 GPa with conservative uncertainty bounds of ±4.5% in stress. The result agrees well with a tabular equation of state developed at Los Alamos National Laboratory.« less

  9. Internal fuse modules for solid tantalum capacitors

    NASA Technical Reports Server (NTRS)

    Dematos, H. V.

    1981-01-01

    Miniature fuse modules were designed for and incorporated into two styles of solid tantalum capacitors. One is an epoxy molded, radial leaded, high frequency decoupling capacitor; the other is an hermetically sealed device with axial lead wires. The fusible element for both devices consists of a fine bimetallic wire which reacts exothermically upon reaching a critical temperature and then disintegrates. The desirability of having fused devices is discussed and design constraints, in particular those which minimize inductance and series resistance while optimizing fuse actuation characteristics, are reviewed. Factors affecting the amount of energy required to actuate the fuse and reliability of acuation are identified.

  10. Alkali oxide-tantalum, niobium and antimony oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Brower, W. S.; Parker, H. S.; Minor, D. B.; Waring, J. L.

    1975-01-01

    The phase equilibrium relations of four systems were investigated in detail. These consisted of sodium and potassium antimonates with antimony oxide and tantalum and niobium oxide with rubidium oxide as far as the ratio 4Rb2O:llB2O5 (B=Nb, Ta). The ternary system NaSbO3-Sb2O4-NaF was investigated extensively to determine the actual composition of the body centered cubic sodium antimonate. Various other binary and ternary oxide systems involving alkali oxides were examined in lesser detail. The phases synthesized were screened by ion exchange methods to determine mobility of the mobility of the alkali ion within the niobium, tantalum or antimony oxide (fluoride) structural framework. Five structure types warranted further investigation; these structure types are (1) hexagonal tungsten bronze (HTB), (2) pyrochlore, (3) the hybrid HTB-pyrochlore hexagonal ordered phases, (4) body centered cubic antimonates and (5) 2K2O:3Nb2O5. Although all of these phases exhibit good ion exchange properties only the pyrochlore was prepared with Na(+) ions as an equilibrium phase and as a low porosity ceramic. Sb(+3) in the channel interferes with ionic conductivity in this case, although relatively good ionic conductivity was found for the metastable Na(+) ion exchanged analogs of RbTa2O5F and KTaWO6 pyrochlore phases.

  11. Onset of carbon-carbon bonding in Ta(5)C(y) (y = 0-6) clusters: a threshold photoionization and density functional theory study.

    PubMed

    Dryza, Viktoras; Alvino, Jason F; Metha, Gregory F

    2010-04-01

    We have used photoionization efficiency spectroscopy to determine ionization energies (IEs) of the gas-phase tantalum-carbide clusters Ta(5)C(y) (y = 0-6). The structures of the clusters observed in the experiment are assigned by comparing the experimental IEs with those of candidate isomers, calculated by density functional theory. Two competing geometries of the underlying Ta(5) cluster are found to be present in the assigned Ta(5)C(y) structures; either a "prolate" or "distorted oblate" trigonal bipyramid geometry. The onset of carbon-carbon bonding in the Ta(5)C(y) series is proposed to occur at y = 6, with the structure of Ta(5)C(6) containing two molecular C(2) units.

  12. Globular cluster ages determined from the Oosterhoff period-metallicity effect using oxygen-enhanced isochrones. III

    NASA Astrophysics Data System (ADS)

    Sandage, Allan

    1993-08-01

    The new brighter calibration of absolute luminosities of RR Lyrae stars by about 0.25 mag as a function of metallicity via the Oosterhoff period effect gives a revised age of the Galactic globular cluster system as 14 Gyr when used with the oxygen-enhanced main-sequence termination models of Bergbush and VandenBerg (1992). There is no correlation of cluster age with metallicity. The presence or absence of age differences between any two clusters is neither proof nor disproof of the Eggen-Lynden Bell-Sandage model of the formation of the Galaxy by collapse. If there were different density regimes within the initial density fluctuation that was the protogalaxy, then there has been a hierarchy of collapse times for the various parts of the present Galaxy. The age of the universe is 15 Gyr, based on the age of the Galaxy at 14 Gyr, to which 1 Gyr is added for the gestation time of the galaxies. The ratio of this age to the inverse Hubble constant with H(0) about 45 km/s Mpc, based on a recent concordant determination using supernovae of type Ia, is close to the critical value of 2/3 required if the deceleration is caused by a mean density just equal to that needed for closure. For the first time, these new data give the possibility that Omega = 1 from this timing test.

  13. Characterization of a unique [FeS] cluster in the electron transfer chain of the oxygen tolerant [NiFe] hydrogenase from Aquifex aeolicus.

    PubMed

    Pandelia, Maria-Eirini; Nitschke, Wolfgang; Infossi, Pascale; Giudici-Orticoni, Marie-Thérèse; Bill, Eckhard; Lubitz, Wolfgang

    2011-04-12

    Iron-sulfur clusters are versatile electron transfer cofactors, ubiquitous in metalloenzymes such as hydrogenases. In the oxygen-tolerant Hydrogenase I from Aquifex aeolicus such electron "wires" form a relay to a diheme cytb, an integral part of a respiration pathway for the reduction of O(2) to water. Amino acid sequence comparison with oxygen-sensitive hydrogenases showed conserved binding motifs for three iron-sulfur clusters, the nature and properties of which were unknown so far. Electron paramagnetic resonance spectra exhibited complex signals that disclose interesting features and spin-coupling patterns; by redox titrations three iron-sulfur clusters were identified in their usual redox states, a [3Fe4S] and two [4Fe4S], but also a unique high-potential (HP) state was found. On the basis of (57)Fe Mössbauer spectroscopy we attribute this HP form to a superoxidized state of the [4Fe4S] center proximal to the [NiFe] site. The unique environment of this cluster, characterized by a surplus cysteine coordination, is able to tune the redox potentials and make it compliant with the [4Fe4S](3+) state. It is actually the first example of a biological [4Fe4S] center that physiologically switches between 3+, 2+, and 1+ oxidation states within a very small potential range. We suggest that the (1 + /2+) redox couple serves the classical electron transfer reaction, whereas the superoxidation step is associated with a redox switch against oxidative stress.

  14. The Mn4Ca-cluster of the photosynthetic oxygen evolving centre: its structure, function and evolution.

    PubMed

    Barber, James

    2016-10-05

    Photosystem II is the chlorophyll containing enzyme in which the very first chemical energy storing reaction of photosynthesis occurs. It does so by splitting water into molecular oxygen and hydrogen equivalents at a catalytic centre composed of four Mn ions and one Ca2+. All the oxygen in the atmosphere is derived from this reaction and without it the biosphere, as we know it, would not exist. Indeed its appearance about 3 billion years ago gave rise to the "big bang of evolution". Thus understanding the structure and functioning of this metal cluster is a major topic in science and here I discuss it in terms of research over of the last twelve years dating back to when it was first proposed to be a Mn3CaO4 cubane with the fourth Mn attached to cubane by one of its oxo bridging bonds. In so doing a number of novel properties emerge for this metallo-protein with implications for its mechanism and evolutionary origin.

  15. An experimental study of the solubility and speciation of tantalum in fluoride-bearing aqueous solutions at elevated temperature

    DOE PAGES

    Timofeev, Alexander; Migdisov, Art. A.; Williams-Jones, A. E.

    2016-10-27

    Here, the solubility of Ta 2O 5 (solid) and the speciation of tantalum in HF-bearing aqueous solutions have been determined at temperatures of 100-250 °C and vapour-saturated water pressure. Tantalum is transported as the species Ta(OH) 5 0 at low HF concentration and pH ~1-3. At higher HF concentration, tantalum mobility is controlled by the species TaF 3(OH) 3- and TaF 5; the presence of TaF 5 0 is only evident at ≤150 °C. Equilibrium constants range from -17.4 ± 0.45 to -16.4 ± 0.12 for the formation of Ta(OH) 5 from crystalline Ta 2O 5 and from -8.24 ±more » 0.64 to -8.55 ± 0.68 for the formation of TaF 3(OH) 3- at 100 and 250 °C, respectively. For TaF 5 0, they were determined to be 0.13 at 100 °C and -0.35 at 150 °C.« less

  16. Tantalum-tungsten oxide thermite composites prepared by sol-gel synthesis and spark plasma sintering

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

    Kuntz, Joshua D.; Gash, Alexander E.; Cervantes, Octavio G.

    2010-08-15

    Energetic composite powders consisting of sol-gel derived nanostructured tungsten oxide were produced with various amounts of micrometer-scale tantalum fuel metal. Such energetic composite powders were ignition-tested and the results show that the powders are not sensitive to friction, spark and/or impact ignition. Initial consolidation experiments, using the High-Pressure Spark Plasma Sintering (HPSPS) technique, on the sol-gel derived nanostructured tungsten oxide produced samples with higher relative density than can be achieved with commercially available tungsten oxide. The sol-gel derived nanostructured tungsten oxide with immobilized tantalum fuel metal (Ta-WO{sub 3}) energetic composite was consolidated to a density of 9.17 g cm{sup -3}more » or 93% relative density. In addition, those samples were consolidated without significant pre-reaction of the constituents, thus retaining their stored chemical energy. (author)« less

  17. Tantalum-Tungsten Oxide Thermite Composite Prepared by Sol-Gel Synthesis and Spark Plasma Sintering

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

    Cervantes, O; Kuntz, J; Gash, A

    2009-02-13

    Energetic composite powders consisting of sol-gel derived nanostructured tungsten oxide were produced with various amounts of micrometer-scale tantalum fuel metal. Such energetic composite powders were ignition tested and results show that the powders are not sensitive to friction, spark and/or impact ignition. Initial consolidation experiments, using the High Pressure Spark Plasma Sintering (HPSPS) technique, on the sol-gel derived nanostructured tungsten oxide produced samples with higher relative density than can be achieved with commercially available tungsten oxide. The sol-gel derived nanostructured tungsten oxide with immobilized tantalum fuel metal (Ta - WO{sub 3}) energetic composite was consolidated to a density of 9.17more » g.cm{sup -3} or 93% relative density. In addition those parts were consolidated without significant pre-reaction of the constituents, thus the sample retained its stored chemical energy.« less

  18. FAST TRACK COMMUNICATION High rate straining of tantalum and copper

    NASA Astrophysics Data System (ADS)

    Armstrong, R. W.; Zerilli, F. J.

    2010-12-01

    High strain rate measurements reported recently for several tantalum and copper crystal/polycrystal materials are shown to follow dislocation mechanics-based constitutive relations, first at lower strain rates, for dislocation velocity control of the imposed plastic deformations and, then at higher rates, transitioning to nano-scale dislocation generation control by twinning or slip. For copper, there is the possibility of added-on slip dislocation displacements to be accounted for from the newly generated dislocations.

  19. Synthesis of Monodispersed Tantalum(V) oxide Nanospheres by an Ethylene Glycol Mediated Route

    EPA Science Inventory

    Tantalum(V) oxide (Ta2O5) nanospheres have been synthesized by a very simple ethylene glycol mediated route. The two-step process involves the formation of glycolate nanoparticles and their subsequent hydrolysis and calcination to generate the final Ta2O5 nanospheres. The synthes...

  20. In situ evolution of highly dispersed amorphous CoO x clusters for oxygen evolution reaction

    DOE PAGES

    Chen, Dawei; Dong, Chung-Li; Zou, Yuqin; ...

    2017-07-24

    Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoO x for the first timemore » in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoO x cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm -2 and the overpotential of only 350 mV at 300 mA cm -1. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoO x cluster. In addition, we studied the reaction mechanism, and it was observed that pure O 2 DBD plasma could lead to the evolution of crystalline CoO x; however, the presence of N 2 and O 2 in DBD plasma could ensure the facile evolution of amorphous CoO x clusters. This study provides a new strategy, therefore, to design amorphous materials for electrocatalysis and beyond.« less

  1. In situ evolution of highly dispersed amorphous CoO x clusters for oxygen evolution reaction

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

    Chen, Dawei; Dong, Chung-Li; Zou, Yuqin

    Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoO x for the first timemore » in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoO x cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm -2 and the overpotential of only 350 mV at 300 mA cm -1. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoO x cluster. In addition, we studied the reaction mechanism, and it was observed that pure O 2 DBD plasma could lead to the evolution of crystalline CoO x; however, the presence of N 2 and O 2 in DBD plasma could ensure the facile evolution of amorphous CoO x clusters. This study provides a new strategy, therefore, to design amorphous materials for electrocatalysis and beyond.« less

  2. Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

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

    Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

    2016-04-04

    This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

  3. Formation and evolution of oxygen-vacancy clusters in lead and tin doped silicon

    NASA Astrophysics Data System (ADS)

    Londos, C. A.; Aliprantis, D.; Sgourou, E. N.; Chroneos, A.; Pochet, P.

    2012-06-01

    Infrared spectroscopy (IR) measurements were used to investigate the effect of lead (Pb), tin (Sn), and (Pb, Sn) codoping on electron radiation-induced defects in silicon (Si). The study was mainly focused on oxygen-vacancy (VOn) clusters and in particular their formation and evolution upon annealing. It was determined that Pb causes a larger reduction in the production of the VO defect than Sn. In (Pb, Sn) co-doped Si isochronal anneals revealed that the evolution of VO increases substantially at ˜170 °C. This is attributed to the release of V from the SnV pair. Interestingly, in the corresponding evolution curves of VO in the Sn- and the Pb-doped samples, this inverse annealing stage is also present for the former while it is not present for the latter. This is attributed to the formation of PbV pairs that do not dissociate below 280 °C. The partial capture of V by Sn in co-doped samples is rationalized through the higher compressive local strain around Pb atoms that leads to a retardation of vacancy diffusion. The conversion of VO to the VO2 defect is substantially reduced in the Pb-doped sample. The evolution curves of VO and VO2 clusters in the isovalent doped Si samples hint the production of VO2 from other mechanisms (i.e., besides VO + Oi → VO2). For larger VOn clusters (n = 3,4), the signals are very weak in the Pb-doped sample, whereas for n ≥ 5, they are not present in the spectra. Conversely, bands related with the VO5 and VOnCs defects are present in the spectra of the Sn-doped and (Pb, Sn) codoped Si.

  4. Characterization of a unique [FeS] cluster in the electron transfer chain of the oxygen tolerant [NiFe] hydrogenase from Aquifex aeolicus

    PubMed Central

    Pandelia, Maria-Eirini; Nitschke, Wolfgang; Infossi, Pascale; Giudici-Orticoni, Marie-Thérèse; Bill, Eckhard; Lubitz, Wolfgang

    2011-01-01

    Iron-sulfur clusters are versatile electron transfer cofactors, ubiquitous in metalloenzymes such as hydrogenases. In the oxygen-tolerant Hydrogenase I from Aquifex aeolicus such electron “wires” form a relay to a diheme cytb, an integral part of a respiration pathway for the reduction of O2 to water. Amino acid sequence comparison with oxygen-sensitive hydrogenases showed conserved binding motifs for three iron-sulfur clusters, the nature and properties of which were unknown so far. Electron paramagnetic resonance spectra exhibited complex signals that disclose interesting features and spin-coupling patterns; by redox titrations three iron-sulfur clusters were identified in their usual redox states, a [3Fe4S] and two [4Fe4S], but also a unique high-potential (HP) state was found. On the basis of 57Fe Mössbauer spectroscopy we attribute this HP form to a superoxidized state of the [4Fe4S] center proximal to the [NiFe] site. The unique environment of this cluster, characterized by a surplus cysteine coordination, is able to tune the redox potentials and make it compliant with the [4Fe4S]3+ state. It is actually the first example of a biological [4Fe4S] center that physiologically switches between 3+, 2+, and 1+ oxidation states within a very small potential range. We suggest that the (1 + /2+) redox couple serves the classical electron transfer reaction, whereas the superoxidation step is associated with a redox switch against oxidative stress. PMID:21444783

  5. Free radicals generated by tantalum implants antagonize the cytotoxic effect of doxorubicin.

    PubMed

    Chen, Muwan; Hein, San; Le, Dang Q S; Feng, Wenzhou; Foss, Morten; Kjems, Jørgen; Besenbacher, Flemming; Zou, Xuenong; Bünger, Cody

    2013-05-01

    Little is known about the interaction between antineoplastic drugs and implants in bone cancer patients. We investigated the interaction between commercially available porous tantalum (Ta) implants and the chemotherapeutic drug, Doxorubicin (DOX). DOX solutions were prepared in the presence of Ta implant. The changes in fluorescence intensity of the DOX chromophore were measured by spectrofluorometry and the efficacy of DOX was evaluated by viability of rabbit rectal tumor cells (VX2). After 5 min interaction of the DOX solution (5 μg/ml) with the Ta implant, the fluorescent intensity of the DOX solution was 85% degraded, and only 20% the drug efficacy to kill VX2 cells was retained. However, after adding a reducing agent, Dithiothreitol (DTT, 10 μg/ml), 80% of the original fluorescence and 50% of the drug efficacy were restored while UV irradiation enhanced drug degradation in the presence of Ta implant. The action of DTT and UV irradiation indicated that reactive oxygen species (ROS) were involved in the drug degradation mechanism. We detected that Ta implants in aqueous medium produced hydroxyl radicals. Cells showed higher intracellular ROS activity when culture medium was incubated with the Ta implant prior to cell culture. It is concluded that the porous Ta implant antagonizes the cytotoxicity of DOX via ROS generation of the porous Ta implant. Copyright © 2013 Elsevier B.V. All rights reserved.

  6. Promotion of osteointegration under diabetic conditions by tantalum coating-based surface modification on 3-dimensional printed porous titanium implants.

    PubMed

    Wang, Lin; Hu, Xiaofan; Ma, Xiangyu; Ma, Zhensheng; Zhang, Yang; Lu, Yizhao; Li, Xiang; Lei, Wei; Feng, Yafei

    2016-12-01

    Clinical evidence indicates a high failure rate for titanium implants (TiI) in diabetic patients, involving the overproduction of reactive oxygen species (ROS) at the implant/bone interface. Tantalum coating on titanium (TaTi) has exerted better tissue integration properties than TiI, but its biological performance under diabetic conditions remains elusive. To investigate whether TaTi may ameliorate diabetes-induced implant destabilization and the underlying mechanisms, primary rabbit osteoblasts cultured on 3-dimensional printed TiI and TaTi were exposed to normal serum (NS), diabetic serum (DS), DS+NAC (a potent ROS inhibitor), and DS+SB203580 (a specific p38 MAPK inhibitor). An in vivo study was performed on diabetic sheep implanted with TiI or TaTi. Diabetes induced mitochondrial-derived ROS overproduction and caused cellular dysfunction and apoptosis, together with the activation of p38 MAPK in osteoblasts on TiI surface. Importantly, TaTi significantly attenuated ROS production and p38 MAPK phosphorylation and exerted more osseointegrative cell behavior than TiI, as shown by improved osteoblast adhesion, increased cell proliferation and differentiation and decreased apoptosis. These results were confirmed in vivo by the enhanced bone healing efficacy of TaTi. Moreover, treatment with NAC or SB203580 on TiI not only inhibited the activation of p38 MAPK but also improved cell function and alleviated apoptotic injury, whereas TaTi combined with NAC or SB203580 failed to further improve osteoblast functional recovery compared with TaTi alone. These results demonstrated that the tantalum coating markedly improved diabetes-induced impaired osteogenesis of TiI, which may be attributed to the suppression of the ROS-mediated p38 MAPK pathway. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Orientation of Calcium in the Mn4Ca Cluster of the Oxygen-Evolving Complex Determined Using Polarized Strontium EXAFS of Photosystem II Membranes†

    PubMed Central

    Cinco, Roehl M.; Robblee, John H.; Messinger, Johannes; Fernandez, Carmen; Holman, Karen L. McFarlane; Sauer, Kenneth; Yachandra, Vittal K.

    2014-01-01

    The oxygen-evolving complex of photosystem II (PS II) in green plants and algae contains a cluster of four Mn atoms in the active site, which catalyzes the photoinduced oxidation of water to dioxygen. Along with Mn, calcium and chloride ions are necessary cofactors for proper functioning of the complex. The current study using polarized Sr EXAFS on oriented Sr-reactivated samples shows that Fourier peak II, which fits best to Mn at 3.5 Å rather than lighter atoms (C, N, O, or Cl), is dichroic, with a larger magnitude at 10° (angle between the PS II membrane normal and the X-ray electric field vector) and a smaller magnitude at 80°. Analysis of the dichroism of the Sr EXAFS yields a lower and upper limit of 0° and 23° for the average angle between the Sr–Mn vectors and the membrane normal and an isotropic coordination number (number of Mn neighbors to Sr) of 1 or 2 for these layered PS II samples. The results confirm the contention that Ca (Sr) is proximal to the Mn cluster and lead to refined working models of the heteronuclear Mn4Ca cluster of the oxygen-evolving complex in PS II. PMID:15491134

  8. Localization and orientation of heavy-atom cluster compounds in protein crystals using molecular replacement

    PubMed Central

    Dahms, Sven O.; Kuester, Miriam; Streb, Carsten; Roth, Christian; Sträter, Norbert; Than, Manuel E.

    2013-01-01

    Heavy-atom clusters (HA clusters) containing a large number of specifically arranged electron-dense scatterers are especially useful for experimental phase determination of large complex structures, weakly diffracting crystals or structures with large unit cells. Often, the determination of the exact orientation of the HA cluster and hence of the individual heavy-atom positions proves to be the critical step in successful phasing and subsequent structure solution. Here, it is demonstrated that molecular replacement (MR) with either anomalous or isomorphous differences is a useful strategy for the correct placement of HA cluster compounds. The polyoxometallate cluster hexasodium α-metatungstate (HMT) was applied in phasing the structure of death receptor 6. Even though the HA cluster is bound in alternate partially occupied orientations and is located at a special position, its correct localization and orientation could be determined at resolutions as low as 4.9 Å. The broad applicability of this approach was demonstrated for five different derivative crystals that included the compounds tantalum tetradeca­bromide and trisodium phosphotungstate in addition to HMT. The correct placement of the HA cluster depends on the length of the intramolecular vectors chosen for MR, such that both a larger cluster size and the optimal choice of the wavelength used for anomalous data collection strongly affect the outcome. PMID:23385464

  9. Evaluation of tantalum 316 stainless steel transition joints

    NASA Technical Reports Server (NTRS)

    Stoner, D. R.

    1972-01-01

    Tubular transition joints providing a metallurgically bonded connection between tantalum and 316 stainless steel pipe sections were comparatively evaluated for durability under thermal cycling conditions approximating the operation of a SNAP-8 mercury boiler. Both coextruded and vacuum brazed transition joints of 50mm (2 inch) diameter were tested by thermal cycling 100 times between 730 C and 120 C(1350 F and 250 F) in a high vacuum environment. The twelve evaluated transition joints survived the full test sequence without developing leaks, although liquid penetrant bond line indications eventually developed in all specimens. The brazed transition joints exhibited the best dimensional stability and bond line durability.

  10. Effect of oxygen impurities on properties of the ternary superconductor SnMo/sub 6/S/sub 8/: Extended x-ray-absorption fine-structure determination of bond distances and local-density cluster calculations

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

    Guenzburger, D.; Ellis, D.E.; Montano, P.A.

    1985-10-01

    Electronic structure calculations were performed for clusters representing the Chevrel-phase SnMo/sub 6/S/sub 8/, with and without oxygen doping. In order to obtain the local structure around the Sn atom, extended x-ray-absorption fine-structure (EXAFS) measurements were made with synchro- tron radiation. The interatomic distances obtained experimentally were used in the calculations. The effect of oxygen doping on the Moessbauer isomer shift and quadrupole splitting values of /sup 119/Sn was investigated theoretically and compared with reported experimental values. The effect of oxygen substitution on the density of states at the Fermi energy of the (Mo/sub 6/S/sub 8/)/sup 2 -/ cluster was alsomore » studied. The results suggest that oxygen doping does not alter significantly the electronic structure of SnMo/sub 6/S/sub 8/.« less

  11. Zinc Tantalum Oxynitride (ZnTaO2N) Photoanode Modified with Cobalt Phosphate Layers for the Photoelectrochemical Oxidation of Alkali Water

    PubMed Central

    T. Weller, Mark

    2018-01-01

    Photoanodes fabricated by the electrophoretic deposition of a thermally prepared zinc tantalum oxynitride (ZnTaO2N) catalyst onto indium tin oxide (ITO) substrates show photoactivation for the oxygen evolution reaction (OER) in alkaline solutions. The photoactivity of the OER is further boosted by the photodeposition of cobalt phosphate (CoPi) layers onto the surface of the ZnTaO2N photoanodes. Structural, morphological, and photoelectrochemical (PEC) properties of the modified ZnTaO2N photoanodes are studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet visible (UV−Vis) diffuse reflectance spectroscopy, and electrochemical techniques. The presence of the CoPi layer significantly improved the PEC performance of water oxidation in an alkaline sulphate solution. The photocurrent-voltage behavior of the CoPi-modified ZnTaO2N anodes was improved, with the influence being more prominent at lower oxidation potentials. A stable photocurrent density of about 2.3 mA·cm−2 at 1.23 V vs. RHE was attained upon visible light illumination. Relative to the ZnTaO2N photoanodes, an almost three-fold photocurrent increase was achieved at the CoPi/ZnTaO2N photoelectrode. Perovskite-based oxynitrides are modified using an oxygen-evolution co-catalyst of CoPi, and provide a new dimension for enhancing the photoactivity of oxygen evolution in solar-assisted water-splitting reactions. PMID:29346306

  12. Studying tantalum-based high-κ dielectrics in terms of capacitance measurements

    NASA Astrophysics Data System (ADS)

    Stojanovska-Georgievska, L.

    2016-08-01

    The trend of rapid development of microelectronics towards nano-miniaturization dictates the inevitable introduction of dielectrics with high permittivity (high-κ dielectrics), as alternative material for replacing SiO2. Therefore, studying these materials in terms of their characteristics, especially in terms of reliability, is of great importance for proper design and manufacture of devices. In this paper, alteration of capacitance in different frequency regimes is used, in order to determine the overall behavior of the material. Samples investigated here are MOS structures containing nanoscale tantalum based dielectrics. Layers of pure Ta2O5, but also Hf and Ti doped tantalum pentoxide, i.e. Ta2O5:Hf and Ta2O5:Ti are studied here. All samples are considered as ultrathin oxide layers with thicknesses less than 15 nm, obtained by radio frequent sputtering on p-type silicon substrate. Measuring capacitive characteristics enables determination of several specific parameters of the structures. The obtained results for capacitance in accumulation, the thickness and time evolution of the interfacial SiO2 layer, values of flatband and threshold voltage, density of oxide charges, interfacial and border states, and reliability properties favor the possibilities for more intensive use of studied materials in new nanoelectronic technologies.

  13. Temperature and field-dependent transport measurements in continuously tunable tantalum oxide memristors expose the dominant state variable

    NASA Astrophysics Data System (ADS)

    Graves, Catherine E.; Dávila, Noraica; Merced-Grafals, Emmanuelle J.; Lam, Si-Ty; Strachan, John Paul; Williams, R. Stanley

    2017-03-01

    Applications of memristor devices are quickly moving beyond computer memory to areas of analog and neuromorphic computation. These applications require the design of devices with different characteristics from binary memory, such as a large tunable range of conductance. A complete understanding of the conduction mechanisms and their corresponding state variable(s) is crucial for optimizing performance and designs in these applications. Here we present measurements of low bias I-V characteristics of 6 states in a Ta/ tantalum-oxide (TaOx)/Pt memristor spanning over 2 orders of magnitude in conductance and temperatures from 100 K to 500 K. Our measurements show that the 300 K device conduction is dominated by a temperature-insensitive current that varies with non-volatile memristor state, with an additional leakage contribution from a thermally-activated current channel that is nearly independent of the memristor state. We interpret these results with a parallel conduction model of Mott hopping and Schottky emission channels, fitting the voltage and temperature dependent experimental data for all memristor states with only two free parameters. The memristor conductance is linearly correlated with N, the density of electrons near EF participating in the Mott hopping conduction, revealing N to be the dominant state variable for low bias conduction in this system. Finally, we show that the Mott hopping sites can be ascribed to oxygen vacancies, where the local oxygen vacancy density responsible for critical hopping pathways controls the memristor conductance.

  14. Large area graphene ion sensitive field effect transistors with tantalum pentoxide sensing layers for pH measurement at the Nernstian limit

    NASA Astrophysics Data System (ADS)

    Fakih, Ibrahim; Sabri, Shadi; Mahvash, Farzaneh; Nannini, Matthieu; Siaj, Mohamed; Szkopek, Thomas

    2014-08-01

    We have fabricated and characterized large area graphene ion sensitive field effect transistors (ISFETs) with tantalum pentoxide sensing layers and demonstrated pH sensitivities approaching the Nernstian limit. Low temperature atomic layer deposition was used to deposit tantalum pentoxide atop large area graphene ISFETs. The charge neutrality point of graphene, inferred from quantum capacitance or channel conductance, was used to monitor surface potential in the presence of an electrolyte with varying pH. Bare graphene ISFETs exhibit negligible response, while graphene ISFETs with tantalum pentoxide sensing layers show increased sensitivity reaching up to 55 mV/pH over pH 3 through pH 8. Applying the Bergveld model, which accounts for site binding and a Guoy-Chapman-Stern picture of the surface-electrolyte interface, the increased pH sensitivity can be attributed to an increased buffer capacity reaching up to 1014 sites/cm2. ISFET response was found to be stable to better than 0.05 pH units over the course of two weeks.

  15. The plastic response of Tantalum in Quasi-Isentropic Compression Ramp and Release

    NASA Astrophysics Data System (ADS)

    Moore, Alexander; Brown, Justin; Lim, Hojun; Lane, J. Matthew D.

    2017-06-01

    The mechanical response of various forms of tantalum under extreme pressures and strain rates is studied using dynamic quasi-isentropic compression loading conditions in atomistic simulations. Ramp compression in bcc metals under these conditions tend to show a significant strengthening effect with increasing pressure; however, due to limitations of experimental methods in such regimes, the underlying physics for this phenomenon is not well understood. Molecular dynamics simulations provide important information about the plasticity mechanisms and can be used to investigate this strengthening. MD simulations are performed on nanocrystalline Ta and single crystal defective Ta with dislocations and point defects to uncover how the material responds and the underlying plasticity mechanisms. The different systems of solid Ta are seen to plastically deform through different mechanisms. Fundamental understanding of tantalum plasticity in these high pressure and strain rate regimes is needed to model and fully understand experimental results. Sandia National Labs is a multi program laboratory managed and operated by Sandia Corp., a wholly owned subsidiary of Lockheed Martin Corp., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  16. Effect of strain rate and dislocation density on the twinning behavior in Tantalum

    DOE PAGES

    Florando, Jeffrey N.; El-Dasher, Bassem S.; Chen, Changqiang; ...

    2016-04-28

    The conditions which affect twinning in tantalum have been investigated across a range of strain rates and initial dislocation densities. Tantalum samples were subjected to a range of strain rates, from 10 –4/s to 10 3/s under uniaxial stress conditions, and under laser-induced shock-loading conditions. In this study, twinning was observed at 77K at strain rates from 1/s to 103/s, and during laser-induced shock experiments. The effect of the initial dislocation density, which was imparted by deforming the material to different amounts of pre-strain, was also studied, and it was shown that twinning is suppressed after a given amount ofmore » pre-strain, even as the global stress continues to increase. These results indicate that the conditions for twinning cannot be represented solely by a critical global stress value, but are also dependent on the evolution of the dislocation density. Additionally, the analysis shows that if twinning is initiated, the nucleated twins may continue to grow as a function of strain, even as the dislocation density continues to increase.« less

  17. Economics of Inhaled Oxygen Use as an Acute Therapy for Cluster Headache in the United States of America.

    PubMed

    O'Brien, Megan; Ford, Janet H; Aurora, Sheena K; Govindan, Sriram; Tepper, Deborah E; Tepper, Stewart J

    2017-10-01

    Cluster headache (CH) is a primary headache disorder associated with low levels of diagnosis and high unmet medical need. The pain attacks, associated anxiety, and fear in anticipation of the attacks are extremely debilitating to a patient with CH. For acute therapy, treatment guidelines recommend inhalation of high flow oxygen during the period of an attack. However, the use of oxygen for treatment of CH remains largely underutilized. The objectives of the study, which covered each of the US states, were to map the current market landscape of medical grade oxygen for use in CH and to develop a cost simulator based on a patient's needs and geography. Desk research was undertaken to obtain price lists and product catalogs from wholesale and retail suppliers of medical grade oxygen across all US states. Base case scenarios for chronic and episodic forms of CH were assumed. A cost simulator was used to calculate the cost of oxygen use using inputs including the state in USA, tank size and price, exacerbations per year, duration of exacerbation, attacks per day, flow rate and duration of flow. Information was also collected to determine if healthcare insurers covered the costs of home oxygen use for CH. Out of the 42 US states where pricing information of medical grade oxygen was available from suppliers, in 38 states the annual cost of high-flow oxygen for a patient with episodic CH was estimated to be <$1000. In 39 states, the annual cost of high-flow oxygen for a patient with chronic CH was estimated to be <$5000. Most of the home oxygen suppliers were familiar with CH and stocked the special non-rebreather masks and regulators necessary for this condition. It was found that many of the private commercial healthcare insurance providers reimbursed the cost of oxygen use for CH. However, the US Centers for Medicare and Medicaid Services (CMS) maintains there is insufficient evidence for coverage and continues to deny coverage for US Medicare and Medicaid patients

  18. In-situ XRD vs ex-situ vacuum annealing of tantalum oxynitride thin films: Assessments on the structural evolution

    NASA Astrophysics Data System (ADS)

    Cunha, L.; Apreutesei, M.; Moura, C.; Alves, E.; Barradas, N. P.; Cristea, D.

    2018-04-01

    The purpose of this work is to discuss the main structural characteristics of a group of tantalum oxynitride (TaNxOy) thin films, with different compositions, prepared by magnetron sputtering, and to interpret and compare the structural changes, by X-ray diffraction (XRD), when the samples are vacuum annealed under two different conditions: i) annealing, followed by ex-situ XRD: one sample of each deposition run was annealed at a different temperature, until a maximum of 800 °C, and the XRD patterns were obtained, at room temperature, after each annealing process; ii) annealing with in-situ XRD: the diffraction patterns are obtained, at certain temperatures, during the annealing process, using always the same sample. In-situ XRD annealing could be an interesting process to perform annealing, and analysing the evolution of the structure with the temperature, when compared to the classical process. A higher structural stability was observed in some of the samples, particularly on those with highest oxygen content, but also on the sample with non-metal (O + N) to metal (Ta) ratio around 0.5.

  19. Oxygen diffusion in alpha-Al2O3. Ph.D. Thesis

    NASA Technical Reports Server (NTRS)

    Cawley, J. D.; Halloran, J. W.; Cooper, A. R.

    1984-01-01

    Oxygen self diffusion coefficients were determined in single crystal alpha-Al2O3 using the gas exchange technique. The samples were semi-infinite slabs cut from five different boules with varying background impurities. The diffusion direction was parallel to the c-axis. The tracer profiles were determined by two techniques, single spectrum proton activation and secondary ion mass spectrometry. The SIMS proved to be a more useful tool. The determined diffusion coefficients, which were insensitive to impurity levels and oxygen partial pressure, could be described by D = .00151 exp (-572kJ/RT) sq m/s. The insensitivities are discussed in terms of point defect clustering. Two independent models are consistent with the findings, the first considers the clusters as immobile point defect traps which buffer changes in the defect chemistry. The second considers clusters to be mobile and oxygen diffusion to be intrinsic behavior, the mechanism for oxygen transport involving neutral clusters of Schottky quintuplets.

  20. Oxidation of Sn doped Cu cluster: A first principle study

    NASA Astrophysics Data System (ADS)

    Parida, Ganesh; Majumder, Chiranjib

    2017-05-01

    Bimetallic clusters have immense potential to exhibit tunable properties in the emerging field of nano catalysis. Using plane wave based pseudopotential approach we have investigated the oxidation behavior of pure and Sn doped Cu13 clusters. The results showed significant modification of the cluster geometry upon interaction with oxygen molecule. The interaction of oxygen with Cu13, Cu12Sn1 and Cu11Sn2 clusters show dissociative chemisorption is more favorable than molecular adsorption. In addition, the adsorption energy is found to decrease with the increase in Sn concentration.

  1. Improving oxygen therapy for children and neonates in secondary hospitals in Nigeria: study protocol for a stepped-wedge cluster randomised trial.

    PubMed

    Graham, Hamish R; Ayede, Adejumoke I; Bakare, Ayobami A; Oyewole, Oladapo B; Peel, David; Gray, Amy; McPake, Barbara; Neal, Eleanor; Qazi, Shamim; Izadnegahdar, Rasa; Falade, Adegoke G; Duke, Trevor

    2017-10-27

    Oxygen is a life-saving, essential medicine that is important for the treatment of many common childhood conditions. Improved oxygen systems can reduce childhood pneumonia mortality substantially. However, providing oxygen to children is challenging, especially in small hospitals with weak infrastructure and low human resource capacity. This trial will evaluate the implementation of improved oxygen systems at secondary-level hospitals in southwest Nigeria. The improved oxygen system includes: a standardised equipment package; training of clinical and technical staff; infrastructure support (including improved power supply); and quality improvement activities such as supportive supervision. Phase 1 will involve the introduction of pulse oximetry alone; phase 2 will involve the introduction of the full, improved oxygen system package. We have based the intervention design on a theory-based analysis of previous oxygen projects, and used quality improvement principles, evidence-based teaching methods, and behaviour-change strategies. We are using a stepped-wedge cluster randomised design with participating hospitals randomised to receive an improved oxygen system at 4-month steps (three hospitals per step). Our mixed-methods evaluation will evaluate effectiveness, impact, sustainability, process and fidelity. Our primary outcome measures are childhood pneumonia case fatality rate and inpatient neonatal mortality rate. Secondary outcome measures include a range of clinical, quality of care, technical, and health systems outcomes. The planned study duration is from 2015 to 2018. Our study will provide quality evidence on the effectiveness of improved oxygen systems, and how to better implement and scale-up oxygen systems in resource-limited settings. Our results should have important implications for policy-makers, hospital administrators, and child health organisations in Africa and globally. Australian New Zealand Clinical Trials Registry: ACTRN12617000341325

  2. PHYSICAL VAPOR DEPOSITION OF TANTALUM ON GUN BARREL STEEL (SYSTEMS ANLAYSIS BRANCH, SUSTAINABLE TECHNOLOGY DIVISION, NRMRL)

    EPA Science Inventory

    This project entails the development of an alternative technology for plating gun barrel steel to replace the process electroplating of chrome (Cr-electroplate) with physical vapor deposition of tantalum (Ta-PVD). Developed by Benet Laboratory at Watervliet Arsenal, this project'...

  3. A proposed CT contrast agent using carboxybetaine zwitterionic tantalum oxide nanoparticles: Imaging, biological, and physicochemical performance

    PubMed Central

    FitzGerald, Paul F.; Butts, Matthew D.; Roberts, Jeannette C.; Colborn, Robert E.; Torres, Andrew S.; Lee, Brian D.; Yeh, Benjamin M.; Bonitatibus, Peter J.

    2016-01-01

    Objectives To produce and evaluate a proposed computed tomography (CT) contrast agent based on carboxybetaine zwitterionic (CZ) coated soluble tantalum oxide nanoparticles (CZ-TaO NPs). We chose tantalum to provide superior imaging performance compared to current iodine-based clinical CT contrast agents. We developed the CZ coating to provide biological and physical performance similar to that of current iodinated contrast agents. The aim of this study was to evaluate the imaging, biological, and physicochemical performance of this proposed contrast agent compared to clinically-used iodinated agents. Materials and Methods We evaluated CT imaging performance of our CZ-TaO NPs compared to an iodinated agent in live rats, imaged centrally-located within a tissue-equivalent plastic phantom that simulated a large patient. To evaluate vascular contrast enhancement, we scanned the rats’ great vessels at high temporal resolution during and following contrast agent injection. We performed several in vivo CZ-TaO NP studies in healthy rats to evaluate tolerability. These studies included injecting the agent at the anticipated clinical dose (ACD) and at 3 times and 6 times the ACD, followed by longitudinal hematology to assess impact to blood cells and organ function (from 4 hours to 1 week). Kidney histological analysis was performed 48 hours after injection at 3 times the ACD. We measured the elimination half-life of CZ-TaO NPs from blood, and we monitored acute kidney injury biomarkers with a kidney injury assay using urine collected from 4 hours to 1 week. We measured tantalum retention in individual organs and in the whole carcass 48 hours after injection at ACD. CZ-TaO NPs were synthesized and analyzed in detail. We used multi-dimensional nuclear magnetic resonance (NMR) to determine surface functionality of the nanoparticles. We measured nanoparticle size and solution properties (osmolality and viscosity) of the agent over a range of tantalum concentrations, including

  4. Isolation of tungsten and tantalum isotopes without supports from. cap alpha. -particle-irradiated hafnium targets

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

    Gasita, S.M.; Iota, B.Z.; Malachkov, A.G.

    1985-11-01

    An extraction procedure has been developed for successive isolation of tungsten (/sup 178/W and /sup 181/W) and tantalum (/sup 179/Ta and /sup 182/Ta) isotopes without supports from ..cap alpha..particle-irradiated hafnium targets. The target, irradiated on a cyclotron, is dissolved in hydrofluoric acid. Tantalum isotopes are extracted with tributyl phosphate (TBP) from 1-5 M HF and are then reextracted with a 1:1 ammonia solution, and hydrofluoric acid is removed by heating. Tungsten isotopes are extracted with a chloroform solution or N-benzoyl-N-phenylhydroxylamine (BPHA) from 11-12 M H/sub 2/SO/sub 4/ or ..cap alpha..-benzoin oxime from 4.5-5.5 M H/sub 2/SO/sub 4/ and are thenmore » reextracted with a l:l ammonia solution. The yield of tungsten isotopes is not less than 95%, and the content of radioactive impurities of other isotopes is not more than 0.1%.« less

  5. Large area graphene ion sensitive field effect transistors with tantalum pentoxide sensing layers for pH measurement at the Nernstian limit

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

    Fakih, Ibrahim, E-mail: ibrahim.fakih@mail.mcgill.ca; Sabri, Shadi; Szkopek, Thomas, E-mail: thomas.szkopek@mcgill.ca

    2014-08-25

    We have fabricated and characterized large area graphene ion sensitive field effect transistors (ISFETs) with tantalum pentoxide sensing layers and demonstrated pH sensitivities approaching the Nernstian limit. Low temperature atomic layer deposition was used to deposit tantalum pentoxide atop large area graphene ISFETs. The charge neutrality point of graphene, inferred from quantum capacitance or channel conductance, was used to monitor surface potential in the presence of an electrolyte with varying pH. Bare graphene ISFETs exhibit negligible response, while graphene ISFETs with tantalum pentoxide sensing layers show increased sensitivity reaching up to 55 mV/pH over pH 3 through pH 8. Applying themore » Bergveld model, which accounts for site binding and a Guoy-Chapman-Stern picture of the surface-electrolyte interface, the increased pH sensitivity can be attributed to an increased buffer capacity reaching up to 10{sup 14} sites/cm{sup 2}. ISFET response was found to be stable to better than 0.05 pH units over the course of two weeks.« less

  6. Verification of conventional equations of state for tantalum under quasi-isentropic compression

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

    Binqiang, Luo; Guiji, Wang; Jianjun, Mo

    2014-11-21

    Shock Hugoniot data have been widely used to calibrate analytic equations of state (EOSs) of condensed matter at high pressures. However, the suitability of particular analytic EOSs under off-Hugoniot states has not been sufficiently verified using experimental data. We have conducted quasi-isentropic compression experiments (ICEs) of tantalum using the compact pulsed power generator CQ-4, and explored the relation of longitudinal stress versus volume of tantalum under quasi-isentropic compression using backward integration and characteristic inverse methods. By subtracting the deviatoric stress and additional pressure caused by irreversible plastic dissipation, the isentropic pressure can be extracted from the longitudinal stress. Several theoreticalmore » isentropes are deduced from analytic EOSs and compared with ICE results to validate the suitability of these analytic EOSs in isentropic compression states. The comparisons show that the Gruneisen EOS with Gruneisen Gamma proportional to volume is accurate, regardless whether the Hugoniot or isentrope is used as the reference line. The Vinet EOS yields better accuracy in isentropic compression states. Theoretical isentropes derived from Tillotson, PUFF, and Birch-Murnaghan EOSs well agree with the experimental isentrope in the range of 0–100 GPa, but deviate gradually with pressure increasing further.« less

  7. M551 metals melting experiment. [space manufacturing of aluminum alloys, tantalum alloys, stainless steels

    NASA Technical Reports Server (NTRS)

    Li, C. H.; Busch, G.; Creter, C.

    1976-01-01

    The Metals Melting Skylab Experiment consisted of selectively melting, in sequence, three rotating discs made of aluminum alloy, stainless steel, and tantalum alloy. For comparison, three other discs of the same three materials were similarly melted or welded on the ground. The power source of the melting was an electron beam unit. Results are presented which support the concept that the major difference between ground base and Skylab samples (i.e., large elongated grains in ground base samples versus nearly equiaxed and equal sized grains in Skylab samples) can be explained on the basis of constitutional supercooling, and not on the basis of surface phenomena. Microstructural observations on the weld samples and present explanations for some of these observations are examined. In particular, ripples and their implications to weld solidification were studied. Evidence of pronounced copper segregation in the Skylab A1 weld samples, and the tantalum samples studied, indicates a weld microhardness (and hence strength) that is uniformly higher than the ground base results, which is in agreement with previous predictions. Photographs are shown of the microstructure of the various alloys.

  8. Effect of strain rate and dislocation density on the twinning behavior in tantalum

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

    Florando, Jeffrey N., E-mail: florando1@llnl.gov; Swift, Damian C.; Barton, Nathan R.

    2016-04-15

    The conditions which affect twinning in tantalum have been investigated across a range of strain rates and initial dislocation densities. Tantalum samples were subjected to a range of strain rates, from 10{sup −4}/s to 10{sup 3}/s under uniaxial stress conditions, and under laser-induced shock-loading conditions. In this study, twinning was observed at 77 K at strain rates from 1/s to 10{sup 3}/s, and during laser-induced shock experiments. The effect of the initial dislocation density, which was imparted by deforming the material to different amounts of pre-strain, was also studied, and it was shown that twinning is suppressed after a givenmore » amount of pre-strain, even as the global stress continues to increase. These results indicate that the conditions for twinning cannot be represented solely by a critical global stress value, but are also dependent on the evolution of the dislocation density. In addition, the analysis shows that if twinning is initiated, the nucleated twins may continue to grow as a function of strain, even as the dislocation density continues to increase.« less

  9. Impact of oxygen stoichiometry on electroforming and multiple switching modes in TiN/TaOx/Pt based ReRAM

    NASA Astrophysics Data System (ADS)

    Sharath, S. U.; Joseph, M. J.; Vogel, S.; Hildebrandt, E.; Komissinskiy, P.; Kurian, J.; Schroeder, T.; Alff, L.

    2016-10-01

    We have investigated the material and electrical properties of tantalum oxide thin films (TaOx) with engineered oxygen contents grown by RF-plasma assisted molecular beam epitaxy. The optical bandgap and the density of the TaOx films change consistently with oxygen contents in the range of 3.63 to 4.66 eV and 12.4 to 9.0 g/cm3, respectively. When exposed to atmosphere, an oxidized Ta2O5-y surface layer forms with a maximal thickness of 1.2 nm depending on the initial oxygen deficiency of the film. X-ray photoelectron spectroscopy studies show that multiple sub-stoichiometric compositions occur in oxygen deficient TaOx thin films, where all valence states of Ta including metallic Ta are possible. Devices of the form Pt/Ta2O5-y/TaOx/TiN exhibit highly tunable forming voltages of 10.5 V to 1.5 V with decreasing oxygen contents in TaOx. While a stable bipolar resistive switching (BRS) occurs in all devices irrespective of oxygen content, unipolar switching was found to coexist with BRS only at higher oxygen contents, which transforms to a threshold switching behaviour in the devices grown under highest oxidation.

  10. In vivo comparison of tantalum, tungsten, and bismuth enteric contrast agents to complement intravenous iodine for double-contrast dual-energy CT of the bowel

    PubMed Central

    Rathnayake, Samira; Mongan, John; Torres, Andrew S.; Colborn, Robert; Gao, Dong-Wei; Yeh, Benjamin M; Fu, Yanjun

    2016-01-01

    To assess the ability of dual-energy CT (DECT) to separate intravenous contrast of bowel wall from intraluminal contrast, we scanned 16 rabbits on a clinical DECT scanner: n=3 using only iodinated intravenous contrast; and n=13 double-contrast enhanced scans using iodinated intravenous contrast and experimental enteric non-iodinated contrast agents in the bowel lumen (5 bismuth-, 4 tungsten-, and 4 tantalum-based). Representative image pairs from conventional CT images and DECT iodine density maps of small bowel (116 pairs from 232 images) were viewed by four abdominal imaging attending radiologists to independently score each comparison pair on a visual analog scale (−100 to +100%) for: 1) preference in small bowel wall visualization; and 2) preference in completeness of intraluminal enteric contrast subtraction. Median small bowel wall visualization was scored 39 and 42 percentage points (95% CI: 30–44% and 36–45%, p<0.001 both) higher at double-contrast DECT than at conventional CT with enteric tungsten and tantalum contrast, respectively. Median small bowel wall visualization at double-contrast DECT was scored 29 and 35 percentage points (95% CI: 20–35% and 33–39%, p<0.001 both) higher with enteric tungsten and tantalum, respectively, than with bismuth contrast. Median completeness of intraluminal enteric contrast subtraction in double-contrast DECT iodine density maps was scored 28 and 29 percentage points (95% CI: 15–31% and 28–33%, p<0.001 both) higher with enteric tungsten and tantalum, respectively, than with bismuth contrast. Results suggest that in vivo double-contrast DECT with iodinated intravenous and either tantalum- or tungsten-based enteric contrast provide better visualization of small bowel than conventional CT. PMID:26892945

  11. Flash melting of tantalum in a diamond cell to 85 GPa

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

    Karandikar, Amol; Boehler, Reinhard

    2016-02-09

    Here, we demonstrate a new level of precision in measuring melting temperatures at high pressure using laser flash-heating followed by Scanning Electron Microscopy and Focused Ion Beam Milling. Furthermore, the new measurements on tantalum put unprecedented constraints on its highly debated melting slope, calling for a reevaluation of theoretical, shock compression and diamond cell approaches to determine melting at high pressure. X-ray analysis of the recovered samples confirmed the absence of chemical reactions, which likely played a significant role in previous experiments.

  12. Low work function, stable compound clusters and generation process

    DOEpatents

    Dinh, Long N.; Balooch, Mehdi; Schildbach, Marcus A.; Hamza, Alex V.; McLean, II, William

    2000-01-01

    Low work function, stable compound clusters are generated by co-evaporation of a solid semiconductor (i.e., Si) and alkali metal (i.e., Cs) elements in an oxygen environment. The compound clusters are easily patterned during deposition on substrate surfaces using a conventional photo-resist technique. The cluster size distribution is narrow, with a peak range of angstroms to nanometers depending on the oxygen pressure and the Si source temperature. Tests have shown that compound clusters when deposited on a carbon substrate contain the desired low work function property and are stable up to 600.degree. C. Using the patterned cluster containing plate as a cathode baseplate and a faceplate covered with phosphor as an anode, one can apply a positive bias to the faceplate to easily extract electrons and obtain illumination.

  13. Effects of the [OC6F5] moiety upon structural geometry: crystal structures of half-sandwich tantalum(V) aryloxide complexes from reaction of Cp*Ta(N(t)Bu)(CH2R)2 with pentafluorophenol.

    PubMed

    Cole, Jacqueline M; Chan, Michael C W; Gibson, Vernon C; Howard, Judith A K

    2011-10-01

    The synthesis, chemical and structural characterization of a series of pentamethylcyclopentadienyl (Cp*) tantalum imido complexes and aryloxide derivatives are presented. Specifically, the imido complexes Cp*Ta(N(t)Bu)(CH(2)R)(2), where R = Ph [dibenzyl(tert-butylamido) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (1)], Me(2)Ph [tert-butylamido)bis(2-methyl-2-phenylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (2)], CMe(3) [(tert-butylamido)bis(2,2-dimethylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (3)], are reported. The crystal structure of (3) reveals α-agostic interactions with the Ta atom. The resulting increase in the tantalum core coordination improves electronic stability. As such it does not react with pentafluorophenol, in contrast to the other two reported imido complexes [(1) and (2)]. Addition of C(6)F(5)OH to (1) yields a dimeric aryl-oxide derivative, [Cp*Ta(CH(2)Ph)(OC(6)H(5))(μ-O)](2) [di-μ-oxido-bis[benzyl(pentafluorophenolato) (η(5)-pentamethylcyclopentadienyl)tantalum(V)] (4)]. Its crystal structure reveals long Ta-O(C(6)H(5)) bonds but short oxo-bridging Ta-O bonds. This is explained by accounting for the fierce electronic competition for the vacant d(π) orbitals of the electrophilic Ta(V) centre. Steric congestion around each metal is alleviated by a large twist angle (77.1°) between the benzyl and pentafluorophenyl ligands and the ordering of each of these groups into stacked pairs. The imido complex (2) reacts with C(6)F(5)OH to produce a mixture of Cp*Ta(OC(6)F(5))(4) [tetrakis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V) (5)] and [Cp*Ta(OC(6)F(5))(2)(μ-O)](2) [di-μ-oxido-bis[bis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V)] (6)]. Steric congestion is offset in both cases by the twisting of its pentafluorophenyl ligands. Particularly strong electronic competition for the empty d(π) metal orbitals in (6) is reflected in its bond geometry, and owes itself to the

  14. Modified porous tantalum rod technique for the treatment of femoral head osteonecrosis

    PubMed Central

    Pakos, Emilios E; Megas, Panayiotis; Paschos, Nikolaos K; Syggelos, Spyridon A; Kouzelis, Antonios; Georgiadis, Georgios; Xenakis, Theodoros A

    2015-01-01

    AIM: To study a modified porous tantalum technique for the treatment of osteonecrosis of the femoral head. METHODS: The porous tantalum rod was combined with endoscopy, curettage, autologous bone grafting and use of bone marrow aspirates from iliac crest aspiration in 49 patients (58 hips) with a mean age of 38 years. The majority of the patients had idiopathic osteonecrosis, followed by corticosteroid-induced osteonecrosis. Thirty-eight hips were of Steinberg stage II disease and 20 hips were of stage III disease. Patients were followed for 5 years and were evaluated clinically with the Merle D’Aubigne and Postel score and radiologically. The primary outcome of the study was survival based on the conversion to total hip arthroplasty (THA). Secondary outcomes included deterioration of the osteonecrosis to a higher disease stage at 5 years compared to the preoperative period and identification of factors that were associated with survival. The Kaplan-Meier survival analysis was performed to evaluate the survivorship of the prosthesis, and the Fisher exact test was performed to test associations between various parameters with survival. RESULTS: No patient developed any serious intraoperative or postoperative complication including implant loosening or migration and donor site morbidity. During the 5-year follow up, 1 patient died, 7 patients had disease progression and 4 hips were converted to THA. The 5-year survival based on conversion to THA was 93.1% and the respective rate based on disease progression was 87.9%. Stage II disease was associated with statistically significant better survival rates compared to stage III disease (P = 0.04). The comparison between idiopathic and non-idiopathic osteonecrosis and between steroid-induced and non-steroid-induced osteonecrosis did not showed any statistically significant difference in survival rates. The clinical evaluation revealed statistically significantly improved Merle d’Aubigne scores at 12 mo postoperatively

  15. Modified porous tantalum rod technique for the treatment of femoral head osteonecrosis.

    PubMed

    Pakos, Emilios E; Megas, Panayiotis; Paschos, Nikolaos K; Syggelos, Spyridon A; Kouzelis, Antonios; Georgiadis, Georgios; Xenakis, Theodoros A

    2015-11-18

    To study a modified porous tantalum technique for the treatment of osteonecrosis of the femoral head. The porous tantalum rod was combined with endoscopy, curettage, autologous bone grafting and use of bone marrow aspirates from iliac crest aspiration in 49 patients (58 hips) with a mean age of 38 years. The majority of the patients had idiopathic osteonecrosis, followed by corticosteroid-induced osteonecrosis. Thirty-eight hips were of Steinberg stage II disease and 20 hips were of stage III disease. Patients were followed for 5 years and were evaluated clinically with the Merle D'Aubigne and Postel score and radiologically. The primary outcome of the study was survival based on the conversion to total hip arthroplasty (THA). Secondary outcomes included deterioration of the osteonecrosis to a higher disease stage at 5 years compared to the preoperative period and identification of factors that were associated with survival. The Kaplan-Meier survival analysis was performed to evaluate the survivorship of the prosthesis, and the Fisher exact test was performed to test associations between various parameters with survival. No patient developed any serious intraoperative or postoperative complication including implant loosening or migration and donor site morbidity. During the 5-year follow up, 1 patient died, 7 patients had disease progression and 4 hips were converted to THA. The 5-year survival based on conversion to THA was 93.1% and the respective rate based on disease progression was 87.9%. Stage II disease was associated with statistically significant better survival rates compared to stage III disease (P = 0.04). The comparison between idiopathic and non-idiopathic osteonecrosis and between steroid-induced and non-steroid-induced osteonecrosis did not showed any statistically significant difference in survival rates. The clinical evaluation revealed statistically significantly improved Merle d'Aubigne scores at 12 mo postoperatively compared to the

  16. Order within disorder: The atomic structure of ion-beam sputtered amorphous tantala (a-Ta₂O₅)

    DOE PAGES

    Bassiri, Riccardo; Liou, Franklin; Abernathy, Matthew R.; ...

    2015-03-01

    Amorphous tantala (a-Ta₂O₅) is a technologically important material often used in high-performance coatings. Understanding this material at the atomic level provides a way to further improve performance. This work details extended X-ray absorption fine structure measurements of a-Ta₂O₅ coatings, where high-quality experimental data and theoretical fits have allowed a detailed interpretation of the nearest-neighbor distributions. It was found that the tantalum atom is surrounded by four shells of atoms in sequence; oxygen, tantalum, oxygen, and tantalum. A discussion is also included on how these models can be interpreted within the context of published crystalline Ta₂O₅ and other a-T₂O₅ studies.

  17. A first principles investigation of the oxygen adsorption on Zr(0001) surface using cluster expansions

    NASA Astrophysics Data System (ADS)

    Samin, Adib J.; Taylor, Christopher D.

    2017-11-01

    The design of corrosion resistant zircalloys is important for a variety of technological applications ranging from medicine to the nuclear industry. Since corrosion resistance is mainly attributed to the formation of a surface oxide layer, developing a detailed understanding of this process may assist in future corrosion resistance design. In this work, we conduct a systematic multi-scale investigation of the early stages of oxide formation. This was accomplished by first using a database of fully relaxed DFT calculations to build a cluster-expansion description of the potential function. The developed potential was reasonably good at predicting DFT energies as evidenced by the cross-validation score of 4.4 meV/site. The effective cluster expansion parameters were indicative of repulsive adsorbate interactions in the adlayer in agreement with the literature. The potential then allowed for a systematic investigation of the oxygen configurations on the Zr(0001) surface via Monte Carlo simulations. The adsorption energy was recorded as a function of coverage and an increasing trend was observed in agreement with DFT predictions and the repulsive nature of interactions in the adlayer. The convex hull diagram was recorded indicating the most stable configuration to occur around a coverage of 0.6 ML. The adsorption isotherm was also recorded and contrasted for two temperatures relevant for different applications.

  18. Microstructural Formations and Phase Transformation Pathways in Hot Isostatically Pressed Tantalum Carbides

    DTIC Science & Technology

    2012-01-01

    and wear-resistant brake liners. The phase diagram for the tantalum–carbon system [5] is shown in Fig. 1a with corresponding crystal structures shown... structure ), with carbon atoms occupying the octahe- dral interstitial sites in a tantalum face-centered cubic (fcc) lattice [2,7]. The carbon-deficient...carbon sublattice. The allotropic phase trans- formation temperature between a-Ta2C (CdI2 antitype structure ) and b (L’3 structure ) is 2300 K [1,7]. In

  19. Preparation of etched tantalum semimicro capacitor stimulation electrodes.

    PubMed

    Robblee, L S; Kelliher, E M; Langmuir, M E; Vartanian, H; McHardy, J

    1983-03-01

    The ideal electrode for stimulation of the nervous system is one that will inject charge by purely capacitive processes. One approach is to exploit the type of metal-oxide combination used in electrolytic capacitors, e.g., Ta/Ta2O5. For this purpose, fine tantalum wire (0.25 mm diam) was etched electrolytically at constant current in a methanol solution of NH4Br containing 1.5 wt % H2O. Electrolytic etching produced a conical tip with a length of ca. 0.5 mm and shaft diameters ranging from 0.10 to 0.16 mm. The etched electrodes were anodized to 10 V (vs. SCE) in 0.1 vol % H3PO4. The capacitance values normalized to geometric area of etched electrodes ranged from 0.13 to 0.33 micro F mm-2. Comparison of these values to the capacitance of "smooth" tantalum anodized to 10 V (0.011 micro F mm-2) indicated that the degree of surface enhancement, or etch ratio, was 12-30. The surface roughness was confirmed by scanning electron microscopy studies which revealed an intricate array of irregularly shaped surface projections about 1-2 micrometers wide. The etched electrodes were capable of delivering 0.06-0.1 micro C of charge with 0.1 ms pulses at a pulse repetition rate of 400 Hz when operated at 50% of the anodization voltage. This quantity of charge corresponded to volumetric charge densities of 20-30 micro C mm-3 and area charge densities of 0.55-0.88 micro C mm-2. Charge storage was proportionately higher at higher fractional values of the formation voltage. Leakage currents at 5 V were ca. 2 nA. Neither long-term passive storage (1500 h) nor extended pulsing time (18 h) had a deleterious effect on electrode performance. The trend in electrical stimulation work is toward smaller electrodes. The procedures developed in this study should be particularly well-suited to the fabrication of even smaller electrodes because of the favorable electrical and geometric characteristics of the etched surface.

  20. Competition between surface chemisorption and cage formation in Fe12O12 clusters

    NASA Astrophysics Data System (ADS)

    Gutsev, G. L.; Weatherford, C. A.; Jena, P.; Johnson, E.; Ramachandran, B. R.

    2013-01-01

    The electronic and geometrical structures of the clusters composed of 12 iron and 12 oxygen atoms are obtained using all-electron density functional theory. It is found that the states with geometrical structures corresponding to oxygen chemisorbed on the ground-state Fe12 cluster surface (Fe12O12) are close in total energy to the states whose geometrical configurations are hollow cages (FeO)12. The lowest total energy state is the ferrimagnetic triplet state of Fe12O12. A ferrimagnetic nonet state of (FeO)12 is only marginally higher in total energy. The clusters are rich in nearly degenerate isomers. Oxygen adsorption dramatically quenches the spin of Fe12 clusters.

  1. Tantalum films with well-controlled roughness grown by oblique incidence deposition

    NASA Astrophysics Data System (ADS)

    Rechendorff, K.; Hovgaard, M. B.; Chevallier, J.; Foss, M.; Besenbacher, F.

    2005-08-01

    We have investigated how tantalum films with well-controlled surface roughness can be grown by e-gun evaporation with oblique angle of incidence between the evaporation flux and the surface normal. Due to a more pronounced shadowing effect the root-mean-square roughness increases from about 2 to 33 nm as grazing incidence is approached. The exponent, characterizing the scaling of the root-mean-square roughness with length scale (α), varies from 0.75 to 0.93, and a clear correlation is found between the angle of incidence and root-mean-square roughness.

  2. Compliance-Free, Digital SET and Analog RESET Synaptic Characteristics of Sub-Tantalum Oxide Based Neuromorphic Device.

    PubMed

    Abbas, Yawar; Jeon, Yu-Rim; Sokolov, Andrey Sergeevich; Kim, Sohyeon; Ku, Boncheol; Choi, Changhwan

    2018-01-19

    A two terminal semiconducting device like a memristor is indispensable to emulate the function of synapse in the working memory. The analog switching characteristics of memristor play a vital role in the emulation of biological synapses. The application of consecutive voltage sweeps or pulses (action potentials) changes the conductivity of the memristor which is considered as the fundamental cause of the synaptic plasticity. In this study, a neuromorphic device using an in-situ growth of sub-tantalum oxide switching layer is fabricated, which exhibits the digital SET and analog RESET switching with an electroforming process without any compliance current (compliance free). The process of electroforming and SET is observed at the positive sweeps of +2.4 V and +0.86 V, respectively, while multilevel RESET is observed with the consecutive negative sweeps in the range of 0 V to -1.2 V. The movement of oxygen vacancies and gradual change in the anatomy of the filament is attributed to digital SET and analog RESET switching characteristics. For the Ti/Ta 2 O 3-x /Pt neuromorphic device, the Ti top and Pt bottom electrodes are considered as counterparts of the pre-synaptic input terminal and a post-synaptic output terminal, respectively.

  3. Influence of Cr doping on the stability and structure of small cobalt oxide clusters.

    PubMed

    Tung, Nguyen Thanh; Tam, Nguyen Minh; Nguyen, Minh Tho; Lievens, Peter; Janssens, Ewald

    2014-07-28

    The stability of mass-selected pure cobalt oxide and chromium doped cobalt oxide cluster cations, ConO+m and Con-1CrO+m (n = 2, 3; m = 2-6 and n = 4; m = 3-8), has been investigated using photodissociation mass spectrometry. Oxygen-rich ConO+m clusters (m ≥ n + 1 for n = 2, 4 and m ≥ n + 2 for n = 3) prefer to photodissociate via the loss of an oxygen molecule, whereas oxygen poorer clusters favor the evaporation of oxygen atoms. Substituting a single Co atom by a single Cr atom alters the dissociation behavior. All investigated Con-1 CrO+m clusters, except CoCrO+2 and CoCrO+3, prefer to decay by eliminating a neutral oxygen molecule. Co2O+2, Co4O+3, Co4O+4, and CoCrO+2 are found to be relatively difficult to dissociate and appear as fragmentation product of several larger clusters, suggesting that they are particularly stable. The geometric structures of pure and Cr doped cobalt oxide species are studied using density functional theory calculations. Dissociation energies for different evaporation channels are calculated and compared with the experimental observations. The influence of the dopant atom on the structure and the stability of the clusters is discussed.

  4. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

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

    Liang, Wenchuan

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S 2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S 2 state with the g~4 electron paramagnetic resonance (EPR) signal (S 2-g4 state) was compared with that in the S 2 state with multiline signal (S 2-MLS state) and the S 1 state. The S 2-g4 statemore » has a higher XAS inflection point energy than that of the S 1 state, indicating the oxidation of Mn in the advance from the S 1 to the S 2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S 2-g4 state is different from that in the S 2-MLS or the S 1 state. In the S 2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S 1 or S 2-MLS states. The third shell of the S 2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S 2-MLS or the S 1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S 1 → S 2 transition.« less

  5. Structural changes in the human vas deferens after tantalum clip occlusion and conventional vasectomy.

    PubMed

    Kothari, L K; Gupta, A S

    1978-02-01

    In 15 human subjects, the vasa deferentia were occluded by applying two tantalum clips on one side and by conventional vasectomy with silk ligatures on the other. After 2 weeks, the occluded segments were recovered for histopathologic examination of serial sections. Obstructing the seminal tract did not, as such, produce any significant change in the vas: the distal and proximal segments appeared to be essentially similar and normal. At the actual site of occlusion, however, tantalum clips produced marked flattening of the tube, complete loss of lining epithelium, distortion of the muscular lamellae, and areas of hemorrhage. The lumen was converted into a narrow slit. Under the ligatures, the damage was largely confined to denudation of the mucosal epithelium. The mucosa of the intersegment left unexcised between two clips showed hyalinization, invasion by macrophages, and degeneration of the epithelium. The changes under the clips suggest that, although clip occlusion may offer several advantages, sterility cannot be reversed merely by removing the clips. The mechanisms of these changes, different in the case of clips and ligatures, are discussed and some possible long-term consequences are considered.

  6. Micro- and nanostructure of a titanium surface electric-spark-doped with tantalum and modified by high-frequency currents

    NASA Astrophysics Data System (ADS)

    Fomin, A. A.; Fomina, M. A.; Koshuro, V. A.; Rodionov, I. V.; Voiko, A. V.; Zakharevich, A. M.; Aman, A.; Oseev, A.; Hirsch, S.; Majcherek, S.

    2016-09-01

    We have studied the characteristics of the porous microstructure of tantalum coatings obtained by means of electric spark spraying on the surface of commercial grade titanium. It is established that, at an electric spark current within 0.8-2.2 A, a mechanically strong tantalum coating microstructure is formed with an average protrusion size of 5.1-5.4 µm and pore sizes from 3.5 to 9.2 µm. On the nanoscale, a structurally heterogeneous state of coatings has been achieved by subsequent thermal modification at 800-830°C with the aid of high-frequency currents. A metal oxide nanostructure with grain sizes from 40 to 120 nm is formed by short-time (~30 s) thermal modification. The coating hardness reaches 9.5-10.5 GPa at an elastic modulus of 400-550 GPa.

  7. Thermal expansion method for lining tantalum alloy tubing with tungsten

    NASA Technical Reports Server (NTRS)

    Watson, G. K.; Whittenberger, J. D.; Mattson, W. F.

    1973-01-01

    A differential-thermal expansion method was developed to line T-111 (tantalum - 8 percent tungsten - 2 percent hafnium) tubing with a tungsten diffusion barrier as part of a fuel element fabrication study for a space power nuclear reactor concept. This method uses a steel mandrel, which has a larger thermal expansion than T-111, to force the tungsten against the inside of the T-111 tube. Variables investigated include lining temperature, initial assembly gas size, and tube length. Linear integrity increased with increasing lining temperature and decreasing gap size. The method should have more general applicability where cylinders must be lined with a thin layer of a second material.

  8. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

    DOE PAGES

    de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

    2017-03-24

    In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

  9. Charge exchange in galaxy clusters

    NASA Astrophysics Data System (ADS)

    Gu, Liyi; Mao, Junjie; de Plaa, Jelle; Raassen, A. J. J.; Shah, Chintan; Kaastra, Jelle S.

    2018-03-01

    Context. Though theoretically expected, the charge exchange emission from galaxy clusters has never been confidently detected. Accumulating hints were reported recently, including a rather marginal detection with the Hitomi data of the Perseus cluster. As previously suggested, a detection of charge exchange line emission from galaxy clusters would not only impact the interpretation of the newly discovered 3.5 keV line, but also open up a new research topic on the interaction between hot and cold matter in clusters. Aim. We aim to perform the most systematic search for the O VIII charge exchange line in cluster spectra using the RGS on board XMM-Newton. Methods: We introduce a sample of 21 clusters observed with the RGS. In order to search for O VIII charge exchange, the sample selection criterion is a >35σ detection of the O VIII Lyα line in the archival RGS spectra. The dominating thermal plasma emission is modeled and subtracted with a two-temperature thermal component, and the residuals are stacked for the line search. The systematic uncertainties in the fits are quantified by refitting the spectra with a varying continuum and line broadening. Results: By the residual stacking, we do find a hint of a line-like feature at 14.82 Å, the characteristic wavelength expected for oxygen charge exchange. This feature has a marginal significance of 2.8σ, and the average equivalent width is 2.5 × 10-4 keV. We further demonstrate that the putative feature can be barely affected by the systematic errors from continuum modeling and instrumental effects, or the atomic uncertainties of the neighboring thermal lines. Conclusions: Assuming a realistic temperature and abundance pattern, the physical model implied by the possible oxygen line agrees well with the theoretical model proposed previously to explain the reported 3.5 keV line. If the charge exchange source indeed exists, we expect that the oxygen abundance could have been overestimated by 8-22% in previous X

  10. On Defect Cluster Aggregation and Non-Reducibilty in Tin-Doped Indium Oxide

    NASA Astrophysics Data System (ADS)

    Warschkow, Oliver; Ellis, Donald E.; Gonzalez, Gabriela; Mason, Thomas O.

    2003-03-01

    The conductivity of tin-doped indium oxide (ITO), a transparent conductor, is critically dependent on the amount of tin-doping and oxygen partial pressure during preparation and annealing. Frank and Kostlin (Appl. Phys. A 27 (1982) 197-206) rationalized the carrier concentration dependence by postulating the formation of two types of neutral defect clusters at medium tin-doping levels: "Reducible" and "non-reducible" defect clusters; so named to indicate their ability to create carriers under reduction. According to Frank and Kostlin, both are composed of a single oxygen interstitial and two tin atoms substituting for indium, positioned in non-nearest and nearest coordination, respectively. This present work, seeking to distinguish reducible and non-reducible clusters by use of an atomistic model, finds only a weak correlation of oxygen interstitial binding energies with the relative positioning of dopants. Instead, the number of tin-dopants in the vicinity of the interstitial has a much larger effect on how strongly it is bound, a simple consequence of Coulomb interactions. We postulate that oxygen interstitials become non-reducible when clustered with three or more Sn_In. This occurs at higher doping levels as reducible clusters aggregate and share tin atoms. A simple probabilistic model, estimating the average number of clusters so aggregated, provides a qualitatively correct description of the carrier density in reduced ITO as a function of Sn doping level.

  11. Phase Transformation Synthesis of Strontium Tantalum Oxynitride-based Heterojunction for Improved Visible Light-Driven Hydrogen Evolution.

    PubMed

    Zeng, Weixuan; Bian, Yuan; Cao, Sheng; Ma, Yongjin; Liu, Yi; Zhu, Anquan; Tan, Pengfei; Pan, Jun

    2018-06-07

    Tantalum oxynitride-based materials, which possess narrow bandgaps and sufficient band energy potentials, have been of immense interest for water splitting. However, the efficiency of photocatalytic reactions is still low due to the fast electron-hole recombination. Here, a Sr2Ta2O7-xNx/SrTaO2N heterostructured photocatalyst with well-matched band structure was in situ constructed by nitridation of hydrothermal-prepared Sr2Ta2O7 nanosheets. Compared to Sr2Ta2O7-xNx and pure SrTaO2N, the Sr2Ta2O7-xNx/SrTaO2N heterostructured photocatalyst exhibited highest rate of hydrogen evolution, which is ca. 2.0 and 76.4 times of Sr2Ta2O7-xNx and pure SrTaO2N under the similar reaction condition, respectively. The enhanced performance arises from the formation of suitable band matched heterojunction accelerated charge separation. This work provides a promising strategy for the construction of tantalum oxynitride-based heterojunction photocatalysts.

  12. Oxygen therapy for cluster headache. A mask comparison trial. A single-blinded, placebo-controlled, crossover study.

    PubMed

    Petersen, Anja S; Barloese, Mads Cj; Lund, Nunu Lt; Jensen, Rigmor H

    2017-03-01

    Purpose The purpose of this article is to investigate possible differences in effect between three types of masks in the acute treatment of cluster headache (CH). Patients and methods Fifty-seven CH patients according to ICHD-II-criteria participated in a single-blinded, semi-randomized, placebo-controlled, crossover inpatient study, and 102 CH attacks were treated with 100% oxygen delivered by demand valve oxygen (DVO), O 2 ptimask or simple mask (15 liters/min) or placebo delivered by DVO for 15 minutes. Primary endpoint: Two-point decrease of pain on a five-point rating scale within 15 minutes. Results Only 10 CH patients had multiple attacks and reached the point of placebo. There were no significant differences between masks in the primary endpoints ( p = 0.412). After 15 minutes 48% had a two-point decrease using the DVO compared to 45% with placebo ( p = 0.867). After 30 minutes 68% were pain free or had pain relief using DVO and 45% by placebo ( p = 0.061). The DVO was preferred by 62% compared to 5% and 33% for simple mask ( p < 0.0001) and O 2 ptimask ( p = 0.061). In the first attack the DVO was significantly better at achieving pain relief at 15 minutes ( p = 0.018). Treatment with DVO or O 2 ptimask reduced the need for rescue medication compared to the simple mask (23%, 19%, 50%, respectively). No treatment-related adverse events were observed. Conclusion The primary endpoint with pain relief at 15 minutes was non-significant; however, a post hoc analysis of the first attack significantly favored DVO. Further, therapy by O 2 ptimask and DVO resulted in a decreased need for rescue medication. We recommend that CH patients be offered DVO or O 2 ptimask before oxygen therapy is abandoned.

  13. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

    PubMed

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

    2017-04-18

    We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Regioselectivity of H Cluster Oxidation

    PubMed Central

    2011-01-01

    The H2-evolving potential of [FeFe] hydrogenases is severely limited by the oxygen sensitivity of this class of enzymes. Recent experimental studies on hydrogenase from C. reinhardtii point to O2-induced structural changes in the [Fe4S4] subsite of the H cluster. Here, we investigate the mechanistic basis of this observation by means of density functional theory. Unexpectedly, we find that the isolated H cluster shows a pathological catalytic activity for the formation of reactive oxygen species such as O2– and HO2–. After protonation of O2–, an OOH radical may coordinate to the Fe atoms of the cubane, whereas H2O2 specifically reacts with the S atoms of the cubane-coordinating cysteine residues. Both pathways are accompanied by significant structural distortions that compromise cluster integrity and thus catalytic activity. These results explain the experimental observation that O2-induced inhibition is accompanied by distortions of the [Fe4S4] moiety and account for the irreversibility of this process. PMID:22106822

  15. Development of advanced high strength tantalum base alloys. Part 1: Screening investigation

    NASA Technical Reports Server (NTRS)

    Buckman, R. W., Jr.

    1971-01-01

    Five experimental tantalum alloy compositions containing 13-18% W+Re+Hf solid solution solute additions with dispersed phase strengthening achieved by carbon or nitrogen additions were prepared as 1.4 inch diameter ingot processed to 3/8 inch diameter rod and evaluated. Elevated temperature tensile and creep strength increased monotonically with increasing solute content. Room temperature elongation decreased for 20% to less than 2% as the solute content was increased above 16%. Phase identification indicated that the precipitating phase in the carbide containing alloys was Ta2C.

  16. Influence of process parameters on plasma electrolytic surface treatment of tantalum for biomedical applications

    NASA Astrophysics Data System (ADS)

    Sowa, Maciej; Woszczak, Maja; Kazek-Kęsik, Alicja; Dercz, Grzegorz; Korotin, Danila M.; Zhidkov, Ivan S.; Kurmaev, Ernst Z.; Cholakh, Seif O.; Basiaga, Marcin; Simka, Wojciech

    2017-06-01

    This work aims to quantify the effect of anodization voltage and electrolyte composition used during DC plasma electrolytic oxidation (PEO), operated as a 2-step process, on the surface properties of the resulting oxide coatings on tantalum. The first step consisted of galvanostatic anodization (150 mA cm-2) of the tantalum workpiece up to several limiting voltages (200, 300, 400 and 500 V). After attaining the limiting voltage, the process was switched to voltage control, which resulted in a gradual decrease of the anodic current density. The anodic treatment was realized in a 0.5 M Ca(H2PO2)2 solution, which was then modified by the addition of 1.15 M Ca(HCOO)2 as well as 1.15 M and 1.5 M Mg(CH3COO)2. The increasing voltage of anodization led to the formation of thicker coatings, with larger pores and enriched with electrolytes species to a higher extent. The solutions containing HCOO- and CH3COO- ions caused the formation of coatings which were slightly hydrophobic (high contact angle). In the case of the samples anodized up to 500 V, scattered crystalline deposits were observed. Bioactive phases, such as hydroxyapatite, were detected in the treated oxide coatings by XRD and XPS.

  17. Development of tungsten-tantalum generator

    NASA Technical Reports Server (NTRS)

    Leblanc, A.; Babich, J.; Jhingran, S. G.

    1985-01-01

    The purpose of this project was to develop a useable tungsten (W)/tantalum (Ta) generator. Ta-178 is formed following the decay of its parent, W-178 (half-life: 21.7d) and has a half life of 9.3 minutes in turn yielding stable Hf-178. The decay of the parent isotope (W-178) occurs entirely by electron capture to the 9.3 minute Ta-178 state, without feeding the high spin Ta-178 isomer (half life 2.2 hours). In Ta-178 decay, 99.2% of the disintegrations proceed by electron capture and 0.18% by positron emission. Electron capture results in a 61.2% branch to the ground state of Hf-178 and 33.7% to the first excited state at 93 1KeV. The most prominent features of the radionuclide's energy spectrum are the hafnium characteristic radiation peaks with energies between 54.6 and 65.0 KeV. The radiation exposure dose of Ta-118 was calculated to be approximately one-twentieth that of Tc-99m on a per millicurie basis. A twenty-fold reduction in radiation exposure from Ta-178 compared with Tc-99m means that the usual administered dose can be increased three or four times, greatly increasing statistical accuracy while reducing radiation exposure by a factor of five.

  18. Conflict minerals in the compute sector: estimating extent of tin, tantalum, tungsten, and gold use in ICT products.

    PubMed

    Fitzpatrick, Colin; Olivetti, Elsa; Miller, Reed; Roth, Richard; Kirchain, Randolph

    2015-01-20

    Recent legislation has focused attention on the supply chains of tin, tungsten, tantalum, and gold (3TG), specifically those originating from the eastern part of the Democratic Republic of Congo. The unique properties of these so-called “conflict minerals” lead to their use in many products, ranging from medical devices to industrial cutting tools. This paper calculates per product use of 3TG in several information, communication, and technology (ICT) products such as desktops, servers, laptops, smart phones, and tablets. By scaling up individual product estimates to global shipment figures, this work estimates the influence of the ICT sector on 3TG mining in covered countries. The model estimates the upper bound of tin, tungsten, tantalum, and gold use within ICT products to be 2%, 0.1%, 15%, and 3% of the 2013 market share, respectively. This result is projected into the future (2018) based on the anticipated increase in ICT device production.

  19. Evanescent field Sensors Based on Tantalum Pentoxide Waveguides – A Review

    PubMed Central

    Schmitt, Katrin; Oehse, Kerstin; Sulz, Gerd; Hoffmann, Christian

    2008-01-01

    Evanescent field sensors based on waveguide surfaces play an important role where high sensitivity is required. Particularly tantalum pentoxide (Ta2O5) is a suitable material for thin-film waveguides due to its high refractive index and low attenuation. Many label-free biosensor systems such as grating couplers and interferometric sensors as well as fluorescence-based systems benefit from this waveguide material leading to extremely high sensitivity. Some biosensor systems based on Ta2O5 waveguides already took the step into commercialization. This report reviews the various detection systems in terms of limit of detection, the applications, and the suitable surface chemistry. PMID:27879731

  20. Titanium modified with layer-by-layer sol-gel tantalum oxide and an organodiphosphonic acid: a coating for hydroxyapatite growth.

    PubMed

    Arnould, C; Volcke, C; Lamarque, C; Thiry, P A; Delhalle, J; Mekhalif, Z

    2009-08-15

    Titanium and its alloys are widely used in surgical implants due to their appropriate properties like corrosion resistance, biocompatibility, and load bearing. Unfortunately when metals are used for orthopedic and dental implants there is the possibility of loosening over a long period of time. Surface modification is a good way to counter this problem. A thin tantalum oxide layer obtained by layer-by-layer (LBL) sol-gel deposition on top of a titanium surface is expected to improve biocorrosion resistance in the body fluid, biocompatibility, and radio-opacity. This elaboration step is followed by a modification of the tantalum oxide surface with an organodiphosphonic acid self-assembled monolayer, capable of chemically binding to the oxide surface, and also improving hydroxyapatite growth. The different steps of this proposed process are characterized by surfaces techniques like contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM).

  1. Oxygen trapped by rare earth tetrahedral clusters in Nd4FeOS6: Crystal structure, electronic structure, and magnetic properties

    NASA Astrophysics Data System (ADS)

    Lin, Qisheng; Taufour, Valentin; Zhang, Yuemei; Wood, Max; Drtina, Thomas; Bud'ko, Sergey L.; Canfield, Paul C.; Miller, Gordon J.

    2015-09-01

    Single crystals of Nd4FeOS6 were grown from an Fe-S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd4MnOSe6-type structure (P63mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å3, Z=2), featuring parallel chains of face-sharing [FeS6×1/2]4- trigonal antiprisms and interlinked [Nd4OS3]4+ cubane-like clusters. Oxygen atoms were found to be trapped by Nd4 clusters in the [Nd4OS3]4+ chains. Structural differences among Nd4MnOSe6-type Nd4FeOS6 and the related La3CuSiS7- and Pr8CoGa3-type structures have been described. Magnetic susceptibility measurements on Nd4FeOS6 suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions.

  2. Stable platinum nanoclusters on genomic DNA–graphene oxide with a high oxygen reduction reaction activity

    PubMed Central

    Tiwari, Jitendra N.; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N.; Kemp, K. Christian; Le, Nhien H.; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S.

    2013-01-01

    Nanosize platinum clusters with small diameters of 2–4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA–graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA–graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA–graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries. PMID:23900456

  3. Influence of Cr doping on the stability and structure of small cobalt oxide clusters

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

    Tung, Nguyen Thanh; Lievens, Peter; Janssens, Ewald, E-mail: ewald.janssens@fys.kuleuven.be

    2014-07-28

    The stability of mass-selected pure cobalt oxide and chromium doped cobalt oxide cluster cations, Co{sub n}O{sub m}{sup +} and Co{sub n−1}CrO{sub m}{sup +} (n = 2, 3; m = 2–6 and n = 4; m = 3–8), has been investigated using photodissociation mass spectrometry. Oxygen-rich Co{sub n}O{sub m}{sup +} clusters (m ⩾ n + 1 for n = 2, 4 and m ⩾ n + 2 for n = 3) prefer to photodissociate via the loss of an oxygen molecule, whereas oxygen poorer clusters favor the evaporation of oxygen atoms. Substituting a single Co atom by a single Cr atommore » alters the dissociation behavior. All investigated Co{sub n−1}CrO{sub m}{sup +} clusters, except CoCrO{sub 2}{sup +} and CoCrO{sub 3}{sup +}, prefer to decay by eliminating a neutral oxygen molecule. Co{sub 2}O{sub 2}{sup +}, Co{sub 4}O{sub 3}{sup +}, Co{sub 4}O{sub 4}{sup +}, and CoCrO{sub 2}{sup +} are found to be relatively difficult to dissociate and appear as fragmentation product of several larger clusters, suggesting that they are particularly stable. The geometric structures of pure and Cr doped cobalt oxide species are studied using density functional theory calculations. Dissociation energies for different evaporation channels are calculated and compared with the experimental observations. The influence of the dopant atom on the structure and the stability of the clusters is discussed.« less

  4. Enhanced Cell Capture on Functionalized Graphene Oxide Nanosheets through Oxygen Clustering.

    PubMed

    Bardhan, Neelkanth M; Kumar, Priyank V; Li, Zeyang; Ploegh, Hidde L; Grossman, Jeffrey C; Belcher, Angela M; Chen, Guan-Yu

    2017-02-28

    With the global rise in incidence of cancer and infectious diseases, there is a need for the development of techniques to diagnose, treat, and monitor these conditions. The ability to efficiently capture and isolate cells and other biomolecules from peripheral whole blood for downstream analyses is a necessary requirement. Graphene oxide (GO) is an attractive template nanomaterial for such biosensing applications. Favorable properties include its two-dimensional architecture and wide range of functionalization chemistries, offering significant potential to tailor affinity toward aromatic functional groups expressed in biomolecules of interest. However, a limitation of current techniques is that as-synthesized GO nanosheets are used directly in sensing applications, and the benefits of their structural modification on the device performance have remained unexplored. Here, we report a microfluidic-free, sensitive, planar device on treated GO substrates to enable quick and efficient capture of Class-II MHC-positive cells from murine whole blood. We achieve this by using a mild thermal annealing treatment on the GO substrates, which drives a phase transformation through oxygen clustering. Using a combination of experimental observations and MD simulations, we demonstrate that this process leads to improved reactivity and density of functionalization of cell capture agents, resulting in an enhanced cell capture efficiency of 92 ± 7% at room temperature, almost double the efficiency afforded by devices made using as-synthesized GO (54 ± 3%). Our work highlights a scalable, cost-effective, general approach to improve the functionalization of GO, which creates diverse opportunities for various next-generation device applications.

  5. Influence of reactive gas admixture on transition metal cluster nucleation in a gas aggregation cluster source

    NASA Astrophysics Data System (ADS)

    Peter, Tilo; Polonskyi, Oleksandr; Gojdka, Björn; Mohammad Ahadi, Amir; Strunskus, Thomas; Zaporojtchenko, Vladimir; Biederman, Hynek; Faupel, Franz

    2012-12-01

    We quantitatively assessed the influence of reactive gases on the formation processes of transition metal clusters in a gas aggregation cluster source. A cluster source based on a 2 in. magnetron is used to study the production rate of titanium and cobalt clusters. Argon served as working gas for the DC magnetron discharge, and a small amount of reactive gas (oxygen and nitrogen) is added to promote reactive cluster formation. We found that the cluster production rate depends strongly on the reactive gas concentration for very small amounts of reactive gas (less than 0.1% of total working gas), and no cluster formation takes place in the absence of reactive species. The influence of discharge power, reactive gas concentration, and working gas pressure are investigated using a quartz micro balance in a time resolved manner. The strong influence of reactive gas is explained by a more efficient formation of nucleation seeds for metal-oxide or nitride than for pure metal.

  6. Raman spectra of ruthenium and tantalum trimers in argon matrices

    NASA Astrophysics Data System (ADS)

    Fang, Li; Shen, Xiaole; Chen, Xiaoyu; Lombardi, John R.

    2000-12-01

    The resonance Raman spectra of ruthenium trimers (Ru 3) in argon matrices have been obtained. Three resonance Raman transitions were observed between 570 and 590 nm. Two of them (303.4 and 603.7 cm -1) are assigned to the totally symmetric vibrational progression, giving k e=1.86 mdyne/ Å. The line at 581.5 cm-1 is assigned as the origin of a low-lying electronic state. We also report on the observation of a resonance Raman spectrum of tantalum trimers (Ta 3). Observed lines include 251.2 and 501.9 cm-1 which we assign to the fundamental and the first overtone of the symmetric stretch in Ta 3. This gives k e=2.25 mdyne/ Å.

  7. Anionic tantalum dihydride complexes: heterobimetallic coupling reactions and reactivity toward small-molecule activation.

    PubMed

    Ostapowicz, Thomas G; Fryzuk, Michael D

    2015-03-02

    The anionic dihydride complex [Cp2TaH2](-) was synthesized as a well-defined molecular species by deprotonation of Cp2TaH3 while different solubilizing agents, such as [2.2.2]cryptand and 18-crown-6, were applied to encapsulate the alkali-metal counterion. The ion pairs were characterized by multiple spectroscopic methods as well as X-ray crystallography, revealing varying degrees of interaction between the hydride ligands of the anion and the respective countercation in solution and in the solid state. The [Cp2TaH2](-) complex anion shows slow exchange of the hydride ligands when kept under a D2 atmosphere, but a very fast reaction is observed when [Cp2TaH2](-) is reacted with CO2, from which Cp2TaH(CO) is obtained as the tantalum-containing reaction product, along with inorganic salts. Furthermore, [Cp2TaH2](-) can act as a synthon in heterobimetallic coupling reactions with transition-metal halide complexes. Thus, the heterobimetallic complexes Cp2Ta(μ-H)2Rh(dippp) and Cp2Ta(μ-H)2Ru(H)(CO)(P(i)Pr3)2 were synthesized and characterized by various spectroscopies and via single-crystal X-ray diffraction. The new hydride bridged tantalum-rhodium heterobimetallic complex is cleaved under a CO atmosphere to yield mononuclear species and slowly exchanges protons and hydride ligands when exposed to D2 gas.

  8. Chemical composition of stars in globular clusters: M5, M13, and M3

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

    Pilachowski, C.A.; Wallerstein, G.; Myckky Leep, E.

    The composition of giant stars in the globular clusters M3, M5, and M13 have been determined by detailed model atmosphere analysis; the average iron deficiencies relative to the Sun are -1.55, -1.33, and -1.42, respectively. Oxygen is overabundant relative to iron in M3 and M5 but not in M13. Differences in the oxygen abundance can account for variation in horizontal-branch morphology; clusters of intermediate metallicity with high oxygen have red horizontal-branch stars, and those with low oxygen have only blue horizontal-branch stars Z/sub cno/ is the second abundance parameter.

  9. Compaction and High-Pressure Response of Granular Tantalum Oxide

    NASA Astrophysics Data System (ADS)

    Vogler, Tracy; Root, Seth; Knudson, Marcus; Thornhill, Tom; Reinhart, William

    2015-06-01

    The dynamic behavior of nearly fully-dense and porous tantalum oxide (Ta2O5) is studied. Two particle morphologies are used to obtain two distinct initial tap densities, which correspond to approximately 40% and 15% of crystalline density. The response is characterized from low pressures, which result in incomplete compaction, to very high pressures where the thermal component of the EOS dominates. Issues related to a possible phase transformation along the Hugoniot and to establishing reasonable error bars on the experimental data will be discussed. The suitability of continuum and mesoscale models to capture the experimental results will be examined. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  10. Methanethiol chemistry on TiO 2-supported Ni clusters

    NASA Astrophysics Data System (ADS)

    Ozturk, O.; Park, J. B.; Black, T. J.; Rodriguez, J. A.; Hrbek, J.; Chen, D. A.

    2008-10-01

    The thermal decomposition of methanethiol on Ni clusters grown on TiO 2(1 1 0) was studied by temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS) and low energy ion scattering (LEIS). On all of the Ni surfaces investigated, methane and hydrogen were observed as gaseous products in the TPD experiments, and the only sulfur-containing species that desorbed from the surface was methanethiol itself at low temperatures. The two pathways for methanethiol reaction were hydrodesulfurization to produce methane and nonselective decomposition, which leaves atomic carbon and sulfur on the surface. From high resolution XPS studies, methyl thiolate was identified as the surface intermediate for reaction on TiO 2 and on all of the Ni surfaces investigated, similar to what is observed on single-crystal Ni surfaces. However, the binding sites for methyl thiolate on the 1 ML (monolayer) Ni clusters were different from those on the Ni clusters at coverages of 2.5 ML and higher, based on the S(2p) binding energies for methyl thiolate. No distinct changes in activity or selectivity were observed for the smaller Ni clusters grown at low coverage compared to the more film-like Ni surfaces other than what could be accounted for by changes in total surface area. Interactions between the Ni clusters and the TiO 2 support had two main effects on chemical activity. First, carbon was oxidized by oxygen from the TiO 2 lattice to produce CO at temperatures above 800 K. Second, annealing induced encapsulation of the Ni clusters by reduced TiO x and chemisorbed oxygen. At 800 K, the Ni clusters were totally encapsulated, resulting in a complete loss of methanethiol activity; partial encapsulation at 700 K caused a smaller decrease in activity accompanied by increased oxidation of carbon by lattice oxygen.

  11. Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity

    DOE PAGES

    Semin, B. K.; Davletshina, L. N.; Seibert, M.; ...

    2017-11-11

    Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extractmore » only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster.« less

  12. Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity

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

    Semin, B. K.; Davletshina, L. N.; Seibert, M.

    Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extractmore » only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster.« less

  13. Thermodynamics of Palladium (Pd) and Tantalum (Ta) Relevant to Secondary Copper Smelting

    NASA Astrophysics Data System (ADS)

    Shuva, M. A. H.; Rhamdhani, M. A.; Brooks, G. A.; Masood, S. H.; Reuter, M. A.

    2017-02-01

    The slag-to-metal distribution ratios of palladium (Pd), L_{{Pd}}^{s/m} , in the range of oxygen partial pressure ( pO2) from 10-10 to 10-7 atm at 1473 K to 1623 K (1200 °C to 1350 °C); distribution ratios of tantalum (Ta), L_{{Ta}}^{s/m} , in the range of pO2 from 10-16 to 10-12 atm at 1673 K and 1873 K (1400 °C and 1600 °C), have been determined in this study. The L_{{Pd}}^{s/m} in FeO x -CaO-SiO2-MgO and copper at 1573 K (1300 °C) and pO2 = 10-8 atm is dependant strongly on basicity of slag, i.e. (CaO + MgO)/SiO2 or optical basicity. The current results suggest that Pd presents in the FeO x -CaO-SiO2-MgO slag predominantly as Pd2+. The activity coefficient of PdO in the slag at 1573 K (1300 °C) and pO2 = 10-8 atm was calculated to be in the range of 3.89 × 10-3 to 2.63 × 10-2. The L_{{Pd}}^{s/m} was also found to increase with increasing of pO2 and with decreasing of temperature. It was observed that Ta mostly partition to slag phase and very small amount of Ta was found in liquid copper at the high temperature and reduced condition studied. It can be suggested that to promote recovery of palladium from Pd-containing e-waste, a slag with lower silica content and basic flux based, high temperature with reducing atmosphere, is highly desired particularly in secondary copper smelting.

  14. A hybrid intelligent method for three-dimensional short-term prediction of dissolved oxygen content in aquaculture.

    PubMed

    Chen, Yingyi; Yu, Huihui; Cheng, Yanjun; Cheng, Qianqian; Li, Daoliang

    2018-01-01

    A precise predictive model is important for obtaining a clear understanding of the changes in dissolved oxygen content in crab ponds. Highly accurate interval forecasting of dissolved oxygen content is fundamental to reduce risk, and three-dimensional prediction can provide more accurate results and overall guidance. In this study, a hybrid three-dimensional (3D) dissolved oxygen content prediction model based on a radial basis function (RBF) neural network, K-means and subtractive clustering was developed and named the subtractive clustering (SC)-K-means-RBF model. In this modeling process, K-means and subtractive clustering methods were employed to enhance the hyperparameters required in the RBF neural network model. The comparison of the predicted results of different traditional models validated the effectiveness and accuracy of the proposed hybrid SC-K-means-RBF model for three-dimensional prediction of dissolved oxygen content. Consequently, the proposed model can effectively display the three-dimensional distribution of dissolved oxygen content and serve as a guide for feeding and future studies.

  15. A Proposed Computed Tomography Contrast Agent Using Carboxybetaine Zwitterionic Tantalum Oxide Nanoparticles: Imaging, Biological, and Physicochemical Performance.

    PubMed

    FitzGerald, Paul F; Butts, Matthew D; Roberts, Jeannette C; Colborn, Robert E; Torres, Andrew S; Lee, Brian D; Yeh, Benjamin M; Bonitatibus, Peter J

    2016-12-01

    The aim of this study was to produce and evaluate a proposed computed tomography (CT) contrast agent based on carboxybetaine zwitterionic (CZ)-coated soluble tantalum oxide (TaO) nanoparticles (NPs). We chose tantalum to provide superior imaging performance compared with current iodine-based clinical CT contrast agents. We developed the CZ coating to provide biological and physical performance similar to that of current iodinated contrast agents. In addition, the aim of this study was to evaluate the imaging, biological, and physicochemical performance of this proposed contrast agent compared with clinically used iodinated agents. We evaluated CT imaging performance of our CZ-TaO NPs compared with that of an iodinated agent in live rats, imaged centrally located within a tissue-equivalent plastic phantom that simulated a large patient. To evaluate vascular contrast enhancement, we scanned the rats' great vessels at high temporal resolution during and after contrast agent injection. We performed several in vivo CZ-TaO NP studies in healthy rats to evaluate tolerability. These studies included injecting the agent at the anticipated clinical dose (ACD) and at 3 times and 6 times the ACD, followed by longitudinal hematology to assess impact to blood cells and organ function (from 4 hours to 1 week). Kidney histological analysis was performed 48 hours after injection at 3 times the ACD. We measured the elimination half-life of CZ-TaO NPs from blood, and we monitored acute kidney injury biomarkers with a kidney injury assay using urine collected from 4 hours to 1 week. We measured tantalum retention in individual organs and in the whole carcass 48 hours after injection at ACD. Carboxybetaine zwitterionic TaO NPs were synthesized and analyzed in detail. We used multidimensional nuclear magnetic resonance to determine surface functionality of the NPs. We measured NP size and solution properties (osmolality and viscosity) of the agent over a range of tantalum concentrations

  16. Mechanical properties of tantalum-based ceramic coatings for biomedical applications

    NASA Astrophysics Data System (ADS)

    Donkov, N.; Walkowicz, J.; Zavaleyev, V.; Zykova, A.; Safonov, V.; Dudin, S.; Yakovin, S.

    2018-03-01

    The properties were studied of Ta, Ta2O5 and Ta/Ta2O5 coatings deposited by reactive magnetron sputtering on stainless steel (AISI 316) substrates. The compositional, structural and morphological parameters of the coatings were investigated by means of X-ray photoemission spectroscopy (XPS), energy dispersive X-ray (EDX) spectroscopy, and scanning electron microscopy (SEM). The roughness parameters, adhesion strength, hardness, elastic modulus, and H/E ratio were evaluated by standard techniques. The hardness parameters of the Ta2O5 and Ta/Ta2O5 coatings increased in comparison with pure Ta films, while the relatively low Young’s modulus was related to high elastic recovery and high resistance to cracking. The tantalum-based coatings possessed good biomechanical parameters for advanced implant and stent applications.

  17. Acetabular revisions using porous tantalum components: A retrospective study with 5-10 years follow-up

    PubMed Central

    Evola, Francesco Roberto; Costarella, Luciano; Evola, Giuseppe; Barchitta, Martina; Agodi, Antonella; Sessa, Giuseppe

    2017-01-01

    AIM To evaluate the clinical and X-ray results of acetabular components and tantalum augments in prosthetic hip revisions. METHODS Fifty-eight hip prostheses with primary failure of the acetabular component were reviewed with tantalum implants. The clinical records and X-rays of these cases were retrospectively reviewed. Bone defect evaluations were based on preoperative CT scans and classified according to Paprosky criteria of Radiolucent lines and periprosthetic gaps; implant mobilization and osteolysis were evaluated by X-ray. An ad hoc database was created and statistical analyses were performed with SPSS software (IBM SPSS Statistics for Windows, version 23.0). Statistical analyses were carried out using the Student’s t test for independent and paired samples. A P value of < 0.05 was considered statistically significant and cumulative survival was calculated by the Kaplan-Meier method. RESULTS The mean follow-up was 87.6 ± 25.6 mo (range 3-120 mo). 25 cases (43.1%) were classified as minor defects, and 33 cases (56.9%) as major defects. The preoperative HHS rating improved significantly from a mean of 40.7 ± 6.1 (range: 29-53) before revision, to a mean of 85.8 ± 6.1 (range: 70-94) at the end of the follow-up (Student’s t test for paired samples: P < 0.001). Considering HHS only at the end of follow-up, no statistically significant difference was observed between patients with a major or minor defect (Student’s t test for independent samples: P > 0.05). Radiolucent lines were found in 4 implants (6.9%). Postoperative acetabular gaps were observed in 5 hips (8.6%). No signs of implant mobilization or areas of periprosthetic osteolysis were found in the x-rays at the final follow-up. Only 3 implants failed: 1 case of infection and 2 cases of instability. Defined as the end-point, cumulative survival at 10 years was 95% (for all reasons) and 100% for aseptic loosening of the acetabular component. CONCLUSION The medium-term use of prosthetic tantalum

  18. Acetabular revisions using porous tantalum components: A retrospective study with 5-10 years follow-up.

    PubMed

    Evola, Francesco Roberto; Costarella, Luciano; Evola, Giuseppe; Barchitta, Martina; Agodi, Antonella; Sessa, Giuseppe

    2017-07-18

    To evaluate the clinical and X-ray results of acetabular components and tantalum augments in prosthetic hip revisions. Fifty-eight hip prostheses with primary failure of the acetabular component were reviewed with tantalum implants. The clinical records and X-rays of these cases were retrospectively reviewed. Bone defect evaluations were based on preoperative CT scans and classified according to Paprosky criteria of Radiolucent lines and periprosthetic gaps; implant mobilization and osteolysis were evaluated by X-ray. An ad hoc database was created and statistical analyses were performed with SPSS software (IBM SPSS Statistics for Windows, version 23.0). Statistical analyses were carried out using the Student's t test for independent and paired samples. A P value of < 0.05 was considered statistically significant and cumulative survival was calculated by the Kaplan-Meier method. The mean follow-up was 87.6 ± 25.6 mo (range 3-120 mo). 25 cases (43.1%) were classified as minor defects, and 33 cases (56.9%) as major defects. The preoperative HHS rating improved significantly from a mean of 40.7 ± 6.1 (range: 29-53) before revision, to a mean of 85.8 ± 6.1 (range: 70-94) at the end of the follow-up (Student's t test for paired samples: P < 0.001). Considering HHS only at the end of follow-up, no statistically significant difference was observed between patients with a major or minor defect (Student's t test for independent samples: P > 0.05). Radiolucent lines were found in 4 implants (6.9%). Postoperative acetabular gaps were observed in 5 hips (8.6%). No signs of implant mobilization or areas of periprosthetic osteolysis were found in the x-rays at the final follow-up. Only 3 implants failed: 1 case of infection and 2 cases of instability. Defined as the end-point, cumulative survival at 10 years was 95% (for all reasons) and 100% for aseptic loosening of the acetabular component. The medium-term use of prosthetic tantalum components in prosthetic hip revisions is

  19. Autoionization following nanoplasma formation in atomic and molecular clusters

    NASA Astrophysics Data System (ADS)

    Schütte, Bernd; Lahl, Jan; Oelze, Tim; Krikunova, Maria; Vrakking, Marc J. J.; Rouzée, Arnaud

    2016-05-01

    Nanoplasmas resulting from the ionization of nano-scale particles by intense laser pulses are typically described by quasiclassical models, where electron emission is understood to take place via thermal processes. Recently, we discovered that, following the interaction of intense near-infrared (NIR) laser pulses with molecular oxygen clusters, electron emission from nanoplasmas can also occur from atomic bound states via autoionization [Schütte et al., Phys. Rev. Lett. 114, 123002 (2015)]. Here we extend these studies and demonstrate that the formation and decay of doubly-excited atoms and ions is a very common phenomenon in nanoplasmas. We report on the observation of autoionization involving spin-orbit excited states in molecular oxygen and carbon dioxide clusters as well as in atomic krypton and xenon clusters ionized by intense NIR pulses, for which we find clear bound-state signatures in the electron kinetic energy spectra. By applying terahertz (THz) streaking, we show that the observed autoionization processes take place on a picosecond to nanosecond timescale after the interaction of the NIR laser pulse with the clusters. Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.

  20. Off-stoichiometric defect clustering in irradiated oxides

    NASA Astrophysics Data System (ADS)

    Khalil, Sarah; Allen, Todd; EL-Azab, Anter

    2017-04-01

    A cluster dynamics model describing the formation of vacancy and interstitial clusters in irradiated oxides has been developed. The model, which tracks the composition of the oxide matrix and the defect clusters, was applied to the early stage formation of voids and dislocation loops in UO2, and the effects of irradiation temperature and dose rate on the evolution of their densities and composition was investigated. The results show that Frenkel defects dominate the nucleation process in irradiated UO2. The results also show that oxygen vacancies drive vacancy clustering while the migration energy of uranium vacancies is a rate-limiting factor for the nucleation and growth of voids. In a stoichiometric UO2 under irradiation, off-stoichiometric vacancy clusters exist with a higher concentration of hyper-stoichiometric clusters. Similarly, off-stoichiometric interstitial clusters form with a higher concentration of hyper-stoichiometric clusters. The UO2 matrix was found to be hyper-stoichiometric due to the accumulation of uranium vacancies.

  1. Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

    NASA Astrophysics Data System (ADS)

    Liu, Siqi; Xu, Yi-Jun

    2016-03-01

    The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters-TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

  2. Fabrication of Nano-Crossbar Resistive Switching Memory Based on the Copper-Tantalum Pentoxide-Platinum Device Structure

    NASA Astrophysics Data System (ADS)

    Olga Gneri, Paula; Jardim, Marcos

    Resistive switching memory has been of interest lately not only for its simple metal-insulator-metal (MIM) structure but also for its promising ease of scalability an integration into current CMOS technologies like the Field Programmable Gate Arrays and other non-volatile memory applications. There are several resistive switching MIM combinations but under this scope of research, attention will be paid to the bipolar resistive switching characteristics and fabrication of Tantalum Pentaoxide sandwiched between platinum and copper. By changing the polarity of the voltage bias, this metal-insulator-metal (MIM) device can be switched between a high resistive state (OFF) and low resistive state (ON). The change in states is induced by an electrochemical metallization process, which causes a formation or dissolution of Cu metal filamentary paths in the Tantalum Pentaoxide insulator. There is very little thorough experimental information about the Cu-Ta 2O5-Pt switching characteristics when scaled to nanometer dimensions. In this light, the MIM structure was fabricated in a two-dimensional crossbar format. Also, with the limited available resources, a multi-spacer technique was formulated to localize the active device area in this MIM configuration to less than 20nm. This step is important in understanding the switching characteristics and reliability of this structure when scaled to nanometer dimensions.

  3. Mid-term results of total knee arthroplasty with a porous tantalum monoblock tibial component.

    PubMed

    Hayakawa, Kazue; Date, Hideki; Tsujimura, Shunzo; Nojiri, Sho; Yamada, Harumoto; Nakagawa, Kenji

    2014-01-01

    The objectives of the present study were to assess the mid-term results of cementless total knee arthroplasty (TKA) with the porous tantalum monoblock tibial component and to examine the time course of bone changes on plain radiographs. The subjects were 32 patients, 29 patients were available for follow-up. We investigated the mid-term results of TKA after a mean follow-up period of 7 years and 8 months. We also examined changes of the bone over time on plain radiographs. The Knee Society Clinical Rating scores showed significant improvement. Bone changes around the tibial component were as follows: new bone formation and longitudinal trabecular thickening in 41.4% (Type A), only longitudinal trabecular thickening in 41.4% (Type B), and no changes in 17.2% (Type C). Type A and B changes were more frequent in patients with osteoarthritis, whereas Type C was only seen in patients with rheumatoid arthritis. Three knees had an initial gap, but this disappeared in all cases, and no new radiolucent lines were detected. Stress shielding was observed in seven knees (21.9%), but there was no implant loosening related to it. When we examined the relationship between the mechanical axis and the locations of the tips of the tibial pegs in patients with or without stress shielding, no significant differences were found. The results of mid-term follow-up have demonstrated favorable bone ingrowth, suggesting that porous tantalum is a promising material for cementless TKA. © 2013.

  4. Size-selective reactivity of subnanometer Ag 4 and Ag 16 clusters on a TiO 2 surface

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

    Chen, Po-Tuan; Tyo, Eric C.; Hayashi, Michitoshi

    Size-selected Ag 4 and Ag 16 clusters on a titania surface have been studied for their potential in CO oxidation using theoretical calculations and X-ray absorption near edge spectroscopy. The first peak at the measured Ag K-edge of Ag 16@TiO 2 is more prominent in air than in carbon monoxide environment, but no variation was found between the spectra of Ag 4@TiO 2 in air and in carbon monoxide environments. Density functional theory calculations show a preference for molecular oxygen adsorption for Ag 4@TiO 2 and that for a dissociative one on Ag 16@TiO 2, while carbon monoxide reactions withmore » adsorbed oxygen reduced the Ag 16@TiO 2 cluster. The dissociated oxygen atoms increased the oxidation state of Ag 16 cluster and resulted in the prominent first peak in Ag K-edge spectrum in quasi-particle theory calculations, with the subsequent carbon monoxide oxidation reversing the character of Ag K-edge spectrum associated with the reduction of the cluster. Finally, the results provide insight into the size selectivity of supported subnanometer silver clusters in their interactions with oxygen and carbon monoxide, with implications on the cluster catalytic properties in oxidative reactions.« less

  5. Size-selective reactivity of subnanometer Ag 4 and Ag 16 clusters on a TiO 2 surface

    DOE PAGES

    Chen, Po-Tuan; Tyo, Eric C.; Hayashi, Michitoshi; ...

    2017-03-08

    Size-selected Ag 4 and Ag 16 clusters on a titania surface have been studied for their potential in CO oxidation using theoretical calculations and X-ray absorption near edge spectroscopy. The first peak at the measured Ag K-edge of Ag 16@TiO 2 is more prominent in air than in carbon monoxide environment, but no variation was found between the spectra of Ag 4@TiO 2 in air and in carbon monoxide environments. Density functional theory calculations show a preference for molecular oxygen adsorption for Ag 4@TiO 2 and that for a dissociative one on Ag 16@TiO 2, while carbon monoxide reactions withmore » adsorbed oxygen reduced the Ag 16@TiO 2 cluster. The dissociated oxygen atoms increased the oxidation state of Ag 16 cluster and resulted in the prominent first peak in Ag K-edge spectrum in quasi-particle theory calculations, with the subsequent carbon monoxide oxidation reversing the character of Ag K-edge spectrum associated with the reduction of the cluster. Finally, the results provide insight into the size selectivity of supported subnanometer silver clusters in their interactions with oxygen and carbon monoxide, with implications on the cluster catalytic properties in oxidative reactions.« less

  6. Catalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving Complex

    ERIC Educational Resources Information Center

    Howard, Derrick L.; Tinoco, Arthur D.; Brudvig, Gary W.; Vrettos, John S.; Allen, Bertha Connie

    2005-01-01

    Bioinorganic models of the manganese Mn4 cluster are important not only as aids in understanding the structure and function of the oxygen-evolving complex (OEC), but also in developing artificial water-oxidation catalysts. The mechanism of water oxidation by photosystem II (PSII) is thought to involve the formation of a high-valent terminal Mn-oxo…

  7. Structural requirements and reaction pathways in dimethyl ether combustion catalyzed by supported Pt clusters.

    PubMed

    Ishikawa, Akio; Neurock, Matthew; Iglesia, Enrique

    2007-10-31

    The identity and reversibility of the elementary steps required for catalytic combustion of dimethyl ether (DME) on Pt clusters were determined by combining isotopic and kinetic analyses with density functional theory estimates of reaction energies and activation barriers to probe the lowest energy paths. Reaction rates are limited by C-H bond activation in DME molecules adsorbed on surfaces of Pt clusters containing chemisorbed oxygen atoms at near-saturation coverages. Reaction energies and activation barriers for C-H bond activation in DME to form methoxymethyl and hydroxyl surface intermediates show that this step is more favorable than the activation of C-O bonds to form two methoxides, consistent with measured rates and kinetic isotope effects. This kinetic preference is driven by the greater stability of the CH3OCH2* and OH* intermediates relative to chemisorbed methoxides. Experimental activation barriers on Pt clusters agree with density functional theory (DFT)-derived barriers on oxygen-covered Pt(111). Measured DME turnover rates increased with increasing DME pressure, but decreased as the O2 pressure increased, because vacancies (*) on Pt surfaces nearly saturated with chemisorbed oxygen are required for DME chemisorption. DFT calculations show that although these surface vacancies are required, higher oxygen coverages lead to lower C-H activation barriers, because the basicity of oxygen adatoms increases with coverage and they become more effective in hydrogen abstraction from DME. Water inhibits reaction rates via quasi-equilibrated adsorption on vacancy sites, consistent with DFT results indicating that water binds more strongly than DME on vacancies. These conclusions are consistent with the measured kinetic response of combustion rates to DME, O2, and H2O, with H/D kinetic isotope effects, and with the absence of isotopic scrambling in reactants containing isotopic mixtures of 18O2-16O2 or 12CH3O12CH3-13CH3O13CH3. Turnover rates increased with Pt

  8. A highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) film with the solvent bath treatment by dimethyl sulfoxide as cathode for polymer tantalum capacitor

    NASA Astrophysics Data System (ADS)

    Ma, Xiaopin; Wang, Xiuyu; Li, Mingxiu; Chen, Tongning; Zhang, Hao; Chen, Qiang; Ding, Bonan; Liu, Yanpeng

    2016-06-01

    The highly conductive poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films were prepared on porous tantalum pentoxide surface as cathode for polymer tantalum capacitors (PTC). The electrical performances of PTC with PEDOT:PSS films as cathode were optimized by dimethyl sulfoxide (DMSO) bath treatment. With the DMSO-bath treatment of PTC, the equivalent series resistance (ESR) of PTC decreased from 25 mΩ to 9 mΩ. The ultralow ESR led to better capacitance-frequency performance. The device reliability investigation revealed the enhanced environmental stability of PTC. The enhanced performances were attributed to the conductivity improvement of PEDOT:PSS cathode films and the removal of excess PSS from PEDOT:PSS films.

  9. Multistate Memristive Tantalum Oxide Devices for Ternary Arithmetic

    PubMed Central

    Kim, Wonjoo; Chattopadhyay, Anupam; Siemon, Anne; Linn, Eike; Waser, Rainer; Rana, Vikas

    2016-01-01

    Redox-based resistive switching random access memory (ReRAM) offers excellent properties to implement future non-volatile memory arrays. Recently, the capability of two-state ReRAMs to implement Boolean logic functionality gained wide interest. Here, we report on seven-states Tantalum Oxide Devices, which enable the realization of an intrinsic modular arithmetic using a ternary number system. Modular arithmetic, a fundamental system for operating on numbers within the limit of a modulus, is known to mathematicians since the days of Euclid and finds applications in diverse areas ranging from e-commerce to musical notations. We demonstrate that multistate devices not only reduce the storage area consumption drastically, but also enable novel in-memory operations, such as computing using high-radix number systems, which could not be implemented using two-state devices. The use of high radix number system reduces the computational complexity by reducing the number of needed digits. Thus the number of calculation operations in an addition and the number of logic devices can be reduced. PMID:27834352

  10. Activation energy of tantalum-tungsten oxide thermite reactions

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

    Cervantes, Octavio G.; Munir, Zuhair A.; Chemical Engineering and Materials Science, University of California, Davis, CA

    2011-01-15

    The activation energy of a sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the high-pressure spark plasma sintering (HPSPS) technique at 300 and 400 C. The ignition temperatures were investigated under high heating rates (500-2000 C min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Samples consolidated at 300 C exhibit an abrupt change in temperature response prior to the main ignition temperature. This change in temperature response is attributed to the crystallization of the amorphous WO{sub 3} in the SG derivedmore » Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465 to 670 C. The activation energies of the SG derived Ta-WO{sub 3} thermite composite consolidated at 300 and 400 C were determined to be 38{+-} 2 kJ mol{sup -1} and 57 {+-} 2 kJ mol{sup -1}, respectively. (author)« less

  11. Multistate Memristive Tantalum Oxide Devices for Ternary Arithmetic.

    PubMed

    Kim, Wonjoo; Chattopadhyay, Anupam; Siemon, Anne; Linn, Eike; Waser, Rainer; Rana, Vikas

    2016-11-11

    Redox-based resistive switching random access memory (ReRAM) offers excellent properties to implement future non-volatile memory arrays. Recently, the capability of two-state ReRAMs to implement Boolean logic functionality gained wide interest. Here, we report on seven-states Tantalum Oxide Devices, which enable the realization of an intrinsic modular arithmetic using a ternary number system. Modular arithmetic, a fundamental system for operating on numbers within the limit of a modulus, is known to mathematicians since the days of Euclid and finds applications in diverse areas ranging from e-commerce to musical notations. We demonstrate that multistate devices not only reduce the storage area consumption drastically, but also enable novel in-memory operations, such as computing using high-radix number systems, which could not be implemented using two-state devices. The use of high radix number system reduces the computational complexity by reducing the number of needed digits. Thus the number of calculation operations in an addition and the number of logic devices can be reduced.

  12. Multistate Memristive Tantalum Oxide Devices for Ternary Arithmetic

    NASA Astrophysics Data System (ADS)

    Kim, Wonjoo; Chattopadhyay, Anupam; Siemon, Anne; Linn, Eike; Waser, Rainer; Rana, Vikas

    2016-11-01

    Redox-based resistive switching random access memory (ReRAM) offers excellent properties to implement future non-volatile memory arrays. Recently, the capability of two-state ReRAMs to implement Boolean logic functionality gained wide interest. Here, we report on seven-states Tantalum Oxide Devices, which enable the realization of an intrinsic modular arithmetic using a ternary number system. Modular arithmetic, a fundamental system for operating on numbers within the limit of a modulus, is known to mathematicians since the days of Euclid and finds applications in diverse areas ranging from e-commerce to musical notations. We demonstrate that multistate devices not only reduce the storage area consumption drastically, but also enable novel in-memory operations, such as computing using high-radix number systems, which could not be implemented using two-state devices. The use of high radix number system reduces the computational complexity by reducing the number of needed digits. Thus the number of calculation operations in an addition and the number of logic devices can be reduced.

  13. Coupled-cluster computations of atomic nuclei

    NASA Astrophysics Data System (ADS)

    Hagen, G.; Papenbrock, T.; Hjorth-Jensen, M.; Dean, D. J.

    2014-09-01

    In the past decade, coupled-cluster theory has seen a renaissance in nuclear physics, with computations of neutron-rich and medium-mass nuclei. The method is efficient for nuclei with product-state references, and it describes many aspects of weakly bound and unbound nuclei. This report reviews the technical and conceptual developments of this method in nuclear physics, and the results of coupled-cluster calculations for nucleonic matter, and for exotic isotopes of helium, oxygen, calcium, and some of their neighbors.

  14. Effect of the conditions of sintering of sodium-reduced tantalum powders on their characteristics

    NASA Astrophysics Data System (ADS)

    Prokhorova, T. Yu.; Orlov, V. M.; Miroshnichenko, M. N.; Kolosov, V. N.

    2014-07-01

    The effect of the granulation and heat treatment of sodium-reduced tantalum powders with a specific surface area of 2.5-3.6 m2/g on the bulk density, the powder flow time, and the specific surface area of the powders and the specific capacitance of the anodes made of them is studied. It is shown that heat treatment of a granulated powder in vacuum at 1100°C or in a mixture with magnesium at 800°C makes it possible to achieve the required powder flow time.

  15. Oxygen-vacancy behavior in La2-xSrxCuO4-y by positron annihilation and oxygen diffusion

    NASA Astrophysics Data System (ADS)

    Smedskjaer, L. C.; Routbort, J. L.; Flandermeyer, B. K.; Rothman, S. J.; Legnini, D. G.; Baker, J. E.

    1987-09-01

    Oxygen-diffusion and positron-annihilation results for La2-xSrxCuO4-y compounds are reported. A qualitative explanation of the observed results is given on the basis of a model in which the oxygen-vacancy concentration in La2-xSrxCuO4-y is determined by Sr2+ ion clustering on the La sublattice. This model also leads to a maximum in the Cu3+ ion concentration as a function of the Sr2+ ion concentration.

  16. How Is Fe-S Cluster Formation Regulated?

    PubMed

    Mettert, Erin L; Kiley, Patricia J

    2015-01-01

    Iron-sulfur (Fe-S) clusters are fundamental to numerous biological processes in most organisms, but these protein cofactors can be prone to damage by various oxidants (e.g., O2, reactive oxygen species, and reactive nitrogen species) and toxic levels of certain metals (e.g., cobalt and copper). Furthermore, their synthesis can also be directly influenced by the level of available iron in the environment. Consequently, the cellular need for Fe-S cluster biogenesis varies with fluctuating growth conditions. To accommodate changes in Fe-S demand, microorganisms employ diverse regulatory strategies to tailor Fe-S cluster biogenesis according to their surroundings. Here, we review the mechanisms that regulate Fe-S cluster formation in bacteria, primarily focusing on control of the Isc and Suf Fe-S cluster biogenesis systems in the model bacterium Escherichia coli.

  17. A hybrid intelligent method for three-dimensional short-term prediction of dissolved oxygen content in aquaculture

    PubMed Central

    Yu, Huihui; Cheng, Yanjun; Cheng, Qianqian; Li, Daoliang

    2018-01-01

    A precise predictive model is important for obtaining a clear understanding of the changes in dissolved oxygen content in crab ponds. Highly accurate interval forecasting of dissolved oxygen content is fundamental to reduce risk, and three-dimensional prediction can provide more accurate results and overall guidance. In this study, a hybrid three-dimensional (3D) dissolved oxygen content prediction model based on a radial basis function (RBF) neural network, K-means and subtractive clustering was developed and named the subtractive clustering (SC)-K-means-RBF model. In this modeling process, K-means and subtractive clustering methods were employed to enhance the hyperparameters required in the RBF neural network model. The comparison of the predicted results of different traditional models validated the effectiveness and accuracy of the proposed hybrid SC-K-means-RBF model for three-dimensional prediction of dissolved oxygen content. Consequently, the proposed model can effectively display the three-dimensional distribution of dissolved oxygen content and serve as a guide for feeding and future studies. PMID:29466394

  18. Clusters of anthropometric indicators of body fat associated with maximum oxygen uptake in adolescents

    PubMed Central

    2018-01-01

    Introduction The aim of this study was to evaluate different clusters of anthropometric indicators (body mass index | BMI |, waist circumference | WC |, waist-to-height ratio | WHtR |, triceps skinfold |TR SF|, subscapular skinfold |SE SF|, sum of the triceps and subscapular skinfolds | ΣTR + SE |, and sum of the triceps, subscapular and suprailiac folds | ΣTR + SE + SI|) associated with the VO2max levels in adolescents. Methods The study included 1,132 adolescents (aged 14–19 years) enrolled in public schools of São José, Santa Catarina, Brazil, in the 2014 academic year. The dependent variable was the cluster of anthropometric indicators (BMI, WC, WHtR, TR SF, SE SF, SI SF, ΣTR + SE and ΣTR + SE + SI) of excess body fat. The independent variable was maximum oxygen uptake (VO2max), estimated by the modified Canadian aerobic fitness test—mCAFT. Control variables were: age, skin color, economic level, maternal education, physical activity and sexual maturation. Multinomial logistic regression was used for associations between the dependent and independent variables. Binary logistic regression was performed to identify the association between adolescents with all anthropometric indicators in excess and independent variables. Results One in ten adolescents presented all anthropometric indicators of excess body fat. Multinomial regression showed that with each increase of one VO2max unit, the odds of adolescents having three, four, five or more anthropometric indicators of excess body fat decreased by 0.92, 0.85 and 0.73 times, respectively. In the binary regression, this fact was reconfirmed, demonstrating that with each increase of one VO2max unit, the odds of adolescents having simultaneously the eight anthropometric indicators of excess body fat decreased by 0.55. Conclusion It was concluded that with each increase of one VO2max unit, adolescents decreased the odds of simultaneously presenting three or more anthropometric indicators of excess body fat

  19. Clusters of anthropometric indicators of body fat associated with maximum oxygen uptake in adolescents.

    PubMed

    Gonçalves, Eliane Cristina de Andrade; Nunes, Heloyse Elaine Gimenes; Silva, Diego Augusto Santos

    2018-01-01

    The aim of this study was to evaluate different clusters of anthropometric indicators (body mass index | BMI |, waist circumference | WC |, waist-to-height ratio | WHtR |, triceps skinfold |TR SF|, subscapular skinfold |SE SF|, sum of the triceps and subscapular skinfolds | ΣTR + SE |, and sum of the triceps, subscapular and suprailiac folds | ΣTR + SE + SI|) associated with the VO2max levels in adolescents. The study included 1,132 adolescents (aged 14-19 years) enrolled in public schools of São José, Santa Catarina, Brazil, in the 2014 academic year. The dependent variable was the cluster of anthropometric indicators (BMI, WC, WHtR, TR SF, SE SF, SI SF, ΣTR + SE and ΣTR + SE + SI) of excess body fat. The independent variable was maximum oxygen uptake (VO2max), estimated by the modified Canadian aerobic fitness test-mCAFT. Control variables were: age, skin color, economic level, maternal education, physical activity and sexual maturation. Multinomial logistic regression was used for associations between the dependent and independent variables. Binary logistic regression was performed to identify the association between adolescents with all anthropometric indicators in excess and independent variables. One in ten adolescents presented all anthropometric indicators of excess body fat. Multinomial regression showed that with each increase of one VO2max unit, the odds of adolescents having three, four, five or more anthropometric indicators of excess body fat decreased by 0.92, 0.85 and 0.73 times, respectively. In the binary regression, this fact was reconfirmed, demonstrating that with each increase of one VO2max unit, the odds of adolescents having simultaneously the eight anthropometric indicators of excess body fat decreased by 0.55. It was concluded that with each increase of one VO2max unit, adolescents decreased the odds of simultaneously presenting three or more anthropometric indicators of excess body fat, regardless of biological, economic and

  20. Recent developments of the quantum chemical cluster approach for modeling enzyme reactions.

    PubMed

    Siegbahn, Per E M; Himo, Fahmi

    2009-06-01

    The quantum chemical cluster approach for modeling enzyme reactions is reviewed. Recent applications have used cluster models much larger than before which have given new modeling insights. One important and rather surprising feature is the fast convergence with cluster size of the energetics of the reactions. Even for reactions with significant charge separation it has in some cases been possible to obtain full convergence in the sense that dielectric cavity effects from outside the cluster do not contribute to any significant extent. Direct comparisons between quantum mechanics (QM)-only and QM/molecular mechanics (MM) calculations for quite large clusters in a case where the results differ significantly have shown that care has to be taken when using the QM/MM approach where there is strong charge polarization. Insights from the methods used, generally hybrid density functional methods, have also led to possibilities to give reasonable error limits for the results. Examples are finally given from the most extensive study using the cluster model, the one of oxygen formation at the oxygen-evolving complex in photosystem II.

  1. Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

    PubMed Central

    Liu, Siqi; Xu, Yi-Jun

    2016-01-01

    The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters–TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability. PMID:26947754

  2. Superconductor to weak-insulator transitions in disordered tantalum nitride films

    NASA Astrophysics Data System (ADS)

    Breznay, Nicholas P.; Tendulkar, Mihir; Zhang, Li; Lee, Sang-Chul; Kapitulnik, Aharon

    2017-10-01

    We study the two-dimensional superconductor-insulator transition (SIT) in thin films of tantalum nitride. At zero magnetic field, films can be disorder-tuned across the SIT by adjusting thickness and film stoichiometry; insulating films exhibit classical hopping transport. Superconducting films exhibit a magnetic-field-tuned SIT, whose insulating ground state at high field appears to be a quantum-corrected metal. Scaling behavior at the field-tuned SIT shows classical percolation critical exponents z ν ≈1.3 , with a corresponding critical field Hc≪Hc 2 , the upper critical field. The Hall effect exhibits a crossing point near Hc, but with a nonuniversal critical value ρxy c comparable to the normal-state Hall resistivity. We propose that high-carrier-density metals will always exhibit this pattern of behavior at the boundary between superconducting and (trivially) insulating ground states.

  3. Cracking in dissimilar laser welding of tantalum to molybdenum

    NASA Astrophysics Data System (ADS)

    Zhou, Xingwen; Huang, Yongde; Hao, Kun; Chen, Yuhua

    2018-06-01

    Dissimilar joining of tantalum (Ta) to molybdenum (Mo) is of great interest in high temperature structural component applications. However, few reports were found about joining of these two hard-to-weld metals. The objective of this experimental study was to assess the weldability of laser butt joining of 0.2 mm-thick Ta and Mo. In order to study cracking mechanism in Ta/Mo joint, similar Ta/Ta and Mo/Mo joints were compared under the same welding conditions. An optical microscope observation revealed presence of intergranular cracks in the Mo/Mo joint, while both transgranular and intergranular cracks were observed in Ta/Mo joint. The cracking mechanism of the Ta/Mo joint was investigated further by micro-hardness testing, micro X-ray diffraction and scanning electron microscopy. The results showed that solidification cracking tendency of Mo is a main reason for crack initiation in the Ta/Mo joint. Low ductility feature in fusion zone most certainly played a role in the transgranular propagation of cracking.

  4. Hydrocode Analysis of Lateral Stress Gauges in Shocked Tantalum

    NASA Astrophysics Data System (ADS)

    Harris, Ernest; Winter, Ron

    2007-06-01

    Experiements published by other workers on the resistance change of manganin stress gauges embedded in a lateral orientation in Tantalum targets have been analysed using an Adaptive Mesh Refinement Hydrocode. It was found that for four experiments the shape of the time profile of the computed lateral stress in the mounting layer closely matched the shape of the experimental lateral stress profiles. However, the calculated lateral stresses at the gauge location in the mounting layer are significantly less than the stresses that would have been produced in the target if no gauge had been present. The perturbation caused by the gauge increased as the strength of the applied shock increased. When the perturbations are taken into account values of flow stress that are significantly smaller than those reported in the original research paper are derived. The work demonstrates that the lateral gauge technique can give valuable information on strength provided high resolution simulation is used to compensate for the perturbations caused by the gauges.

  5. First principles study of vibrational dynamics of ceria-titania hybrid clusters

    NASA Astrophysics Data System (ADS)

    Majid, Abdul; Bibi, Maryam

    2017-04-01

    Density functional theory based calculations were performed to study vibrational properties of ceria, titania, and ceria-titania hybrid clusters. The findings revealed the dominance of vibrations related to oxygen when compared to those of metallic atoms in the clusters. In case of hybrid cluster, the softening of normal modes related to exterior oxygen atoms in ceria and softening/hardening of high/low frequency modes related to titania dimmers are observed. The results calculated for monomers conform to symmetry predictions according to which three IR and three Raman active modes were detected for TiO2, whereas two IR active and one Raman active modes were observed for CeO2. The comparative analysis indicates that the hybrid cluster CeTiO4 contains simultaneous vibrational fingerprints of the component dimmers. The symmetry, nature of vibrations, IR and Raman activity, intensities, and atomic involvement in different modes of the clusters are described in detail. The study points to engineering of CeTiO4 to tailor its properties for technological visible region applications in photocatalytic and electrochemical devices.

  6. The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

    DTIC Science & Technology

    2016-01-04

    AFRL-AFOSR-VA-TR-2016-0075 The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters KIT BOWEN JOHNS HOPKINS UNIV BALTIMORE MD...Hydride and Boron Aluminum Hydride Clusters 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0324 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) KIT...of both Aluminum Hydride Cluster Anions and Boron Aluminum Hydride Cluster Anions with Oxygen: Anionic Products The anionic products of reactions

  7. Super-oxidation of silicon nanoclusters: magnetism and reactive oxygen species at the surface

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

    Lepeshkin, Sergey; Baturin, Vladimir; Tikhonov, Evgeny

    2016-01-01

    Oxidation of silicon nanoclusters depending on the temperature and oxygen pressure is explored from first principles using the evolutionary algorithm, and structural and thermodynamic analysis. From our calculations of 90 SinOm clusters we found that under normal conditions oxidation does not stop at the stoichiometric SiO2 composition, as it does in bulk silicon, but goes further placing extra oxygen atoms on the cluster surface. These extra atoms are responsible for light emission, relevant to reactive oxygen species and many of them are magnetic. We argue that the super-oxidation effect is size-independent and discuss its relevance to nanotechnology and miscellaneous applications,more » including biomedical ones.« less

  8. Effects of Cluster Environment on Chemical Abundances in Virgo Cluster Spirals

    NASA Astrophysics Data System (ADS)

    Kennicutt, R. C.; Skillman, E. D.; Shields, G. A.; Zaritsky, D.

    1995-12-01

    We have obtained new chemical abundance measurements of HII regions in Virgo cluster spiral galaxies, in order to test whether the cluster environment has significantly influenced the gas-phase abundances and chemical evolution of spiral disks. The sample of 9 Virgo spirals covers a narrow range of morphological type (Sbc - Sc) but shows broad ranges in HI deficiencies and radii in the cluster. This allows us to compare the Virgo sample as a whole to field spirals, using a large sample from Zaritsky, Kennicutt, & Huchra, and to test for systematic trends with HI content and location within the cluster. The Virgo spirals show a wide dispersion in mean disk abundances and abundance gradients. Strongly HI deficient spirals closest to the cluster core show anomalously high oxygen abundances (by 0.3 to 0.5 dex), while outlying spirals with normal HI content show abundances similar to those of field spirals. The most HI depleted spirals also show weaker abundance gradients on average, but the formal significance of this trend is marginal. We find a strong correlation between mean abundance and HI/optical diameter ratio that is quite distinct from the behavior seen in field galaxies. This suggests that dynamical processes associated with the cluster environment are more important than cluster membership in determining the evolution of chemical abundances and stellar populations in spiral galaxies. Simple chemical evolution models are calculated to predict the magnitude of the abundance enhancement expected if ram-pressure stripping or curtailment of infall is responsible for the gas deficiencies. The increased abundances of the spirals in the cluster core may have significant effects on their use as cosmological standard candles.

  9. Structure, stability and magnetism of cobalt doped (ZnO)n clusters.

    PubMed

    Yang, Jack; Zhang, Y B; Li, Sean

    2011-03-01

    Clusters of magnetic impurities are believed to play an important role in retaining ferromagnetism in diluted magnetic semiconductors (DMS), the origin of which has been a long debated issue. Controlling the dopant homogeneity in magnetic semiconductors is therefore a critical issue for the fabrication of high performance DMS. The current paper presents a first principle study on the stability and magnetic properties of Co doped (ZnO)n (n = 12 and 15) clusters using density functional theory. The results show that cobalt ions in these clusters tend to increase their stabilities by maximizing their co-ordination numbers to oxygen. This will likely to be the case for (ZnO)n clusters with n other than 12 and 15 in order for Co to reside in a stable local crystal field. Expansive (shrinkage) stress is introduced when cobalt resides in exohedral substitutional (endohedral interstitial) sites; such strain can be offset by the cluster deformation. Bidoped cluster is found to be unstable due to the increase of system strain energy. All the doped clusters were found to preserve 3 microg of magnetic moments from Co in the overall clusters, but with part of the local moments on cobalt re-distributed onto neighboring oxygen atoms. Current findings may provide a better understanding on the structural chemistry of magnetic dopants in nanocrystallined DMS materials.

  10. Equilibrating metal-oxide cluster ensembles for oxidation reactions using oxygen in water

    Treesearch

    Ira A. Weinstock; Elena M. G. Barbuzzi; Michael W. Wemple; Jennifer J. Cowan; Richard S. Reiner; Dan M. Sonnen; Robert A. Heintz; James S. Bond; Craig L. Hill

    2001-01-01

    Although many enzymes can readily and selectively use oxygen in water--the most familiar and attractive of all oxidants and solvents, respectively–-the design of synthetic catalysts for selective water-based oxidation processes utilizing molecular oxygen remains a daunting task. Particularly problematic is the fact that oxidation of substrates by O2 involves radical...

  11. Creation of a 3Mn/1Fe cluster in the oxygen-evolving complex of photosystem II and investigation of its functional activity.

    PubMed

    Semin, B К; Davletshina, L N; Seibert, M; Rubin, A B

    2018-01-01

    Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H 2 Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH5.7) than at neutral pH (3Mn/RC are extracted at pH6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H 2 Q action, since H 2 Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H 2 Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O 2 at a low rate in the presence of exogenous Ca 2+ (at about 27% of the rate of O 2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O 2 by the 3Mn/1Fe cluster or apparent O 2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes

  12. Searching for the birthplaces of open clusters with ages of several billion years

    NASA Astrophysics Data System (ADS)

    Acharova, I. A.; Shevtsova, E. S.

    2016-01-01

    We discuss the possibility of finding the birthplaces of open clusters (OC) with ages of several billion years. The proposed method is based on the comparison of the results of the chemical evolution modeling of the Galactic disk with the parameters of the cluster. Five OCs older than 7 Gyr are known: NGC6791, BH176, Collinder 261, Berkeley 17, and Berkeley 39. The oxygen and iron abundances in NGC6791 and the oxygen abundance in BH176 are twice the solar level, the heavy-element abundances in other clusters are close to the corresponding solar values. According to chemical evolution models, at the time of the formation of the objects considered the regions where the oxygen and iron abundances reached the corresponding levels extended out to 5 kpc from the Galactic center.At present time theOCs considered are located several kpc from the Galactic center. Some of these clusters are located extremely high, about 1 kpc above the disk midplane, i.e., they have been subject to some mechanism that has carried them into orbits uncharacteristic of this type of objects. It follows from a comparison with the results of chemical evolution that younger clusters with ages of 4-5 Gyr, e.g., NGC1193,M67, and others, may have formed in a broad range of Galactocentric distances. Their large heights above the disk midplane is sufficient to suggest that these clusters have moved away from their likely birthplaces. Clusters are carried far away from the Galactic disk until the present time: about 40 clusters with ages from 0 to 2 Gyr are observed at heights ranging from 300 to 750 pc.

  13. Formation, structure and bond dissociation thresholds of gas-phase vanadium oxide cluster ions

    NASA Astrophysics Data System (ADS)

    Bell, R. C.; Zemski, K. A.; Justes, D. R.; Castleman, A. W.

    2001-01-01

    The formation and structure of gas-phase vanadium oxide cluster anions are examined using a guided ion beam mass spectrometer coupled with a laser vaporization source. The dominant peaks in the anion total mass distribution correspond to clusters having stoichiometries of the form (VO2)n(VO3)m(O2)q-. Collision-induced dissociation studies of the vanadium oxide species V2O4-6-, V3O6-9-, V4O8-10-, V5O11-13-, V6O13-15-, and V7O16-18- indicate that VO2, VO3, and V2O5 units are the main building blocks of these clusters. There are many similarities between the anion mass distribution and that of the cation distribution studied previously. The principal difference is a shift to higher oxygen content by one additional oxygen atom for the stoichiometric anions (VxOy-) as compared to the cations with the same number of vanadium atoms, which is attributed to the extra pair of electrons of the anionic species. The oxygen-rich clusters, VxOy(O2)-, are shown to more tightly adsorb molecular oxygen than those of the corresponding cationic clusters. In addition, the bond dissociation thresholds for the vanadium oxide clusters ΔE(V+-O)=6.09±0.28 eV, ΔE(OV+-O)=3.51±0.36 eV, and ΔE(O2V--O)=5.43±0.31 eV are determined from the energy-dependent collision-induced dissociation cross sections with Xe as the collision partner. To the best of our knowledge, this is the first bond dissociation energy reported for the breaking of the V-O bond of a vanadium oxide anion.

  14. The effect of low energy helium ion irradiation on tungsten-tantalum (W-Ta) alloys under fusion relevant conditions

    NASA Astrophysics Data System (ADS)

    Gonderman, S.; Tripathi, J. K.; Novakowski, T. J.; Sizyuk, T.; Hassanein, A.

    2017-08-01

    Currently, tungsten remains the best candidate for plasma-facing components (PFCs) for future fusion devices because of its high melting point, low erosion, and strong mechanical properties. However, continued investigation has shown tungsten to undergo severe morphology changes under fusion-like conditions. These results motivate the study of innovative PFC materials which are resistant to surface morphology evolution. The goal of this work is to examine tungsten-tantalum (W-Ta) alloys, a potential PFC material, and their response to low energy helium ion irradiation. Specifically, W-Ta samples are exposed to 100 eV helium irradiations with a flux of 1.15 × 1021 ions m-2 s-1, at 873 K, 1023 K, and 1173 K for 1 h duration. Scanning electron microscopy (SEM) reveals significant changes in surface deterioration due to helium ion irradiation as a function of both temperature and tantalum concentration in W-Ta samples. X-Ray Diffraction (XRD) studies show a slight lattice parameter expansion in W-Ta alloy samples compared to pure W samples. The observed lattice parameter expansion in W-Ta alloy samples (proportional to increasing Ta wt.% concentrations) reflect significant differences observed in the evolution of surface morphology, i.e., fuzz development processes for both increasing Ta wt.% concentration and target temperature. These results suggest a correlation between the observed morphology differences and the induced crystal structure change caused by the presence of tantalum. Shifts in the XRD peaks before and after 100 eV helium irradiation with a flux of 1.15 × 1021 ions m-2 s-1, 1023 K, for 1 h showed a significant difference in the magnitude of the shift. This has suggested a possible link between the atomic spacing of the material and the accumulated damage. Ongoing research is needed on W-Ta alloys and other innovative materials for their application as irradiation resistant materials in future fusion or irradiation environments.

  15. Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation.

    PubMed

    Tian, Shubo; Fu, Qiang; Chen, Wenxing; Feng, Quanchen; Chen, Zheng; Zhang, Jian; Cheong, Weng-Chon; Yu, Rong; Gu, Lin; Dong, Juncai; Luo, Jun; Chen, Chen; Peng, Qing; Draxl, Claudia; Wang, Dingsheng; Li, Yadong

    2018-06-15

    Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a "precursor-preselected" wet-chemistry strategy to synthesize highly dispersed Fe 2 clusters that are supported on mesoporous carbon nitride (mpg-C 3 N 4 ). The obtained Fe 2 /mpg-C 3 N 4 sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe 2 clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd 2 and Ir 2 , which lays the foundation for discovering diatomic cluster catalysts.

  16. Tantalum Sulfide Nanosheets as a Theranostic Nanoplatform for Computed Tomography Imaging-Guided Combinatorial Chemo-Photothermal Therapy.

    PubMed

    Liu, Yanlan; Ji, Xiaoyuan; Liu, Jianhua; Tong, Winnie W L; Askhatova, Diana; Shi, Jinjun

    2017-10-19

    Near-infrared (NIR)-absorbing metal-based nanomaterials have shown tremendous potential for cancer therapy, given their facile and controllable synthesis, efficient photothermal conversion, capability of spatiotemporal-controlled drug delivery, and intrinsic imaging function. Tantalum (Ta) is among the most biocompatible metals and arouses negligible adverse biological responses in either oxidized or reduced forms, and thus Ta-derived nanomaterials represent promising candidates for biomedical applications. However, Ta-based nanomaterials by themselves have not been explored for NIR-mediated photothermal ablation therapy. In this work, we report an innovative Ta-based multifunctional nanoplatform composed of biocompatible tantalum sulfide (TaS 2 ) nanosheets (NSs) for simultaneous NIR hyperthermia, drug delivery, and computed tomography (CT) imaging. The TaS 2 NSs exhibit multiple unique features including (i) efficient NIR light-to-heat conversion with a high photothermal conversion efficiency of 39%. (ii) high drug loading (177% by weight), (iii) controlled drug release triggered by NIR light and moderate acidic pH, (iv) high tumor accumulation via heat-enhanced tumor vascular permeability, (v) complete tumor ablation and negligible side effects, and (vi) comparable CT imaging contrast efficiency to the widely clinically used agent iobitridol. We expect that this multifunctional NS platform can serve as a promising candidate for imaging-guided cancer therapy and selection of cancer patients with high tumor accumulation.

  17. Characteristics of laser produced plasmas of hafnium and tantalum in the 1-7 nm region

    NASA Astrophysics Data System (ADS)

    Li, Bowen; Otsuka, Takamitsu; Sokell, Emma; Dunne, Padraig; O'Sullivan, Gerry; Hara, Hiroyuki; Arai, Goki; Tamura, Toshiki; Ono, Yuichi; Dinh, Thanh-Hung; Higashiguchi, Takeshi

    2017-11-01

    Soft X-ray (SXR) spectra from hafnium and tantalum laser produced plasmas were recorded in the 1-7 nm region using two Nd:YAG lasers with pulse lengths of 170 ps and 10 ns, respectively, operating at a range of power densities. The maximum focused peak power density was 2. 3 × 1014 W cm-2 for 170 ps pulses and 1. 8 × 1012 W cm-2 for 10 ns pulses, respectively. Two intense quasicontinuous intensity bands resulting from n = 4 - n = 4 and n = 4 - n = 5 unresolved transition arrays (UTAs) dominate both sets of experimental spectra. Comparison with calculations performed with the Cowan suite of atomic structure codes as well as consideration of previous experimental and theoretical results aided identification of the most prominent features in the spectra. For the 10 ns spectrum, the highest ion stage that could be identified from the n = 4 - n = 5 arrays were lower than silver-like Hf25+ and Ta26+ (which has a 4 d 104 f ground configuration) indicating that the plasma temperature attained was too low to produce ions with an outermost 4 d subshell, while for the 170 ps plasmas the presence of significantly higher stages was deduced and lines due to 4 d-5 p transitions were clearly evident. Furthermore, we show an enhancement of emission from tantalum using dual laser irradiation, and the effect of pre-pulse durations and delay times between two pulses are demonstrated.

  18. Tibiocalcaneal Arthrodesis With a Porous Tantalum Spacer and Locked Intramedullary Nail for Post-Traumatic Global Avascular Necrosis of the Talus.

    PubMed

    Cohen, Michael M; Kazak, Marat

    2015-01-01

    Global avascular necrosis of the talus is a devastating complication that usually occurs as a result of a post-traumatic or metabolic etiology. When conservative options fail, tibiocalcaneal arthrodesis is generally indicated in conjunction with massive bone grafting to maintain the functional length of the extremity. Several bone grafting options are available, including the use of a freeze-dried or fresh-frozen femoral head allograft or autograft obtained from the iliac crest or fibula, all of which pose their own inherent risks. The noted complications with massive bone grafting techniques have included graft collapse, infection, immune response, donor site morbidity, and nonunion. In an effort to avoid many of these complications, we present a case report involving post-traumatic talar avascular necrosis in a 59-year-old male who was successfully treated with the use of a porous tantalum spacer, an autogenic morselized fibular bone graft, and 30 mL of bone marrow aspirate in conjunction with a retrograde tibiocalcaneal nail. Porous tantalum is an attractive substitute for bone grafting because of its structural integrity, biocompatibility, avoidance of donor site complications, and lack of an immune response. The successful use of porous tantalum has been well-documented in hip and knee surgery. We present a practical surgical approach to tibiotalocalcaneal arthrodesis with a large segmental deficit. To our knowledge, this is the first published report describing an alternative surgical technique to address global avascular necrosis of the talus that could have additional applications in salvaging the ankle with a large bone deficiency. Copyright © 2015 American College of Foot and Ankle Surgeons. Published by Elsevier Inc. All rights reserved.

  19. Superconductor to weak-insulator transitions in disordered tantalum nitride films

    DOE PAGES

    Breznay, Nicholas P.; Tendulkar, Mihir; Zhang, Li; ...

    2017-10-31

    Here, we study the two-dimensional superconductor-insulator transition (SIT) in thin films of tantalum nitride. At zero magnetic field, films can be disorder-tuned across the SIT by adjusting thickness and film stoichiometry; insulating films exhibit classical hopping transport. Superconducting films exhibit a magnetic-field-tuned SIT, whose insulating ground state at high field appears to be a quantum-corrected metal. Scaling behavior at the field-tuned SIT shows classical percolation critical exponents zν ≈ 1.3, with a corresponding critical field H c << H c2, the upper critical field. The Hall effect exhibits a crossing point near H c, but with a nonuniversal critical valuemore » ρ c xy comparable to the normal-state Hall resistivity. We propose that high-carrier-density metals will always exhibit this pattern of behavior at the boundary between superconducting and (trivially) insulating ground states.« less

  20. Comparison of the Manganese Cluster in Oxygen-Evolving Photosystem II with Distorted Cubane Manganese Compounds through X-ray Absorption Spectroscopy

    PubMed Central

    Cinco, Roehl M.; Rompel, Annette; Visser, Hendrik; Aromí, Guillem; Christou, George; Sauer, Kenneth; Klein, Melvin P.; Yachandra, Vittal K.

    2014-01-01

    X-ray absorption spectroscopy has been employed to assess the degree of similarity between the oxygen-evolving complex (OEC) in photosystem II (PS II) and a family of synthetic manganese complexes containing the distorted cubane [Mn4O3X] core (X = benzoate, acetate, methoxide, hydroxide, azide, fluoride, chloride, or bromide). These [Mn4(μ3-O)3(μ3-X)] cubanes possess C3v symmetry except for the X = benzoate species, which is slightly more distorted with only Cs symmetry. In addition, Mn4O3Cl complexes containing three or six terminal Cl ligands at three of the Mn were included in this study. The Mn K-edge X-ray absorption near edge structure (XANES) from the oxygen-ligated complexes begin to resemble general features of the PS II (S1 state) spectrum, although the second derivatives are distinct from those in PS II. The extended X-ray absorption fine structure (EXAFS) of these Mn compounds also displays superficial resemblance to that of PS II, but major differences emerge on closer examination of the phases and amplitudes. The most obvious distinction is the smaller magnitude of the Fourier transform (FT) of the PS II EXAFS compared to the FTs from the distorted cubanes. Curve fitting of the Mn EXAFS spectra verifies the known core structures of the Mn cubanes, and shows that the number of the crucial 2.7 and 3.3 Å Mn–Mn distances differs from that observed in the OEC. The EXAFS method detects small changes in the core structures as X is varied in this series, and serves to exclude the distorted cubane of C3v symmetry as a topological model for the Mn catalytic cluster of the OEC. Instead, the method shows that even more distortion of the cubane framework, altering the ratio of the Mn–Mn distances, is required to resemble the Mn cluster in PS II. PMID:11671305

  1. Diffusion of oxygen interstitials in UO2+x using kinetic Monte Carlo simulations: Role of O/M ratio and sensitivity analysis

    NASA Astrophysics Data System (ADS)

    Behera, Rakesh K.; Watanabe, Taku; Andersson, David A.; Uberuaga, Blas P.; Deo, Chaitanya S.

    2016-04-01

    Oxygen interstitials in UO2+x significantly affect the thermophysical properties and microstructural evolution of the oxide nuclear fuel. In hyperstoichiometric Urania (UO2+x), these oxygen interstitials form different types of defect clusters, which have different migration behavior. In this study we have used kinetic Monte Carlo (kMC) to evaluate diffusivities of oxygen interstitials accounting for mono- and di-interstitial clusters. Our results indicate that the predicted diffusivities increase significantly at higher non-stoichiometry (x > 0.01) for di-interstitial clusters compared to a mono-interstitial only model. The diffusivities calculated at higher temperatures compare better with experimental values than at lower temperatures (< 973 K). We have discussed the resulting activation energies achieved for diffusion with all the mono- and di-interstitial models. We have carefully performed sensitivity analysis to estimate the effect of input di-interstitial binding energies on the predicted diffusivities and activation energies. While this article only discusses mono- and di-interstitials in evaluating oxygen diffusion response in UO2+x, future improvements to the model will primarily focus on including energetic definitions of larger stable interstitial clusters reported in the literature. The addition of larger clusters to the kMC model is expected to improve the comparison of oxygen transport in UO2+x with experiment.

  2. The electro-thermal stability of tantalum relative to aluminum and titanium in cylindrical liner ablation experiments at 550 kA

    NASA Astrophysics Data System (ADS)

    Steiner, Adam M.; Campbell, Paul C.; Yager-Elorriaga, David A.; Cochrane, Kyle R.; Mattsson, Thomas R.; Jordan, Nicholas M.; McBride, Ryan D.; Lau, Y. Y.; Gilgenbach, Ronald M.

    2018-03-01

    Presented are the results from the liner ablation experiments conducted at 550 kA on the Michigan Accelerator for Inductive Z-Pinch Experiments. These experiments were performed to evaluate a hypothesis that the electrothermal instability (ETI) is responsible for the seeding of magnetohydrodynamic instabilities and that the cumulative growth of ETI is primarily dependent on the material-specific ratio of critical temperature to melting temperature. This ratio is lower in refractory metals (e.g., tantalum) than in non-refractory metals (e.g., aluminum or titanium). The experimental observations presented herein reveal that the plasma-vacuum interface is remarkably stable in tantalum liner ablations. This stability is particularly evident when contrasted with the observations from aluminum and titanium experiments. These results are important to various programs in pulsed-power-driven plasma physics that depend on liner implosion stability. Examples include the magnetized liner inertial fusion (MagLIF) program and the cylindrical dynamic material properties program at Sandia National Laboratories, where liner experiments are conducted on the 27-MA Z facility.

  3. Scattering Response of Sucrose Clusters with Intense XFEL Pulses in Water Window

    NASA Astrophysics Data System (ADS)

    Ho, Phay; Benedikt Daurer, Benedikt; Bielecki, Johan; Hantke, Max; Maia, Filipe; Knight, Chris; Hajdu, Janos; Young, Linda; Bostedt, Christoph

    2017-04-01

    We present a combined experimental and theoretical study about the effects of non-linear x-ray ionization dynamics on the scattering response of molecular clusters in the soft x-ray regime that includes and goes beyond the water window. Nanosized sucrose clusters were irradiated with intense XFEL pulses (photon energy from 500 to 1500 eV and pulse duration of 180 fs). Surprisingly, the measured scattering signals near the oxygen K-edge in the water window are found to be substantially smaller than those at higher photon energies. We employ Monte-Carlo/Molecular Dynamics calculations to investigate the x-ray processes as a function of pulse parameters (photon energy, bandwidth and pulse duration) and cluster size. We demonstrate the important role of resonant excitation (RE) in the molecular scattering response in the water window. In particular, 1s ->2p RE cycling enabled in the oxygen atom/ion provide additional ionization pathways which, combined with the long pulse duration, lead to substantial reduction in scattering power of sugar clusters for photon energies just below the oxygen K-edge. Supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US Dept of Energy, Contract DE-AC02-06CH11357.

  4. Oxygen vacancy chain and conductive filament formation in hafnia

    NASA Astrophysics Data System (ADS)

    Xue, Kan-Hao; Miao, Xiang-Shui

    2018-04-01

    The stability and aggregation mechanisms of oxygen vacancy chains are studied for hafnia using self-energy corrected density functional theory. While oxygen vacancies tend not to align along the c-axis of monoclinic HfO2, oxygen vacancy chains along a-axis and b-axis are energetically favorable, with cohesive energies of 0.05 eV and 0.03 eV per vacancy, respectively. Nevertheless, with an increase of the cross section area, intensive oxygen vacancy chains become much more stable in hafnia, which yields phase separation into Hf-clusters and HfO2. Compared with disperse single vacancy chains, intensive oxygen vacancy chains made of 4, 6, and 8 single vacancy chains are energetically more favorable by 0.17, 0.20, and 0.30 eV per oxygen vacancy, respectively. On the other hand, while a single oxygen vacancy chain exhibits a tiny electronic energy gap of around 0.5 eV, metallic conduction emerges for the intensive vacancy chain made of 8 single vacancy chains, which possesses a filament cross section area of ˜0.4 nm2. This sets a lower area limit for Hf-cluster filaments from metallic conduction point of view, but in real hafnia resistive RAM devices the cross section area of the filaments can generally be much larger (>5 nm2) for the sake of energy minimization. Our work sets up a bridge between oxygen vacancy ordering and phase separation in hafnia, and shows a clear trend of filament stabilization with larger dimensions. The results could explain the threshold switching phenomenon in hafnia when a small AFM tip was used as the top electrode, as well as the undesired multimode operation in resistive RAM cells with 3 nm-thick hafnia.

  5. Evaluation of Series T22 Wet Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander

    2017-01-01

    Several types of advanced wet tantalum capacitors, and series T22 in particular, are designed without internal Teflon sealing that is used for military grade, CLR style capacitors. This raises concerns regarding hermeticity of the single seal parts and their capability to withstand high internal gas pressures that might develop during operation in space. To address these issues, T22 series capacitors rated to 50 V and 125 V were subjected to highly accelerated life testing (HALT) at 125 C and rated voltage and step stress random vibration testing (RVT). To simulate conditions of storage or operation under increased internal gas pressure, the parts were stored at temperature of 150 C for 2500 hr (HTS150). Electrical characteristics of the parts were measured through the storage testing and the hermeticity leak rate was tested before and after HTS150. To assess thermo-mechanical robustness of the part, capacitors were manually soldered onto printed wired boards (PWB) and stressed by 1000 temperature cycles between -55 C and +125 C. The effect of temperature cycling was assessed by additional HALT at different temperatures. Results show that T22 series capacitors have robust design and can satisfy requirements for space applications.

  6. Development of Coatings for Tantalum Alloy Nozzle Vanes

    NASA Technical Reports Server (NTRS)

    Stetson, A. R.; Wimber, R. T.

    1967-01-01

    A group of silicide coatings developed for the T222 tantalum-base alloy have afforded over 600 hours of protection at 1600 and 2400 F during cyclic exposure in air. These coatings were applied in two steps. A modifier alloy was applied by slurry techniques and was sintered in vacuum prior to siliciding by pack cementation in argon. Application of the modifier alloy by pack cementation was found to be much less effective. The addition of titanium and vanadium to molybdenum and tungsten yielded beneficial modifier alloys, whereas the addition of chromium showed no improvement. After siliciding, the 15Ti- 35W-15V-35Mo modifier alloy exhibited the best performance; one sample survived 1064 hours of oxidation at 2400 F. This same coating was the only coating to reproducibly provide 600 hours of protection at both 1600 and 2400 F; in the second and third of three experiments, involving oxidation of three to five specimens at each temperature in each experiment, no failures were observed in 600 hours of testing. The slurry coatings were also shown to protect the Cb752 and D43 columbium-base alloys.

  7. Cluster formation of network-modifier cations in cesium silicate glasses

    NASA Astrophysics Data System (ADS)

    Jardón-Álvarez, Daniel; Sanders, Kevin J.; Phyo, Pyae; Baltisberger, Jay H.; Grandinetti, Philip J.

    2018-03-01

    Natural abundance 29Si two-dimensional magic-angle flipping (2D MAF) NMR spectra were measured in a series of ten cesium silicate glass compositions xCs2O.(1 - x)SiO2, where x is 0.067, 0.113, 0.175, 0.179, 0.218, 0.234, 0.263, 0.298, 0.31, and 0.36. The Q3 shielding anisotropy decreases with increasing Cs content—interpreted as an increase in the non-bridging oxygen (NBO) bond length from increasing Cs coordination (clustering) around the NBO. The 29Si 2D MAF spectra for four glass compositions x = 0.218, 0.234, 0.263, 0.298 exhibit a second co-existing and distinctly smaller shielding anisotropy corresponding to a significantly longer Si-NBO length arising from a higher degree of Cs clustering around the NBO. This second Q3 site appears at a Cs2O mole fraction close to the critical mole fraction of x = 0.24 associated with the percolation threshold of non-bridging oxygen in random close packing of oxygen, thus suggesting that the longer Si-NBO length is associated with an infinite size spanning cluster while the sites with larger anisotropies are associated with shorter Si-NBO lengths and belong to finite size clusters. The equilibrium constant of the Q3 disproportionation reaction was determined as k3 = 0.005, indicating a Qn anionic species distribution close to a binary model as expected for a low field strength modifier such as cesium. It is also found that evolution of the isotropic Q4 and line shapes with increasing Cs content are consistent with a random connectivity model between Qn of differing number of bridging oxygen, n.

  8. Hydrocode Analysis of Lateral Stress Gauges in Shocked Tantalum

    NASA Astrophysics Data System (ADS)

    Harris, E. J.; Winter, R. E.

    2007-12-01

    Experiments published by other workers, on the resistance change of manganin stress gauges embedded in a lateral orientation in tantalum targets shocked to a range of stresses, have been analysed using an adaptive mesh refinement hydrocode. It was found that for all of the four experiments the shape of the time profile of the computed lateral stress in the mounting layer closely matched the shape of the experimental lateral stress profiles. However, the calculated lateral stresses at the gauge location in the mounting layer are significantly less than the lateral stresses that would have been produced in the target if no gauge had been present. The perturbation caused by the gauge increased as the strength of the applied shock increased. When the perturbations are taken into account values of flow stress that are significantly smaller than those reported in the original research paper are derived. The work shows that the lateral gauge technique can give valuable information on strength provided high resolution simulation is used to compensate for the perturbations caused by the gauges.

  9. Electrical characterization of glass, teflon, and tantalum capacitors at high temperatures

    NASA Technical Reports Server (NTRS)

    Hammoud, A. N.; Baumann, E. D.; Myers, I. T.; Overton, E.

    1991-01-01

    Dielectric materials and electrical components and devices employed in radiation fields and the space environment are often exposed to elevated temperatures among other things. Therefore, these systems must withstand the high temperature exposure while still providing good electrical and other functional properties. Experiments were carried out to evaluate glass, teflon, and tantalum capacitors for potential use in high temperature applications. The capacitors were characterized in terms of their capacitance and dielectric loss as a function of temperature up to 200 C. At a given temperature, these properties were obtained in a frequency range of 50 Hz to 100 kHz. The DC leakage current measurements were also performed in a temperature range from 20 to 200 C. The obtained results are discussed and conclusions are made concerning the suitability of the capacitors investigated for high temperature applications.

  10. Study on the property of low friction complex graphite-like coating containing tantalum

    NASA Astrophysics Data System (ADS)

    Wang, Zuoping; Feng, Lajun; Shen, Wenning

    2018-03-01

    In order to enhance equipment lifetime under low oil or even dry conditions, tantalum was introduced into the graphite-like coating (GLC) by sputtering mosaic targets. The results showed that the introduction of Ta obviously reduced the friction coefficient and hardness of the GLC, while improved the wearability. When the atomic percentage of Ta was larger than 3%, the steady friction coefficient was lower than 0.01, suggesting the coating exhibited super lubricity. When the content of Ta was about 5.0%, the average friction coefficient was 0.02 by a sliding friction test under load of 20 N in unlubricated condition. Its average friction coefficient reduced by 75%, compared with that of control GLC (0.0825).

  11. Two-dimensional tantalum disulfide: controlling structure and properties via synthesis

    NASA Astrophysics Data System (ADS)

    Zhao, Rui; Grisafe, Benjamin; Krishna Ghosh, Ram; Holoviak, Stephen; Wang, Baoming; Wang, Ke; Briggs, Natalie; Haque, Aman; Datta, Suman; Robinson, Joshua

    2018-04-01

    Tantalum disulfide (TaS2) is a transition metal dichalcogenide (TMD) that exhibits phase transition induced electronic property modulation at low temperature. However, the appropriate phase must be grown to enable the semiconductor/metal transition that is of interest for next generation electronic applications. In this work, we demonstrate direct and controllable synthesis of ultra-thin 1T-TaS2 and 2H-TaS2 on a variety of substrates (sapphire, SiO2/Si, and graphene) via powder vapor deposition. The synthesis process leads to single crystal domains ranging from 20 to 200 nm thick and 1-10 µm on a side. The TaS2 phase (1T or 2H) is controlled by synthesis temperature, which subsequently is shown to control the electronic properties. Furthermore, this work constitutes the first demonstration of a metal-insulator phase transition in directly synthesized 1T-TaS2 films and domains by electronic means.

  12. Fabrication and characterization of powder metallurgy tantalum components prepared by high compaction pressure technique

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

    Kim, Youngmoo; Agency for Defense Development, Yuseong, P.O. Box 35, Yuseong-gu, Daejeon 34186, Republic of Korea.; Lee, Dongju

    2016-04-15

    The present study has investigated the consolidation behaviors of tantalum powders during compaction and sintering, and the characteristics of sintered components. For die compaction, the densification behaviors of the powders are simulated by finite element analyses based on the yield function proposed by Shima and Oyane. Accordingly, the green density distribution for coarser particles is predicted to be more uniform because they exhibits higher initial relative tap density owing to lower interparticle friction. It is also found that cold isostatic pressing is capable of producing higher dense compacts compared to the die pressing. However, unlike the compaction behavior, the sinteredmore » density of smaller particles is found to be higher than those of coarser ones owing to their higher specific surface area. The maximum sintered density was found to be 0.96 of theoretical density where smaller particles were pressed isostatically at 400 MPa followed by sintering at 2000 °C. Moreover, the effects of processing conditions on grain size and texture were also investigated. The average grain size of the sintered specimen is 30.29 μm and its texture is less than 2 times random intensity. Consequently, it is concluded that the higher pressure compaction technique is beneficial to produce high dense and texture-free tantalum components compared to hot pressing and spark plasma sintering. - Highlights: • Higher Ta density is obtained from higher pressure and sintering temperature. • High compaction method enables P/M Ta to achieve the density of 16.00 g·cm{sup −3}. • A P/M Ta component with fine microstructure and random orientation is developed.« less

  13. Effects of Processing Variables on Tantalum Nitride by Reactive-Ion-Assisted Magnetron Sputtering Deposition

    NASA Astrophysics Data System (ADS)

    Wei, Chao‑Tsang; Shieh, Han‑Ping D.

    2006-08-01

    The binary compound tantalum nitride (TaN) and ternary compounds tantalum tungsten nitrides (Ta1-xWxNy) exhibit interesting properties such as high melting point, high hardness, and chemical inertness. Such nitrides were deposited on a tungsten carbide (WC) die and silicon wafers by ion-beam-sputter evaporation of the respective metal under nitrogen ion-assisted deposition (IAD). The effects of N2/Ar flux ratio, post annealing, ion-assisted deposition, deposition rate, and W doping in coating processing variables on hardness, load critical scratching, oxidation resistance, stress and surface roughness were investigated. The optimum N2/Ar flux ratios in view of the hardness and critical load of TaN and Ta1-xWxNy films were ranged from 0.9 to 1.0. Doping W into TaN to form Ta1-xWxNy films led significant increases in hardness, critical load, oxidation resistance, and reduced surface roughness. The optimum doping ratio was [W/(W+Ta)]=0.85. From the deposition rate and IAD experiments, the stress in the films is mainly contributed by sputtering atoms. The lower deposition rate at a high N2/Ar flux ratio resulted in a higher compressive stress. A high compressive residual stress accounts for a high hardness. The relatively high compressive stress was attributed primarily to peening by atoms, ions and electrons during film growth, the Ta1-xWxNy films showed excellent hardness and strength against a high temperature, and sticking phenomena can essentially be avoided through their use. Ta1-xWxNy films showed better performance than the TaN film in terms of mechanical properties and oxidation resistance.

  14. Spark plasma sintering of tantalum carbide and graphene reinforced tantalum carbide composites

    NASA Astrophysics Data System (ADS)

    Kalluri, Ajith Kumar

    Tantalum carbide (TaC), an ultra-high temperature ceramic (UHTC), is well known for its exceptional properties such as high hardness (15-19 GPa), melting point (3950 °C), elastic modulus (537 GPa), chemical resistance, and thermal shock resistance. To make TaC to be the future material for hypersonic vehicles, it is required to improve its thermal conductivity, strength, and fracture toughness. Researchers have previously reinforced TaC ceramic with carbides of silicon and boron as well as carbon nanotubes (CNTs), however, these reinforcements either undergo chemical changes or induce defects in the matrix during processing. In addition, these reinforcements exhibit a very minimal improvement in the properties. In the present work, we attempted to improve TaC fracture toughness by reinforcing with graphene nano-platelets (GNPs) and processing through spark plasma sintering at high temperature of 2000 °C, pressure of 70 MPa, and soaking time of 10 min. In addition, we investigated the active densification mechanism during SPS of TaC powder and the effect of ball milling time on mechanical properties of sintered TaC. A relative density of >96% was achieved using SPS of monolithic TaC (<3 μm). Ball milling improved the sintering kinetics and improved the mechanical properties (microhardness, bi-axial flexural strength, and indentation fracture toughness). Activation energy (100 kJ/mol) and stress exponent (1.2) were obtained using the analytical model developed for power-law creep. Grain boundary sliding is proposed as active densification mechanism based on these calculations. Reinforcing GNPs (2-6 vol.% ) in the TaC matrix improved relative density (99.8% for TaC-6 vol.% GNP). Also ˜150% and ˜180% increase in flexural strength and fracture toughness, respectively, was observed for TaC-6 vol.% GNP composite. The significant improvement in these properties is attributed to improved densification and toughening mechanisms such as sheet pull-out and crack

  15. Phenotypes of comorbidity in OSAS patients: combining categorical principal component analysis with cluster analysis.

    PubMed

    Vavougios, George D; George D, George; Pastaka, Chaido; Zarogiannis, Sotirios G; Gourgoulianis, Konstantinos I

    2016-02-01

    Phenotyping obstructive sleep apnea syndrome's comorbidity has been attempted for the first time only recently. The aim of our study was to determine phenotypes of comorbidity in obstructive sleep apnea syndrome patients employing a data-driven approach. Data from 1472 consecutive patient records were recovered from our hospital's database. Categorical principal component analysis and two-step clustering were employed to detect distinct clusters in the data. Univariate comparisons between clusters included one-way analysis of variance with Bonferroni correction and chi-square tests. Predictors of pairwise cluster membership were determined via a binary logistic regression model. The analyses revealed six distinct clusters: A, 'healthy, reporting sleeping related symptoms'; B, 'mild obstructive sleep apnea syndrome without significant comorbidities'; C1: 'moderate obstructive sleep apnea syndrome, obesity, without significant comorbidities'; C2: 'moderate obstructive sleep apnea syndrome with severe comorbidity, obesity and the exclusive inclusion of stroke'; D1: 'severe obstructive sleep apnea syndrome and obesity without comorbidity and a 33.8% prevalence of hypertension'; and D2: 'severe obstructive sleep apnea syndrome with severe comorbidities, along with the highest Epworth Sleepiness Scale score and highest body mass index'. Clusters differed significantly in apnea-hypopnea index, oxygen desaturation index; arousal index; age, body mass index, minimum oxygen saturation and daytime oxygen saturation (one-way analysis of variance P < 0.0001). Binary logistic regression indicated that older age, greater body mass index, lower daytime oxygen saturation and hypertension were associated independently with an increased risk of belonging in a comorbid cluster. Six distinct phenotypes of obstructive sleep apnea syndrome and its comorbidities were identified. Mapping the heterogeneity of the obstructive sleep apnea syndrome may help the early identification of at

  16. [Comparison of core decompression with stem cell transplantation and tantalum rod implanting in treating stage II non-traumatic osteonecrosis of femoral head].

    PubMed

    He, Bang-Jian; Li, Ju; Lyu, Yi; Tong, Pei-Jian

    2016-12-25

    To compare clinical effects of core decompression with stem cell transplantation and tantalum rod implanting in treating stage II non-traumatic osteonecrosis of femoral head. From March 2012 to September 2012, 45 patients(55 hips)with stage ARCO II non-traumatic osteonecrosis of femoral head were treated and divided into core decompression with stem cell transplantation group(group A) and tantalum rod implanting group(group B) according to number table. In group A, there were 23 cases(28 hips) , including 12 males and 11 females aged from 23 to 51 years old with an average of (36.87±9.52) years, the courses of disease ranged from 2 to 28 months with an average of (17.13±7.74) months, preoperative Harris score was for 35 to 70 with an average of(54.74±11.81), treated with core decompression with stem cell transplantation. In group B, there were 22 cases(27 hips), including 11 males and 11 females aged from 26 to 46 years old with an average of (35.59±7.39) years, the courses of disease ranged from 3 to 26 months with an average of(16.00±7.46) months, preoperative Harris score was for 35 to 76 with an average of (57.18±12.95), treated with core tantalum rod implanting. Operative time, blood loss, hospital stays, hospitalization expenses were observed and compared after treatment between two groups, the clinical effects were evaluated according to Harris criteria. All patients were followed up from 6 to 12 months with an average of 10.8 months. There were significant difference in hospitalization expenses between two groups( P <0.05), while there was no significant statistical difference in blood loss and hospital stay ( P >0.05). At the final following-up, Harris score in group A was(83.04±8.97), 6 cases obtained excellent results, 14 good, 2 good and 1 poor;while Harris score in group A was(84.41±9.94), and 9 cases obtained excellent results, 9 good, 3 good and 1 poor; there was no statistical meaning differences between two groups( P >0.05). Core

  17. Chemical abundances in the globular clusters M3, M13, and NGC 6752

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

    Bell, R.A.; Dickens, R.J.

    The abundances of iron, carbon, nitrogen, and oxygen have been investigated in red giant stars in the globular clusters M3, M13, and NGC 6752. The results are based on application of spectrum synthesis and theoretical colors to observed spectra, DDO colors, and infrared CO measurements. Carbon is depleted by a factor of about 3 relative to other metals in most giants studied, with no evidence for the discontinuity along the giant branch at M/sub v/approx. =-0.7 found for more metal-poor clusters. This contrasts with the greater depletion of about a factor of 6 for the more metal-poor cluster stars, amore » difference which is expected if meridional mixing is responsible for the carbon depletion. The spectroscopic results for nitrogen are imprecise, but the colors suggest enhancements of a factor of 3. The iron abundances for M3 and M13 stars have been determined from published equivalent widths, yielding (Fe/H) close to -1.4 for both clusters. The uncertainties in M3 and M13 CO colors and (O I) equivalent widths make it impossible to derive accurate oxygen abundances, but the depletion of carbon is real and is not caused by an overabundance of oxygen.« less

  18. Graph-Theoretic Analysis of Monomethyl Phosphate Clustering in Ionic Solutions.

    PubMed

    Han, Kyungreem; Venable, Richard M; Bryant, Anne-Marie; Legacy, Christopher J; Shen, Rong; Li, Hui; Roux, Benoît; Gericke, Arne; Pastor, Richard W

    2018-02-01

    All-atom molecular dynamics simulations combined with graph-theoretic analysis reveal that clustering of monomethyl phosphate dianion (MMP 2- ) is strongly influenced by the types and combinations of cations in the aqueous solution. Although Ca 2+ promotes the formation of stable and large MMP 2- clusters, K + alone does not. Nonetheless, clusters are larger and their link lifetimes are longer in mixtures of K + and Ca 2+ . This "synergistic" effect depends sensitively on the Lennard-Jones interaction parameters between Ca 2+ and the phosphorus oxygen and correlates with the hydration of the clusters. The pronounced MMP 2- clustering effect of Ca 2+ in the presence of K + is confirmed by Fourier transform infrared spectroscopy. The characterization of the cation-dependent clustering of MMP 2- provides a starting point for understanding cation-dependent clustering of phosphoinositides in cell membranes.

  19. Effects of alloy composition in alleviating embrittlement problems associated with the tantalum alloy T-111

    NASA Technical Reports Server (NTRS)

    Stephens, J. R.

    1975-01-01

    The causes of aging embrittlement in T-111 (Ta-8W-2Hf) and the effect of alloy modification were investigated. Results show that T-111 possesses a critical combination of tungsten and hafnium that leads to loss in ductility at -196 C after aging near 1040 C. It was found that this occurs because tungsten enhances hafnium segregation to grain boundaries, which also leads to increased susceptibility to hydrogen embrittlement. Aging embrittlement was not observed in tantalum alloys with reduced tungsten or hafnium contents; most of the alloys studied have lower strengths than T-111 and exhibit susceptibility to hydrogen embrittlement.

  20. Rhodium clustering process on defective (8,0) SWCNT: Analysis of chemical and physical properties using density functional theory

    NASA Astrophysics Data System (ADS)

    Ambrusi, Ruben E.; Luna, C. Romina; Sandoval, Mario G.; Bechthold, Pablo; Pronsato, M. Estela; Juan, Alfredo

    2017-12-01

    The Spin-polarized density functional theory is used to study the effect of a single vacancy in a (8,0) single-walled carbon nanotube (SWCNT) on the Rh clustering process. The vacancy is considered oxygenated and non-oxygenated and, in each case, different Rhn cluster sizes (n = 1-4) are taken into account. For the analysis of these systems some physical and chemical properties are calculated, such as binding energy (Eb), work function (WF), magnetic moment, charge transfer, bond length, band gap (Eg), and density of state (DOS). From this analysis it can be concluded that: a single Rh atom and Rh2 dimer are adsorbed on vacancy without oxygen, whereas Rh3 and Rh4 clusters prefer to be adsorbed on oxygenated vacancy. In all cases, Rh adsorption induces a magnetic moment. When the Rh atom and Rh2 dimer are bonded to the defective SWCNT, it has been found that they show a semiconductor behavior that could be interesting to use in the spintronic area. In the case of Rh3 and Rh4 clusters our results show a metallic behavior suggesting that these systems are good candidates for nanotube contact.

  1. Variation of oxygen content in selected potassium fluorido-oxido-tantalate phases

    NASA Astrophysics Data System (ADS)

    Boča, Miroslav; Moncoĺ, Ján; Netriová, Zuzana; Velič, Dušan; Jerigová, Monika; Nunney, Tim S.; Baily, Christopher J.; Kubíková, Blanka; Šimko, František; Janderka, Pavel

    2011-12-01

    The compound K 3[TaO 4]•K 3[TaF 4O 2] crystallises in a tetragonal system (space group I-4) with cell parameters a = 6.2220(3) Å and c = 8.7625(34) Å, respectively. The crystal structure consists of two anions, [TaO 4] 3- and [TaF 4O 2] 3- and cations K +. The tantalum atoms lie in special positions and serve as centres of both anions, which are substitution disorders. XPS measurements confirmed the existence of different binding energies corresponding to the different bonds of Ta sbnd O and Ta sbnd F. Oxygen is bound more strongly in [TaF 4O 2] 3-. By combination of single crystal analysis, XRD, SIMS and XPS it was suggested that previously reported cubic phase K 3TaOF 6 is in fact K 3TaO 2F 4 and previously reported tetragonal phase K 3TaO 2F 4 is in fact K 3[TaO 4]•K 3[TaF 4O 2].

  2. High diversity of ammonia-oxidizing archaea in permanent and seasonal oxygen-deficient waters of the eastern South Pacific.

    PubMed

    Molina, Verónica; Belmar, Lucy; Ulloa, Osvaldo

    2010-09-01

    The community structure of putative aerobic ammonia-oxidizing archaea (AOA) was explored in two oxygen-deficient ecosystems of the eastern South Pacific: the oxygen minimum zone off Peru and northern Chile (11°S-20°S), where permanent suboxic and low-ammonium conditions are found at intermediate depths, and the continental shelf off central Chile (36°S), where seasonal oxygen-deficient and relatively high-ammonium conditions develop in the water column, particularly during the upwelling season. The AOA community composition based on the ammonia monooxygenase subunit A (amoA) genes changed according to the oxygen concentration in the water column and the ecosystem studied, showing a higher diversity in the seasonal low-oxygen waters. The majority of the archaeal amoA genotypes was affiliated to the uncultured clusters A (64%) and B (35%), with Cluster A AOA being mainly associated with higher oxygen and ammonium concentrations and Cluster B AOA with permanent oxygen- and ammonium-poor waters. Q-PCR assays revealed that AOA are an abundant community (up to 10(5) amoA copies ml(-1) ), while bacterial amoA genes from β proteobacteria were undetected. Our results thus suggest that a diverse uncultured AOA community, for which, therefore, we do not have any physiological information, to date, is an important component of the nitrifying community in oxygen-deficient marine ecosystems, and particularly in rich coastal upwelling ones. © 2010 Society for Applied Microbiology and Blackwell Publishing Ltd.

  3. Cluster reactivity experiments: Employing mass spectrometry to investigate the molecular level details of catalytic oxidation reactions

    PubMed Central

    Johnson, Grant E.; Tyo, Eric C.; Castleman, A. W.

    2008-01-01

    Mass spectrometry is the most widely used tool in the study of the properties and reactivity of clusters in the gas phase. In this article, we demonstrate its use in investigating the molecular-level details of oxidation reactions occurring on the surfaces of heterogeneous catalysts via cluster reactivity experiments. Guided ion beam mass spectrometry (GIB-MS) employing a quadrupole–octopole–quadrupole (Q–O–Q) configuration enables mass-selected cluster ions to be reacted with various chemicals, providing insight into the effect of size, stoichiometry, and ionic charge state on the reactivity of catalyst materials. For positively charged tungsten oxide clusters, it is shown that species having the same stoichiometry as the bulk, WO3+, W2O6+, and W3O9+, exhibit enhanced activity and selectivity for the transfer of a single oxygen atom to propylene (C3H6), suggesting the formation of propylene oxide (C3H6O), an important monomer used, for example, in the industrial production of plastics. Furthermore, the same stoichiometric clusters are demonstrated to be active for the oxidation of CO to CO2, a reaction of significance to environmental pollution abatement. The findings reported herein suggest that the enhanced oxidation reactivity of these stoichiometric clusters may be due to the presence of radical oxygen centers (W–O●) with elongated metal–oxygen bonds. The unique insights gained into bulk-phase oxidation catalysis through the application of mass spectrometry to cluster reactivity experiments are discussed. PMID:18687883

  4. Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

    PubMed

    Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

    2016-12-01

    This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

  5. Plentiful magnetic moments in oxygen deficient SrTiO 3

    DOE PAGES

    Ganesh, Panchapakesan; Lopez-Bezanilla, Alejandro; Littlewood, Peter B.

    2015-10-06

    In this research, correlated band theory is employed to investigate the magnetic and electronic properties of different arrangements of oxygen di- and tri-vacancy clusters in SrTiO 3. Hole and electron doping of oxygen deficient SrTiO 3 yields various degrees of magnetization as a result of the interaction between localized magnetic moments at the defect sites. Different kinds of Ti atomic orbital hybridization are described as a function of the doping level and defect geometry. We find that magnetism in SrTiO 3–δ is sensitive to the arrangement of neighbouring vacancy sites, charge carrier density, and vacancy-vacancy interaction. Permanent magnetic moments inmore » the absence of vacancy doping electrons are observed. Our description of the charged clusters of oxygen vacancies widens the previous descriptions of mono- and multi-vacancies and points out the importance of the controlled formation at the atomic level of defects for the realization of transition metal oxide based devices with a desirable magnetic performance.« less

  6. Atomic Oxygen Durability Evaluation of a UV Curable Ceramer Protective Coating

    NASA Technical Reports Server (NTRS)

    Banks, Bruce A.; Karniotis, Christina A.; Dworak, David; Soucek, Mark

    2004-01-01

    The exposure of most silicones to atomic oxygen in low Earth orbit (LEO) results in the oxidative loss of methyl groups with a gradual conversion to oxides of silicon. Typically there is surface shrinkage of oxidized silicone protective coatings which leads to cracking of the partially oxidized brittle surface. Such cracks widen and branch crack with continued atomic oxygen exposure ultimately allowing atomic oxygen to reach any hydrocarbon polymers under the silicone coating. A need exists for a paintable silicone coating that is free from such surface cracking and can be effectively used for protection of polymers and composites in LEO. A new type of silicone based protective coating holding such potential was evaluated for atomic oxygen durability in an RF atomic oxygen plasma exposure facility. The coating consisted of a UV curable inorganic/organic hybrid coating, known as a ceramer, which was fabricated using a methyl substituted polysiloxane binder and nanophase silicon-oxo-clusters derived from sol-gel precursors. The polysiloxane was functionalized with a cycloaliphatic epoxide in order to be cured at ambient temperature via a cationic UV induced curing mechanism. Alkoxy silane groups were also grafted onto the polysiloxane chain, through hydrosilation, in order to form a network with the incorporated silicon-oxo-clusters. The prepared polymer was characterized by H-1 and Si-29 NMR, FT-IR, and electrospray ionization mass spectroscopy. The paper will present the results of atomic oxygen protection ability of thin ceramer coatings on Kapton H as evaluated over a range of atomic oxygen fluence levels.

  7. Analysis of LAC Observations of Clusters of Galaxies and Supernova Remnants

    NASA Technical Reports Server (NTRS)

    Hughes, J.

    1996-01-01

    The following publications are included and serve as the final report: The X-ray Spectrum of Abell 665; Clusters of Galaxies; Ginga Observation of an Oxygen-rich Supernova Remnant; Ginga Observations of the Coma Cluster and Studies of the Spatial Distribution of Iron; A Measurement of the Hubble Constant from the X-ray Properties and the Sunyaev-Zel'dovich Effect of Abell 2218; Non-polytropic Model for the Coma Cluster; and Abundance Gradients in Cooling Flow Clusters: Ginga LAC (Large Area Counter) and Einstein SSS (Solid State Spectrometer) Spectra of A496, A1795, A2142, and A2199.

  8. Water Oxidation Catalysis via Size-Selected Iridium Clusters

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

    Halder, Avik; Liu, Cong; LIU, ZHUN

    The detailed mechanism and efficacy of four electron electrochemical water oxidation depend critically upon the detailed atomic structure of each catalytic site, which are numerous and diverse in most metal oxides anodes. In order to limit the diversity of sites, arrays of discrete iridium clusters with identical metal atom number (Ir-2, Ir-4, or Ir-8) were deposited in submonolayer coverage on conductive oxide supports, and the electrochemical properties and activity of each was evaluated. Exceptional electroactivity for the oxygen evolving reaction (OER) was observed for all cluster samples in acidic electrolyte. Reproducible cluster-size-dependent trends in redox behavior were also resolved. First-principlesmore » computational models of the individual discrete-size clusters allow correlation of catalytic-site structure and multiplicity with redox behavior.« less

  9. Strain-Rate Dependence of Deformation-Twinning in Tantalum

    NASA Astrophysics Data System (ADS)

    Abeywardhana, Jayalath; Germann, Tim; Ravelo, Ramon

    2017-06-01

    Large-Scale molecular dynamics (MD) simulations are used to model quasi-isentropic compression and expansion (QIC) in tantalum crystals varying the rate of deformation between the range 108 -1012s-1 and compressive pressures up to 100 GPa. The atomic interactions were modeled employing an embedded-atom method (EAM) potential of Ta. Isentropic expansion was done employing samples initially compressed to pressures of 60 and 100 GPa followed by uniaxial and quasi-isentropically expansion to zero pressure. The effect of initial dislocation density on twinning was also examined by varying the initial defect density of the Ta samples (1010 -1012cm-2). At these high-strain rates, a threshold in strain-rate on deformation twining is observed. Under expansion or compression, deformation twinning increases with strain rate for strain-rates >109s-1 . Below this value, small fraction of twins nucleates but anneal out with time. Samples with lower fraction of twins equilibrate to defect states containing higher screw dislocation densities from those with initially higher twinning fractions. This work was supported by the Department of Energy under contract DE-AC52-06NA25396 and by the Air Force Office of Scientific Research under AFOSR Award No. FA9550-12-1-0476.

  10. Phase transformation in tantalum under extreme laser deformation

    DOE PAGES

    Lu, C. -H.; Hahn, E. N.; Remington, B. A.; ...

    2015-10-19

    The structural and mechanical response of metals is intimately connected to phase transformations. For instance, the product of a phase transformation (martensite) is responsible for the extraordinary range of strength and toughness of steel, making it a versatile and important structural material. Although abundant in metals and alloys, the discovery of new phase transformations is not currently a common event and often requires a mix of experimentation, predictive computations, and luck. High-energy pulsed lasers enable the exploration of extreme pressures and temperatures, where such discoveries may lie. The formation of a hexagonal (omega) phase was observed in recovered monocrystalline body-centeredmore » cubic tantalum of four crystallographic orientations subjected to an extreme regime of pressure, temperature, and strain-rate. This was accomplished using high-energy pulsed lasers. The omega phase and twinning were identified by transmission electron microscopy at 70 GPa (determined by a corresponding VISAR experiment). It is proposed that the shear stresses generated by the uniaxial strain state of shock compression play an essential role in the transformation. In conclusion, molecular dynamics simulations show the transformation of small nodules from body-centered cubic to a hexagonal close-packed structure under the same stress state (pressure and shear).« less

  11. Phase Transformation in Tantalum under Extreme Laser Deformation

    PubMed Central

    Lu, C.-H.; Hahn, E. N.; Remington, B. A.; Maddox, B. R.; Bringa, E. M.; Meyers, M. A.

    2015-01-01

    The structural and mechanical response of metals is intimately connected to phase transformations. For instance, the product of a phase transformation (martensite) is responsible for the extraordinary range of strength and toughness of steel, making it a versatile and important structural material. Although abundant in metals and alloys, the discovery of new phase transformations is not currently a common event and often requires a mix of experimentation, predictive computations, and luck. High-energy pulsed lasers enable the exploration of extreme pressures and temperatures, where such discoveries may lie. The formation of a hexagonal (omega) phase was observed in recovered monocrystalline body-centered cubic tantalum of four crystallographic orientations subjected to an extreme regime of pressure, temperature, and strain-rate. This was accomplished using high-energy pulsed lasers. The omega phase and twinning were identified by transmission electron microscopy at 70 GPa (determined by a corresponding VISAR experiment). It is proposed that the shear stresses generated by the uniaxial strain state of shock compression play an essential role in the transformation. Molecular dynamics simulations show the transformation of small nodules from body-centered cubic to a hexagonal close-packed structure under the same stress state (pressure and shear). PMID:26478106

  12. Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

    PubMed

    Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

    2014-06-25

    Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated

  13. Cross-scale MD simulations of dynamic strength of tantalum

    NASA Astrophysics Data System (ADS)

    Bulatov, Vasily

    2017-06-01

    Dislocations are ubiquitous in metals where their motion presents the dominant and often the only mode of plastic response to straining. Over the last 25 years computational prediction of plastic response in metals has relied on Discrete Dislocation Dynamics (DDD) as the most fundamental method to account for collective dynamics of moving dislocations. Here we present first direct atomistic MD simulations of dislocation-mediated plasticity that are sufficiently large and long to compute plasticity response of single crystal tantalum while tracing the underlying dynamics of dislocations in all atomistic details. Where feasible, direct MD simulations sidestep DDD altogether thus reducing uncertainties of strength predictions to those of the interatomic potential. In the specific context of shock-induced material dynamics, the same MD models predict when, under what conditions and how dislocations interact and compete with other fundamental mechanisms of dynamic response, e.g. twinning, phase-transformations, fracture. In collaboration with: Luis Zepeda-Ruiz, Lawrence Livermore National Laboratory; Alexander Stukowski, Technische Universitat Darmstadt; Tomas Oppelstrup, Lawrence Livermore National Laboratory. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

  14. Reactive Pendant Mn═O in a Synthetic Structural Model of a Proposed S4 State in the Photosynthetic Oxygen Evolving Complex.

    PubMed

    Vaddypally, Shivaiah; Kondaveeti, Sandeep K; Karki, Santosh; Van Vliet, Megan M; Levis, Robert J; Zdilla, Michael J

    2017-04-05

    The molecular mechanism of the Oxygen Evolving Center of photosystem II has been under debate for decades. One frequently cited proposal is the nucleophilic attack by water hydroxide on a pendant Mn═O moiety, though no chemical example of this reactivity at a manganese cubane cluster has been reported. We describe here the preparation, characterization, and a reactivity study of a synthetic manganese cubane cluster with a pendant manganese-oxo moiety. Reaction of this cluster with alkenes results in oxygen and hydrogen atom transfer reactions to form alcohol- and ketone-based oxygen-containing products. Nitrene transfer from core imides is negligible. The inorganic product is a cluster identical to the precursor, but with the pendant Mn═O moiety replaced by a hydrogen abstracted from the organic substrate, and is isolated in quantitative yield. 18 O and 2 H isotopic labeling studies confirm the transfer of atoms between the cluster and the organic substrate. The results suggest that the core cubane structure of this model compound remains intact, and that the pendant Mn═O moiety is preferentially reactive.

  15. Analytical fingerprint for tantalum ores from African deposits

    NASA Astrophysics Data System (ADS)

    Melcher, F.; Graupner, T.; Sitnikova, M.; Oberthür, T.; Henjes-Kunst, F.; Gäbler, E.; Rantitsch, G.

    2009-04-01

    Illegal mining of gold, diamonds, copper, cobalt and, in the last decade, "coltan" has fuelled ongoing armed conflicts and civil war in a number of African countries. Following the United Nations initiative to fingerprint the origin of conflict materials and to develop a traceability system, our working group is investigating "coltan" (i.e. columbite-tantalite) mineralization especially in Africa, also within the wider framework of establishing certified trading chains (CTC). Special attention is directed towards samples from the main Ta-Nb-Sn provinces in Africa: DR Congo, Rwanda, Mozambique, Ethiopia, Egypt and Namibia. The following factors are taken into consideration in a methodological approach capable of distinguishing the origin of tantalum ores and concentrates with the utmost probability: (1) Quality and composition of coltan concentrates vary considerably. (2) Mineralogical and chemical compositions of Ta-Nb ores are extremely complex due to the wide range of the columbite-tantalite solid solution series and its ability to incorporate many additional elements. (3) Coltan concentrates may contain a number of other tantalum-bearing minerals besides columbite-tantalite. In our approach, coltan concentrates are analyzed in a step-by-step mode. State-of-the-art analytical tools employed are automated scanning electron microscopy (Mineral Liberation Analysis; MLA), electron microprobe analysis (major and trace elements), laser ablation-ICP-MS (trace elements, isotopes), and TIMS (U-Pb dating). Mineral assemblages in the ore concentrates, major and trace element concentration patterns, and zoning characteristics in the different pegmatites from Africa distinctly differ from each other. Chondrite-normalized REE distribution patterns vary significantly between columbite, tantalite, and microlite, and also relative to major element compositions of columbites. Some locations are characterized by low REE concentrations, others are highly enriched. Samples with

  16. Influence of tantalum underlayer on magnetization dynamics in Ni{sub 81}Fe{sub 19} films

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

    Kwon, Jae Hyun; Deorani, Praveen; Yoon, Jungbum

    2015-07-13

    The effect of tantalum (Ta) underlayer is investigated in Ni{sub 81}Fe{sub 19} thin films for magnetization dynamics. The damping parameters extracted from spin wave measurements increase systematically with increasing Ta thickness, whereas the damping parameters from ferromagnetic resonance measurements are found to be weakly dependent on the Ta thickness. The difference is attributed to propagating properties of spin wave and short spin diffusion length in Ta. The group velocity of spin waves is found to be constant for different Ta thicknesses, and nonreciprocity of spin waves is not affected by the Ta thickness. The experimental observations are supported by micromagneticmore » simulations.« less

  17. Study the effect of nitrogen flow rate on tribological properties of tantalum nitride based coatings

    NASA Astrophysics Data System (ADS)

    Chauhan, Dharmesh B.; Chauhan, Kamlesh V.; Sonera, Akshay L.; Makwana, Nishant S.; Dave, Divyeshkumar P.; Rawal, Sushant K.

    2018-05-01

    Tantalum Nitride (TaN) based coatings are well-known for their high temperature stability and chemical inertness. We have studied the effect of nitrogen flow rate variation on the structural and tribological properties of TaN based coating deposited by RF magnetron sputtering process. The nitrogen flow rate was varied from 5 to 30 sccm. X-ray diffractometer (XRD) and Atomic Force Microscopy (AFM) were used to determine structure and surface topography of coating. Pin on disc tribometer was used to determine tribological properties of coating. TaN coated brass and mild steel substrates shows higher wear resistance compared to uncoated substrates of brass and mild steel.

  18. Neutron displacement cross-sections for tantalum and tungsten at energies up to 1 GeV

    NASA Astrophysics Data System (ADS)

    Broeders, C. H. M.; Konobeyev, A. Yu.; Villagrasa, C.

    2005-06-01

    The neutron displacement cross-section has been evaluated for tantalum and tungsten at energies from 10 -5 eV up to 1 GeV. The nuclear optical model, the intranuclear cascade model combined with the pre-equilibrium and evaporation models were used for the calculations. The number of defects produced by recoil atoms nuclei in materials was calculated by the Norgett, Robinson, Torrens model and by the approach combining calculations using the binary collision approximation model and the results of the molecular dynamics simulation. The numerical calculations were done using the NJOY code, the ECIS96 code, the MCNPX code and the IOTA code.

  19. Strength of shock-loaded single-crystal tantalum [100] determined using in situ broadband x-ray Laue diffraction.

    PubMed

    Comley, A J; Maddox, B R; Rudd, R E; Prisbrey, S T; Hawreliak, J A; Orlikowski, D A; Peterson, S C; Satcher, J H; Elsholz, A J; Park, H-S; Remington, B A; Bazin, N; Foster, J M; Graham, P; Park, N; Rosen, P A; Rothman, S R; Higginbotham, A; Suggit, M; Wark, J S

    2013-03-15

    The strength of shock-loaded single crystal tantalum [100] has been experimentally determined using in situ broadband x-ray Laue diffraction to measure the strain state of the compressed crystal, and elastic constants calculated from first principles. The inferred strength reaches 35 GPa at a shock pressure of 181 GPa and is in excellent agreement with a multiscale strength model [N. R. Barton et al., J. Appl. Phys. 109, 073501 (2011)], which employs a hierarchy of simulation methods over a range of length scales to calculate strength from first principles.

  20. Effect of polarity of electric current on friction behavior of two gallium-lubricated tantalum slipring assemblies

    NASA Technical Reports Server (NTRS)

    Przybyszewski, J.

    1972-01-01

    Computer-processed data from low-speed (10 rpm) slipring experiments with two similar (but of opposite polarity) gallium-lubricated tantalum slipring assemblies (hemisphere against disk) carrying 50 amperes dc in vacuum (10 to the minus 9th power torr) showed that the slipring assembly with the anodic hemisphere had significantly lower peak-to-peak values and standard deviations of coefficient-of-friction samples (a measure of smoothness of operation) than the slipring assembly with the cathodic hemisphere. Similar data from an experiment with the same slipring assemblies running currentless showed more random differences in the frictional behavior between the two assemblies.

  1. Carbon, oxygen and intrinsic defect interactions in germanium-doped silicon

    NASA Astrophysics Data System (ADS)

    Londos, C. A.; Sgourou, E. N.; Chroneos, A.; Emtsev, V. V.

    2011-10-01

    Production and annealing of oxygen-vacancy (VO) and oxygen-carbon (CiOi, CiOiI) defects in germanium-doped Czochralski-grown silicon (Cz-Si) containing carbon are investigated. All the samples were irradiated with 2 MeV fast electrons. Radiation-produced defects are studied using infrared spectroscopy by monitoring the relevant bands in optical spectra. For the VO defects, it is established that the doping with Ge affects the thermal stability of VO (830 cm-1) defects as well as their fraction converted to VO2 (888 cm-1) defects. In Ge-free samples containing carbon, it was found that carbon impurity atoms do not affect the thermal stability of VO defects, although they affect the fraction of VO defects that is converted to VO2 complexes. Considering the oxygen-carbon complexes, it is established that the annealing of the 862 cm-1 band associated with the CiOi defects is accompanied with the emergence of the 1048 cm-1 band, which has earlier been assigned to the CsO2i center. The evolution of the CiOiI bands is also traced. Ge doping does not seem to affect the thermal stability of the CiOi and CiOiI defects. Density functional theory (DFT) calculations provide insights into the stability of the defect clusters (VO, CiOi, CiOiI) at an atomic level. Both experimental and theoretical results are consistent with the viewpoint that Ge affects the stability of the VO but does not influence the stability of the oxygen-carbon clusters. DFT calculations demonstrate that C attracts both Oi and VO pairs predominately forming next nearest neighbor clusters in contrast to Ge where the interactions with Oi and VO are more energetically favorable at nearest neighbor configurations.

  2. Computational Investigation of Amine–Oxygen Exciplex Formation

    PubMed Central

    Haupert, Levi M.; Simpson, Garth J.; Slipchenko, Lyudmila V.

    2012-01-01

    It has been suggested that fluorescence from amine-containing dendrimer compounds could be the result of a charge transfer between amine groups and molecular oxygen [Chu, C.-C.; Imae, T. Macromol. Rapid Commun. 2009, 30, 89.]. In this paper we employ equation-of-motion coupled cluster computational methods to study the electronic structure of an ammonia–oxygen model complex to examine this possibility. The results reveal several bound electronic states with charge transfer character with emission energies generally consistent with previous observations. However, further work involving confinement, solvent, and amine structure effects will be necessary for more rigorous examination of the charge transfer fluorescence hypothesis. PMID:21812447

  3. Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

    PubMed

    Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

    2014-10-21

    Iron-sulfur cluster proteins exhibit a range of physicochemical properties that underpin their functional diversity in biology, which includes roles in electron transfer, catalysis, and gene regulation. Transcriptional regulators that utilize iron-sulfur clusters are a growing group that exploit the redox and coordination properties of the clusters to act as sensors of environmental conditions including O2, oxidative and nitrosative stress, and metabolic nutritional status. To understand the mechanism by which a cluster detects such analytes and then generates modulation of DNA-binding affinity, we have undertaken a combined strategy of in vivo and in vitro studies of a range of regulators. In vitro studies of iron-sulfur cluster proteins are particularly challenging because of the inherent reactivity and fragility of the cluster, often necessitating strict anaerobic conditions for all manipulations. Nevertheless, and as discussed in this Account, significant progress has been made over the past decade in studies of O2-sensing by the fumarate and nitrate reduction (FNR) regulator and, more recently, nitric oxide (NO)-sensing by WhiB-like (Wbl) and FNR proteins. Escherichia coli FNR binds a [4Fe-4S] cluster under anaerobic conditions leading to a DNA-binding dimeric form. Exposure to O2 converts the cluster to a [2Fe-2S] form, leading to protein monomerization and hence loss of DNA binding ability. Spectroscopic and kinetic studies have shown that the conversion proceeds via at least two steps and involves a [3Fe-4S](1+) intermediate. The second step involves the release of two bridging sulfide ions from the cluster that, unusually, are not released into solution but rather undergo oxidation to sulfane (S(0)) subsequently forming cysteine persulfides that then coordinate the [2Fe-2S] cluster. Studies of other [4Fe-4S] cluster proteins that undergo oxidative cluster conversion indicate that persulfide formation and coordination may be more common than previously

  4. Application of a Multiscale Model of Tantalum Deformation at Megabar Pressures

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

    Cavallo, R M; Park, H; Barton, N R

    A new multiscale simulation tool has been developed to model the strength of tantalum under high-pressure dynamic compression. This new model combines simulations at multiple length scales to explain macroscopic properties of materials. Previously known continuum models of material response under load have built upon a mixture of theoretical physics and experimental phenomenology. Experimental data, typically measured at static pressures, are used as a means of calibration to construct models that parameterize the material properties; e.g., yield stress, work hardening, strain-rate dependence, etc. The pressure dependence for most models enters through the shear modulus, which is used to scale themore » flow stress. When these models are applied to data taken far outside the calibrated regions of phase space (e.g., strain rate or pressure) they often diverge in their predicted behavior of material deformation. The new multiscale model, developed at Lawrence Livermore National Laboratory, starts with interatomic quantum mechanical potential and is based on the motion and multiplication of dislocations. The basis for the macroscale model is plastic deformation by phonon drag and thermally activated dislocation motion and strain hardening resulting from elastic interactions among dislocations. The dislocation density, {rho}, and dislocation velocity, {nu}, are connected to the plastic strain rate {var_epsilon}{sup p}, via Orowan's equation: {var_epsilon}{sup p} = {rho}b{nu}/M, where b is the Burger's vector, the shear magnitude associated with a dislocation, and M is the Taylor factor, which accounts for geometric effects in how slip systems accommodate the deformation. The evolution of the dislocation density and velocity is carried out in the continuum model by parameterized fits to smaller scale simulations, each informed by calculations on smaller length scales down to atomistic dimensions. We apply this new model for tantalum to two sets of experiments and

  5. Corrosion of oxide dispersion strengthened iron-chromium steels and tantalum in fluoride salt coolant: An in situ compatibility study for fusion and fusion-fission hybrid reactor concepts

    NASA Astrophysics Data System (ADS)

    El-Dasher, Bassem; Farmer, Joseph; Ferreira, James; de Caro, Magdalena Serrano; Rubenchik, Alexander; Kimura, Akihiko

    2011-12-01

    Primary candidate classes of materials for future nuclear power plants, whether they be fission, fusion or hybrids, include oxide dispersion strengthened (ODS) ferritic steels which rely on a dispersion of nano-oxide particles in the matrix for both mechanical strength and swelling resistance, or tantalum alloys which have an inherent neutron-induced swelling resistance and high temperature strength. For high temperature operation, eutectic molten lithium containing fluoride salts are attractive because of their breeding capability as well as their relatively high thermal capacity, which allow for a higher average operating temperature that increases power production. In this paper we test the compatibility of Flinak (LiF-NaF-KF) salts on ODS steels, comparing the performance of current generation ODS steels developed at Kyoto University with the commercial alloy MA956. Pure tantalum was also tested for comparative purposes. In situ data was obtained for temperatures ranging from 600 to 900 °C using a custom-built high temperature electrochemical impedance spectroscopy cell. Results for ODS steels show that steel/coolant interfacial resistance increases from 600 to 800 °C due to an aluminum enriched layer forming at the surface, however an increase in temperature to 900 °C causes this layer to break up and aggressive attack to occur. Performance of current generation ODS steels surpassed that of the MA956 ODS steel, with an in situ impedance behavior similar or better than that of pure tantalum.

  6. Triptans for acute cluster headache

    PubMed Central

    Law, Simon; Derry, Sheena; Moore, R Andrew

    2014-01-01

    Background Cluster headache is an uncommon, but severely painful and disabling condition, with rapid onset. Validated treatment options are limited, and first-line therapy includes inhaled oxygen. Alternative therapies such as intranasal lignocaine and ergotamine are not as commonly used and are less well studied. Triptans are successfully used to treat migraine attacks and, because of this, they may also be useful for cluster headache. Objectives To determine the efficacy and tolerability of triptans for the acute treatment of cluster headaches. Search methods We searched Cochrane CENTRAL, MEDLINE and EMBASE for studies through 22 January 2010. Selection criteria Randomised, double-blind, placebo-controlled studies of triptans for acute treatment of cluster headache episodes. Data collection and analysis Two review authors independently assessed study quality and extracted data. Numbers of participants with different levels of pain relief, requiring rescue medication and experiencing adverse events and headache-associated symptoms in treatment and control groups were used to calculate relative risk and numbers needed to treat (NNT) and harm (NNH). Main results All six included studies used a single dose of triptan to treat an attack of moderate to severe pain intensity. In total 231 participants received zolmitriptan 5 mg, 223 received zolmitriptan 10 mg, 131 received sumatriptan 6 mg, 88 received sumatriptan 12 mg, and 326 received placebo. Zolmitriptan was administered either orally or intranasally, and sumatriptan either subcutaneously or intranasally. Overall, the triptans studied were better than placebo for headache relief and pain-free responses, with an NNT of 2.4 for 15 minute pain relief with subcutaneous sumatriptan 6 mg (75% with sumatriptan and 32% with placebo), and 2.8 for 30 minute pain relief with intranasal zolmitriptan 10 mg (62% with zolmitriptan and 26% with placebo). Fewer participants need rescue medication with triptan than with placebo

  7. Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction

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

    Cervantes, O; Kuntz, J; Gash, A

    2010-02-25

    The activation energy of a high melting temperature sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the High Pressure Spark Plasma Sintering (HPSPS) technique to 300 and 400 C to produce pellets with dimensions of 5 mm diameter by 1.5 mm height. A custom built ignition setup was developed to measure ignition temperatures at high heating rates (500-2000 C {center_dot} min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Unlike the 400 C samples, results show that the samples consolidated to 300more » C undergo an abrupt change in temperature response prior to ignition. This change in temperature response has been attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465-670 C. The activation energy of the SG derived Ta-WO{sup 3} thermite composite consolidated to 300 and 400 C were determined to be 37.787 {+-} 1.58 kJ {center_dot} mol{sup -1} and 57.381 {+-} 2.26 kJ {center_dot} mol{sup -1}, respectively.« less

  8. Reactions of sulfur dioxide with neutral vanadium oxide clusters in the gas phase. I. Density functional theory study.

    PubMed

    Jakubikova, Elena; Bernstein, Elliot R

    2007-12-27

    Thermodynamics of reactions of vanadium oxide clusters with SO2 are studied at the BPW91/LANL2DZ level of theory. BPW91/LANL2DZ is insufficient to properly describe relative V-O and S-O bond strengths of vanadium and sulfur oxides. Calibration of theoretical results with experimental data is necessary to compute reliable enthalpy changes for reactions between VxOy and SO2. Theoretical results indicate SO2 to SO conversion occurs for oxygen-deficient clusters and SO2 to SO3 conversion occurs for oxygen-rich clusters. Stable intermediate structures of VOy (y = 1 - 4) clusters with SO2 are also obtained at the BPW91/TZVP level of theory. Some possible mechanisms for SO3 formation and catalyst regeneration for condensed-phase systems are suggested. These results are in agreement with, and complement, gas-phase experimental studies of neutral vanadium oxide clusters.

  9. Copper drift in high-dielectric-constant tantalum oxide thin films under bias temperature stress

    NASA Astrophysics Data System (ADS)

    Jain, Pushkar; Juneja, Jasbir S.; Mallikarjunan, A.; Rymaszewski, E. J.; Lu, T.-M.

    2006-04-01

    The use of high-dielectric-constant (high-κ) materials for embedded capacitors is becoming increasingly important. Tantalum oxide (Ta2O5) is a prominent candidate as a high-κ material for embedded capacitor use. Metal drift in Ta2O5 (κ˜25) was investigated by bias temperature stress and triangular voltage sweep testing techniques on metal/Ta2O5/SiO2/Si structures. At a temperature of 300°C and 0.75MV/cm bias conditions, Al, Ta, and Ti do not diffuse in Ta2O5, but Cu clearly showed a drift. The Cu drift is attributed to the lack of a stable Cu oxide which can limit Cu ion generation and penetration.

  10. Evolution of Fe/S cluster biogenesis in the anaerobic parasite Blastocystis

    PubMed Central

    Tsaousis, Anastasios D.; Ollagnier de Choudens, Sandrine; Gentekaki, Eleni; Long, Shaojun; Gaston, Daniel; Stechmann, Alexandra; Vinella, Daniel; Py, Béatrice; Fontecave, Marc; Barras, Frédéric; Lukeš, Julius; Roger, Andrew J.

    2012-01-01

    Iron/sulfur cluster (ISC)-containing proteins are essential components of cells. In most eukaryotes, Fe/S clusters are synthesized by the mitochondrial ISC machinery, the cytosolic iron/sulfur assembly system, and, in photosynthetic species, a plastid sulfur-mobilization (SUF) system. Here we show that the anaerobic human protozoan parasite Blastocystis, in addition to possessing ISC and iron/sulfur assembly systems, expresses a fused version of the SufC and SufB proteins of prokaryotes that it has acquired by lateral transfer from an archaeon related to the Methanomicrobiales, an important lineage represented in the human gastrointestinal tract microbiome. Although components of the Blastocystis ISC system function within its anaerobic mitochondrion-related organelles and can functionally replace homologues in Trypanosoma brucei, its SufCB protein has similar biochemical properties to its prokaryotic homologues, functions within the parasite’s cytosol, and is up-regulated under oxygen stress. Blastocystis is unique among eukaryotic pathogens in having adapted to its parasitic lifestyle by acquiring a SUF system from nonpathogenic Archaea to synthesize Fe/S clusters under oxygen stress. PMID:22699510

  11. Exploring the effect of oxygen-containing functional groups on the water-holding capacity of lignite.

    PubMed

    Liu, Jie; Jiang, Xiangang; Cao, Yu; Zhang, Chen; Zhao, Guangyao; Zhao, Maoshuang; Feng, Li

    2018-05-07

    Graphene oxide with different degrees of oxidation was prepared and selected as a model compound of lignite to study quantitatively, using both experiment and theoretical calculation methods, the effect on water-holding capacity of oxygen-containing functional groups. The experimental results showed that graphite can be oxidized, and forms epoxy groups most easily, followed by hydroxyl and carboxyl groups. The prepared graphene oxide forms a membrane-state as a single layer structure, with an irregular surface. The water-holding capacity of lignite increased with the content of oxygen-containing functional groups. The influence on the configuration of water molecule clusters and binding energy of water molecules of different oxygen-containing functional groups was calculated by density functional theory. The calculation results indicated that the configuration of water molecule clusters was totally changed by oxygen-containing functional groups. The order of binding energy produced by oxygen-containing functional groups and water molecules was as follows: carboxyl > edge phenol hydroxyl >epoxy group. Finally, it can be concluded that the potential to form more hydrogen bonds is the key factor influencing the interaction energy between model compounds and water molecules.

  12. Investigation of the cluster formation in lithium niobate crystals by computer modeling method

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

    Voskresenskii, V. M.; Starodub, O. R., E-mail: ol-star@mail.ru; Sidorov, N. V.

    The processes occurring upon the formation of energetically equilibrium oxygen-octahedral clusters in the ferroelectric phase of a stoichiometric lithium niobate (LiNbO{sub 3}) crystal have been investigated by the computer modeling method within the semiclassical atomistic model. An energetically favorable cluster size (at which a structure similar to that of a congruent crystal is organized) is shown to exist. A stoichiometric cluster cannot exist because of the electroneutrality loss. The most energetically favorable cluster is that with a Li/Nb ratio of about 0.945, a value close to the lithium-to-niobium ratio for a congruent crystal.

  13. Simulations of X-ray diffraction of shock-compressed single-crystal tantalum with synchrotron undulator sources.

    PubMed

    Tang, M X; Zhang, Y Y; E, J C; Luo, S N

    2018-05-01

    Polychromatic synchrotron undulator X-ray sources are useful for ultrafast single-crystal diffraction under shock compression. Here, simulations of X-ray diffraction of shock-compressed single-crystal tantalum with realistic undulator sources are reported, based on large-scale molecular dynamics simulations. Purely elastic deformation, elastic-plastic two-wave structure, and severe plastic deformation under different impact velocities are explored, as well as an edge release case. Transmission-mode diffraction simulations consider crystallographic orientation, loading direction, incident beam direction, X-ray spectrum bandwidth and realistic detector size. Diffraction patterns and reciprocal space nodes are obtained from atomic configurations for different loading (elastic and plastic) and detection conditions, and interpretation of the diffraction patterns is discussed.

  14. Cluster-cluster clustering

    NASA Technical Reports Server (NTRS)

    Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C. S.

    1985-01-01

    The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales.

  15. Investigation of the refractive index repeatability for tantalum pentoxide coatings, prepared by physical vapor film deposition techniques.

    PubMed

    Stenzel, O; Wilbrandt, S; Wolf, J; Schürmann, M; Kaiser, N; Ristau, D; Ehlers, H; Carstens, F; Schippel, S; Mechold, L; Rauhut, R; Kennedy, M; Bischoff, M; Nowitzki, T; Zöller, A; Hagedorn, H; Reus, H; Hegemann, T; Starke, K; Harhausen, J; Foest, R; Schumacher, J

    2017-02-01

    Random effects in the repeatability of refractive index and absorption edge position of tantalum pentoxide layers prepared by plasma-ion-assisted electron-beam evaporation, ion beam sputtering, and magnetron sputtering are investigated and quantified. Standard deviations in refractive index between 4*10-4 and 4*10-3 have been obtained. Here, lowest standard deviations in refractive index close to our detection threshold could be achieved by both ion beam sputtering and plasma-ion-assisted deposition. In relation to the corresponding mean values, the standard deviations in band-edge position and refractive index are of similar order.

  16. Identification of vacancy-oxygen complexes in oxygen-implanted silicon probed with slow positrons

    NASA Astrophysics Data System (ADS)

    Fujinami, M.; Miyagoe, T.; Sawada, T.; Suzuki, R.; Ohdaira, T.; Akahane, T.

    2004-04-01

    Defects and their annealing behavior for low (2×1015/cm2) and high (1.7×1018/cm2) doses of 180 keV oxygen-implanted silicon have been investigated by the coincidence Doppler broadening (CDB) and lifetime measurements in variable-energy positron annihilation spectroscopy. In the low-dose sample, divacancies are induced throughout the entire implantation region. In the vacancy-oxygen coexisting region (300-500 nm depths), by raising the annealing temperature to 600 °C, vacancy-oxygen VxOy complexes with one vacant site are formed and, simultaneously, the migration of oxygen begins to takes place. In the vacancy-rich region (-200 nm depths), the evolution of simple vacancy clusters to V4 is mainly observed below 600 °C. From CDB and lifetime measurements, it has been proven that after annealing at 800 °C, the VxOy complexes are formed throughout the implanted region and they contain four vacant sites and a high ratio of y to x. On the other hand, high-dose implantation at 550 °C produces the VxOy complexes with a lifetime of a 430 ps in the near-surface region (less than 200 nm deep) and annealing at 1100 °C leads to the highest ratio of y to x. These complexes cannot be annealed out even by annealing at 1350 °C, and their structure is found to be very similar to that for the electron-irradiated amorphous SiO2.

  17. Incipient plasticity of single-crystal tantalum as a function of temperature and orientation

    DOE PAGES

    Franke, O.; Alcalá, J.; Dalmau, R.; ...

    2014-08-28

    The nanocontact plastic behavior of single-crystalline Ta (1 0 0), Ta (1 1 0) and Ta (1 1 1) was studied as a function of temperature and indentation rate. Tantalum, a representative body centred cubic (BCC) metal, reveals a unique deformation behavior dominated by twinning and the generation of stacking faults. Experiments performed at room temperature exhibit a single pop-in event, while at 200 °C, above the critical temperature, a transition to multiple pop-ins was observed. The experimental results are discussed with respect to the orientation as well as temperature and correlated to the defect structures using both anisotropic finitemore » element and MD simulations. In addition, the serrated flow observed at 200 °C is related to differences in the quasi-elastic reloading originating from changes in the defect mechanism.« less

  18. A multiscale strength model for tantalum over an extended range of strain rates

    NASA Astrophysics Data System (ADS)

    Barton, N. R.; Rhee, M.

    2013-09-01

    A strength model for tantalum is developed and exercised across a range of conditions relevant to various types of experimental observations. The model is based on previous multiscale modeling work combined with experimental observations. As such, the model's parameterization includes a hybrid of quantities that arise directly from predictive sub-scale physics models and quantities that are adjusted to align the model with experimental observations. Given current computing and experimental limitations, the response regions for sub-scale physics simulations and detailed experimental observations have been largely disjoint. In formulating the new model and presenting results here, attention is paid to integrated experimental observations that probe strength response at the elevated strain rates where a previous version of the model has generally been successful in predicting experimental data [Barton et al., J. Appl. Phys. 109(7), 073501 (2011)].

  19. Development of a fused slurry silicide coating for the protection of tantalum alloys

    NASA Technical Reports Server (NTRS)

    Packer, C. M.; Perkins, R. A.

    1974-01-01

    Results are reported of a research program to develop a reliable high-performance, fused slurry silicide protective coating for a tantalum-10 tungsten alloy for use at 1427 to 1538 C at 0.1 to 10 torr air pressure under cyclic temperature conditions. A review of silicide coating performance under these conditions indicated that the primary wear-out mode is associated with widening of hairline fissures in the coating. Consideration has been given to modifying the oxidation products that form on the coating surface to provide a seal for these fissures and to minimize their widening. On the basis of an analysis of the phase relationships between silica and various other oxides, a coating having the slurry composition 2.5Mn-33Ti-64.5Si was developed that is effective in the pressure range from 1 to 10 torr.

  20. Biological nitrogen fixation in the oxygen-minimum region of the eastern tropical North Pacific ocean.

    PubMed

    Jayakumar, Amal; Chang, Bonnie X; Widner, Brittany; Bernhardt, Peter; Mulholland, Margaret R; Ward, Bess B

    2017-10-01

    Biological nitrogen fixation (BNF) was investigated above and within the oxygen-depleted waters of the oxygen-minimum zone of the Eastern Tropical North Pacific Ocean. BNF rates were estimated using an isotope tracer method that overcame the uncertainty of the conventional bubble method by directly measuring the tracer enrichment during the incubations. Highest rates of BNF (~4 nM day -1 ) occurred in coastal surface waters and lowest detectable rates (~0.2 nM day -1 ) were found in the anoxic region of offshore stations. BNF was not detectable in most samples from oxygen-depleted waters. The composition of the N 2 -fixing assemblage was investigated by sequencing of nifH genes. The diazotrophic assemblage in surface waters contained mainly Proteobacterial sequences (Cluster I nifH), while both Proteobacterial sequences and sequences with high identities to those of anaerobic microbes characterized as Clusters III and IV type nifH sequences were found in the anoxic waters. Our results indicate modest input of N through BNF in oxygen-depleted zones mainly due to the activity of proteobacterial diazotrophs.

  1. Oxygen abundances in halo giants. I - Giants in the very metal-poor globular clusters M92 and M15 and the metal-poor halo field

    NASA Astrophysics Data System (ADS)

    Sneden, Christopher; Kraft, Robert P.; Prosser, Charles F.; Langer, G. E.

    1991-12-01

    Oxygen, iron, vanadium, and scandium abundances are derived for very metal-poor giants in the globular clusters M92 and M15, and giants of comparable metallicity in the local halo field. The forbidden O I line dublet (6300, 6363) and nearby metallic lines in spectra are analyzed using line analysis and spectral synthesis codes. The Fe/H abundance for M92 is estimated at -2.25 +/-0.02 based on nine giants with a range of 500 K in effective temperature. No evidence for star-to-star variations in the Fe/H abundance was found. O-rich and O-poor stars appear intermixed in the H-R diagram. O - N nuclear synthesis and mixing to the surface are proposed as the best explanation for the low-oxygen giants. The nitrogen abundances obtained earlier for nine of the ten halo field giants in this sample are incompatible with the very large nitrogen abundances expected of the O/Fe abundance of about + 1.2 in halo field subdwarfs, as found by Abia and Rebolo (1989), and not more than 0.6 in halo giants, as found in this and other studies.

  2. Formation, Fragmentation, and Structures of YxOy(+) (x = 1, 2, y = 1 - 13) Clusters: Collision-Induced Dissociation Experiments and Density Functional Theory Calculations.

    PubMed

    Glodić, Pavle; Mihesan, Claudia; Klontzas, Emmanouel; Velegrakis, Michalis

    2016-02-25

    Yttrium oxide cluster cations have been experimentally and theoretically studied. We produced small, oxygen-rich yttrium oxide clusters, YxOy+ (x = 1, 2, y = 1–13), by mixing the laser-produced yttrium plasma with a molecular oxygen jet. Mass spectrometry measurements showed that the most stable clusters are those consisting of one yttrium and an odd number of oxygen atoms of the form YO(+)(2k+1) (k = 0–6). Additionally, we performed collision induced dissociation experiments, which indicated that the loss of pairs of oxygen atoms down to a YO+ core is the preferred fragmentation channel for all clusters investigated. Furthermore, we conduct DFT calculations and we obtained two types of low-energy structures: one containing an yttrium cation core and the other composed of YO+ core and O2 ligands, being in agreement with the observed fragmentation pattern. Finally, from the fragmentation studies, total collision cross sections are obtained and these are compared with geometrical cross sections of the calculated structures.

  3. Characteristics and production of tantalum powders for solid-electrolyte capacitors

    NASA Astrophysics Data System (ADS)

    Yoon, Jae Sik; Kim, Byung Il

    The effects of using K 2TaF 7 as the raw material and sodium as the reducing agent on the characteristics of tantalum powder are investigated. Batch-type metallothermic reduction (BTMR) is used to charge the reactor with the raw material and the reducing agent, and external continuous supply metallothermic reduction (ESMR) is used to supply the raw material and the reducing agent at a constant rate at the temperature of the reduction reaction. In the case of ESMR, the yield increases by several tens of percent because of the uniform reaction between the raw material and the reducing agent. It is possible to obtain a powder of over 99.5% purity. The powder particles obtained with BTMR are relatively large (4-6 μm) and have a coarse lamellar shape, while those prepared via ESMR are of uniform 1-2 μm size with a coral-like shape. Measurements of the electric properties show that the leakage current and the dielectric dissipation are low with higher reliability in ESMR than in BTMR, and the capacitance is 26,000 and 8400 CV for ESMR and in BTMR, respectively.

  4. Equation of State and Viscosity of Tantalum and Iron from First Principles

    NASA Astrophysics Data System (ADS)

    Miljacic, Ljubomir; Demers, Steven; van de Walle, Axel

    2011-03-01

    To understand and model at continuum level the high-energy-density dynamic response in transition metals like Tantalum and Iron, as it arises in hypervelocity impact experiments, an accurate prediction of the underlying thermodynamic and kinetic properties for a range of temperatures and pressures is of critical importance. The relevant time scale of atomic motion in a dense gas, liquid, and solid is accessible with ab-initio Molecular Dynamics (MD) simulations. We calculate EoS for Ta and Fe via Thermodynamical Integration in 2D (V,T) phase space throughout different single and two-component phases. To reduce the ab-initio demand in selected regions of the space, we fit available gas-liquid data to the Peng-Robinson model and treat the solid phase within the Boxed-quasi-harmonic approximation. In the fluid part of the 2D phase space, we calculate shear viscosity via Green-Kubo relations, as time integration of the stress autocorrelation function.

  5. Performance of Surface-Mount Ceramic and Solid Tantalum Capacitors for Cryogenic Applications

    NASA Technical Reports Server (NTRS)

    Patterson, Richard L.; MacDonald, Thomas L.; Hammoud, Ahmad; Gerber, Scott

    1998-01-01

    Low temperature electronics are of great interest for space exploration programs. These include missions to the outer planets, earth-orbiting and deep-space probes, remote-sensing and communication satellites. Terrestrial applications would also benefit from the availability of low temperature electronics. Power components capable of low temperature operation would, thus, enhance the technologies needed for the development of advanced power systems suitable for use in harsh environments. In this work, ceramic and solid tantalum capacitors were evaluated in terms of their dielectric properties as a function of temperature and at various frequencies. The surface-mount devices were characterized in terms of their capacitance stability and dissipation factor in the frequency range of 50 Hz to 100 kHz at temperatures ranging from room temperature (20 deg. C) to about liquid nitrogen temperature (-190 deg. C). The results are discussed and conclusions made concerning the suitability of the capacitors investigated for low temperature applications.

  6. Modulation of strain, resistance, and capacitance of tantalum oxide film by converse piezoelectric effect

    NASA Astrophysics Data System (ADS)

    Jia, Yanmin; Tian, Xiangling; Si, Jianxiao; Huang, Shihua; Wu, Zheng; Zhu, Chenchen

    2011-07-01

    We deposited tantalum oxide film on a laminate structure composed of a Si substrate and a piezoelectric 0.72Pb(Mg1/3Nb2/3)O3-0.28PbTiO3 single crystal and achieved in situ modulation of the resistance and capacitance of the Ta2O5 film. The modulation arises from the induced lattice strain in the Ta2O5 film, which is induced by the electric-field-induced strain in the piezoelectric crystal. Under an external electric field of ˜2 kV/cm, the longitudinal gauge factor of the Ta2O5 film is ˜3300. The control of the strain using the converse piezoelectric effect may be further extended to tune the intrinsic strain of other oxide thin films.

  7. A study of tantalum pentoxide Ta 2O 5 structures up to 28 GPa

    DOE PAGES

    Stavrou, Elissaios; Zaug, Joseph M.; Bastea, Sorin; ...

    2017-05-02

    In this study, tantalum pentoxide Ta 2O 5 with the orthorhombic L-Ta 2O 5 structure has been experimentally studied up to 28.3 GPa (at ambient temperature) using synchrotron angle-dispersive powder X-ray diffraction (XRD). The ambient pressure phase remains stable up to 25 GPa where with increased pressure a crystalline to amorphous phase transition occurs. A detailed equation of state (EOS), including pressure dependent lattice parameters, is reported. The results of this study were compared with a previous high-pressure XRD study by Li et al. A clear discrepancy between the ambient-pressure crystal structures and, consequently, the reported EOSs between the twomore » studies was revealed. Finally, he origin of this discrepancy is attributed to two different crystal structures used to index the XRD patterns.« less

  8. Catalysis applications of size-selected cluster deposition

    DOE PAGES

    Vajda, Stefan; White, Michael G.

    2015-10-23

    In this Perspective, we review recent studies of size-selected cluster deposition for catalysis applications performed at the U.S. DOE National Laboratories, with emphasis on work at Argonne National Laboratory (ANL) and Brookhaven National Laboratory (BNL). The focus is on the preparation of model supported catalysts in which the number of atoms in the deposited clusters is precisely controlled using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques. This approach is particularly effective for investigations of small nanoclusters, 0.5-2 nm (<200 atoms), where the rapid evolution of the atomic and electronic structure makes it essential to havemore » precise control over cluster size. Cluster deposition allows for independent control of cluster size, coverage, and stoichiometry (e.g., the metal-to-oxygen ratio in an oxide cluster) and can be used to deposit on any substrate without constraints of nucleation and growth. Examples are presented for metal, metal oxide, and metal sulfide cluster deposition on a variety of supports (metals, oxides, carbon/diamond) where the reactivity, cluster-support electronic interactions, and cluster stability and morphology are investigated. Both UHV and in situ/operando studies are presented that also make use of surface-sensitive X-ray characterization tools from synchrotron radiation facilities. Novel applications of cluster deposition to electrochemistry and batteries are also presented. This review also highlights the application of modern ab initio electronic structure calculations (density functional theory), which can essentially model the exact experimental system used in the laboratory (i.e., cluster and support) to provide insight on atomic and electronic structure, reaction energetics, and mechanisms. As amply demonstrated in this review, the powerful combination of atomically precise cluster deposition and theory is able to address fundamental aspects of size

  9. Dynamic fracture of tantalum under extreme tensile stress.

    PubMed

    Albertazzi, Bruno; Ozaki, Norimasa; Zhakhovsky, Vasily; Faenov, Anatoly; Habara, Hideaki; Harmand, Marion; Hartley, Nicholas; Ilnitsky, Denis; Inogamov, Nail; Inubushi, Yuichi; Ishikawa, Tetsuya; Katayama, Tetsuo; Koyama, Takahisa; Koenig, Michel; Krygier, Andrew; Matsuoka, Takeshi; Matsuyama, Satoshi; McBride, Emma; Migdal, Kirill Petrovich; Morard, Guillaume; Ohashi, Haruhiko; Okuchi, Takuo; Pikuz, Tatiana; Purevjav, Narangoo; Sakata, Osami; Sano, Yasuhisa; Sato, Tomoko; Sekine, Toshimori; Seto, Yusuke; Takahashi, Kenjiro; Tanaka, Kazuo; Tange, Yoshinori; Togashi, Tadashi; Tono, Kensuke; Umeda, Yuhei; Vinci, Tommaso; Yabashi, Makina; Yabuuchi, Toshinori; Yamauchi, Kazuto; Yumoto, Hirokatsu; Kodama, Ryosuke

    2017-06-01

    The understanding of fracture phenomena of a material at extremely high strain rates is a key issue for a wide variety of scientific research ranging from applied science and technological developments to fundamental science such as laser-matter interaction and geology. Despite its interest, its study relies on a fine multiscale description, in between the atomic scale and macroscopic processes, so far only achievable by large-scale atomic simulations. Direct ultrafast real-time monitoring of dynamic fracture (spallation) at the atomic lattice scale with picosecond time resolution was beyond the reach of experimental techniques. We show that the coupling between a high-power optical laser pump pulse and a femtosecond x-ray probe pulse generated by an x-ray free electron laser allows detection of the lattice dynamics in a tantalum foil at an ultrahigh strain rate of [Formula: see text] ~2 × 10 8 to 3.5 × 10 8 s -1 . A maximal density drop of 8 to 10%, associated with the onset of spallation at a spall strength of ~17 GPa, was directly measured using x-ray diffraction. The experimental results of density evolution agree well with large-scale atomistic simulations of shock wave propagation and fracture of the sample. Our experimental technique opens a new pathway to the investigation of ultrahigh strain-rate phenomena in materials at the atomic scale, including high-speed crack dynamics and stress-induced solid-solid phase transitions.

  10. Dynamic fracture of tantalum under extreme tensile stress

    DOE PAGES

    Albertazzi, Bruno; Ozaki, Norimasa; Zhakhovsky, Vasily; ...

    2017-06-02

    The understanding of fracture phenomena of a material at extremely high strain rates is a key issue for a wide variety of scientific research ranging from applied science and technological developments to fundamental science such as laser-matter interaction and geology. Despite its interest, its study relies on a fine multiscale description, in between the atomic scale and macroscopic processes, so far only achievable by large-scale atomic simulations. Direct ultrafast real-time monitoring of dynamic fracture (spallation) at the atomic lattice scale with picosecond time resolution was beyond the reach of experimental techniques. We show that the coupling between a high-power opticalmore » laser pump pulse and a femtosecond x-ray probe pulse generated by an x-ray free electron laser allows detection of the lattice dynamics in a tantalum foil at an ultrahigh strain rate of Embedded Image ~2 × 10 8 to 3.5 × 10 8 s -1. A maximal density drop of 8 to 10%, associated with the onset of spallation at a spall strength of ~17 GPa, was directly measured using x-ray diffraction. The experimental results of density evolution agree well with large-scale atomistic simulations of shock wave propagation and fracture of the sample. Our experimental technique opens a new pathway to the investigation of ultrahigh strain-rate phenomena in materials at the atomic scale, including high-speed crack dynamics and stress-induced solid-solid phase transitions.« less

  11. Dynamic fracture of tantalum under extreme tensile stress

    PubMed Central

    Albertazzi, Bruno; Ozaki, Norimasa; Zhakhovsky, Vasily; Faenov, Anatoly; Habara, Hideaki; Harmand, Marion; Hartley, Nicholas; Ilnitsky, Denis; Inogamov, Nail; Inubushi, Yuichi; Ishikawa, Tetsuya; Katayama, Tetsuo; Koyama, Takahisa; Koenig, Michel; Krygier, Andrew; Matsuoka, Takeshi; Matsuyama, Satoshi; McBride, Emma; Migdal, Kirill Petrovich; Morard, Guillaume; Ohashi, Haruhiko; Okuchi, Takuo; Pikuz, Tatiana; Purevjav, Narangoo; Sakata, Osami; Sano, Yasuhisa; Sato, Tomoko; Sekine, Toshimori; Seto, Yusuke; Takahashi, Kenjiro; Tanaka, Kazuo; Tange, Yoshinori; Togashi, Tadashi; Tono, Kensuke; Umeda, Yuhei; Vinci, Tommaso; Yabashi, Makina; Yabuuchi, Toshinori; Yamauchi, Kazuto; Yumoto, Hirokatsu; Kodama, Ryosuke

    2017-01-01

    The understanding of fracture phenomena of a material at extremely high strain rates is a key issue for a wide variety of scientific research ranging from applied science and technological developments to fundamental science such as laser-matter interaction and geology. Despite its interest, its study relies on a fine multiscale description, in between the atomic scale and macroscopic processes, so far only achievable by large-scale atomic simulations. Direct ultrafast real-time monitoring of dynamic fracture (spallation) at the atomic lattice scale with picosecond time resolution was beyond the reach of experimental techniques. We show that the coupling between a high-power optical laser pump pulse and a femtosecond x-ray probe pulse generated by an x-ray free electron laser allows detection of the lattice dynamics in a tantalum foil at an ultrahigh strain rate of ε. ~2 × 108 to 3.5 × 108 s−1. A maximal density drop of 8 to 10%, associated with the onset of spallation at a spall strength of ~17 GPa, was directly measured using x-ray diffraction. The experimental results of density evolution agree well with large-scale atomistic simulations of shock wave propagation and fracture of the sample. Our experimental technique opens a new pathway to the investigation of ultrahigh strain-rate phenomena in materials at the atomic scale, including high-speed crack dynamics and stress-induced solid-solid phase transitions. PMID:28630909

  12. Widom line, dynamical crossover, and percolation transition of supercritical oxygen via molecular dynamics simulations.

    PubMed

    Raman, Abhinav S; Li, Huiyong; Chiew, Y C

    2018-01-07

    Supercritical oxygen, a cryogenic fluid, is widely used as an oxidizer in jet propulsion systems and is therefore of paramount importance in gaining physical insights into processes such as transcritical and supercritical vaporization. It is well established in the scientific literature that the supercritical state is not homogeneous but, in fact, can be demarcated into regions with liquid-like and vapor-like properties, separated by the "Widom line." In this study, we identified the Widom line for oxygen, constituted by the loci of the extrema of thermodynamic response functions (heat capacity, volumetric thermal expansion coefficient, and isothermal compressibility) in the supercritical region, via atomistic molecular dynamics simulations. We found that the Widom lines derived from these response functions all coincide near the critical point until about 25 bars and 15-20 K, beyond which the isothermal compressibility line begins to deviate. We also obtained the crossover from liquid-like to vapor-like behavior of the translational diffusion coefficient, shear viscosity, and rotational relaxation time of supercritical oxygen. While the crossover of the translational diffusion coefficient and shear viscosity coincided with the Widom lines, the rotational relaxation time showed a crossover that was largely independent of the Widom line. Further, we characterized the clustering behavior and percolation transition of supercritical oxygen molecules, identified the percolation threshold based on the fractal dimension of the largest cluster and the probability of finding a cluster that spans the system in all three dimensions, and found that the locus of the percolation threshold also coincided with the isothermal compressibility Widom line. It is therefore clear that supercritical oxygen is far more complex than originally perceived and that the Widom line, dynamical crossovers, and percolation transitions serve as useful routes to better our understanding of the

  13. Widom line, dynamical crossover, and percolation transition of supercritical oxygen via molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Raman, Abhinav S.; Li, Huiyong; Chiew, Y. C.

    2018-01-01

    Supercritical oxygen, a cryogenic fluid, is widely used as an oxidizer in jet propulsion systems and is therefore of paramount importance in gaining physical insights into processes such as transcritical and supercritical vaporization. It is well established in the scientific literature that the supercritical state is not homogeneous but, in fact, can be demarcated into regions with liquid-like and vapor-like properties, separated by the "Widom line." In this study, we identified the Widom line for oxygen, constituted by the loci of the extrema of thermodynamic response functions (heat capacity, volumetric thermal expansion coefficient, and isothermal compressibility) in the supercritical region, via atomistic molecular dynamics simulations. We found that the Widom lines derived from these response functions all coincide near the critical point until about 25 bars and 15-20 K, beyond which the isothermal compressibility line begins to deviate. We also obtained the crossover from liquid-like to vapor-like behavior of the translational diffusion coefficient, shear viscosity, and rotational relaxation time of supercritical oxygen. While the crossover of the translational diffusion coefficient and shear viscosity coincided with the Widom lines, the rotational relaxation time showed a crossover that was largely independent of the Widom line. Further, we characterized the clustering behavior and percolation transition of supercritical oxygen molecules, identified the percolation threshold based on the fractal dimension of the largest cluster and the probability of finding a cluster that spans the system in all three dimensions, and found that the locus of the percolation threshold also coincided with the isothermal compressibility Widom line. It is therefore clear that supercritical oxygen is far more complex than originally perceived and that the Widom line, dynamical crossovers, and percolation transitions serve as useful routes to better our understanding of the

  14. TUNGSTEN BRONZE RELATED NON-NOBLE ELECTROCATALYSTS.

    DTIC Science & Technology

    FUEL CELLS, *CATALYSTS), (*OXYGEN, *ELECTRODES), (* SILICIDES , ELECTRODES), (*CARBIDES, ELECTRODES), (*TUNGSTEN COMPOUNDS, *ELECTROCHEMISTRY...CATALYSTS, TITANIUM COMPOUNDS, ZIRCONIUM COMPOUNDS, VANADIUM COMPOUNDS, NIOBIUM COMPOUNDS, TUNGSTEN COMPOUNDS, TANTALUM COMPOUNDS, MOLYBDENUM COMPOUNDS, SULFURIC ACID, CRYSTAL GROWTH, SODIUM COMPOUNDS

  15. XMM-Newton Observations of the Cluster of Galaxies Sersic 159-03

    NASA Technical Reports Server (NTRS)

    Kaastra, J. S.; Ferrigno, C.; Tamura, T.; Paerels, F. B. S.; Peterson, J. R.; Mittaz, J. P. D.

    2000-01-01

    The cluster of galaxies Sersic 159-03 was observed with the XMM-Newton X-ray observatory as part of the Guaranteed Time program. X-ray spectra taken with the EPIC and RGS instruments show no evidence for the strong cooling flow derived from previous X-ray observations. There is a significant lack of cool gas below 1.5 keV as compared to standard isobaric cooling flow models. While the oxygen is distributed more or less uniformly over the cluster, iron shows a strong concentration in the center of the cluster, slightly offset from the brightness center but within the central cD galaxy. This points to enhanced type Ia supernova activity in the center of the cluster. There is also an elongated iron-rich structure ex- tending to the east of the cluster, showing the inhomogeneity of the iron distribution. Finally, the temperature drops rapidly beyond 4' from the cluster center.

  16. Cysteine desulfurase IscS2 plays a role in oxygen resistance in Clostridium difficile.

    PubMed

    Giordano, Nicole; Hastie, Jessica L; Smith, Ashley D; Foss, Elissa D; Gutierrez-Munoz, Daniela F; Carlson, Paul E

    2018-06-04

    Clostridium difficile is an anaerobic, spore-forming bacterium capable of colonizing the gastrointestinal tract of humans following disruption of the normal microbiota, typically from antibiotic therapy for an unrelated infection. With approximately 500,000 confirmed infections leading to 29,000 deaths per year in the United States, C. difficile infection (CDI) is an urgent public health threat. We previously determined C. difficile survives in up to 3% oxygen. Low levels of oxygen are present in the intestinal tract with the higher concentrations being associated with the epithelial cell surface. Additionally, antibiotic treatment, the greatest risk factor for CDI, increases intestinal oxygen concentration. Therefore, we hypothesized that the C. difficile genome encodes mechanisms for survival during oxidative stress. Previous data have shown that cysteine desulfurases involved in iron-sulfur cluster assembly are involved in protecting bacteria from oxidative stress. In this study, deletion of a putative cysteine desulfurase ( Cd 630_12790/IscS2) involved in the iron sulfur cluster (Isc) system caused a severe growth defect in the presence of 2% oxygen. Additionally, this mutant delayed colonization in a conventional mouse model of CDI, and failed to colonize in a germ-free model, which has higher intestinal oxygen levels. These data imply an undefined role for this cysteine desulfurase in protecting C. difficile from low levels of oxygen in the gut. This is a work of the U.S. Government and is not subject to copyright protection in the United States. Foreign copyrights may apply.

  17. Analysis of the M-shell spectra emitted by a short-pulse laser-created tantalum plasma

    PubMed

    Busquet; Jiang; Coinsertion Markte CY; Kieffer; Klapisch; Bar-Shalom; Bauche-Arnoult; Bachelier

    2000-01-01

    The spectrum of tantalum emitted by a subpicosecond laser-created plasma, was recorded in the regions of the 3d-5f, 3d-4f, and 3d-4p transitions. The main difference with a nanosecond laser-created plasma spectrum is a broad understructure appearing under the 3d-5f transitions. An interpretation of this feature as a density effect is proposed. The supertransition array model is used for interpreting the spectrum, assuming local thermodynamic equilibrium (LTE) at some effective temperature. An interpretation of the 3d-4f spectrum using the more detailed unresolved transition array formalism, which does not assume LTE, is also proposed. Fitted contributions of the different ionic species differ slightly from the LTE-predicted values.

  18. Simulations of X-ray diffraction of shock-compressed single-crystal tantalum with synchrotron undulator sources

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

    Tang, M. X.; Zhang, Y. Y.; E, J. C.

    Polychromatic synchrotron undulator X-ray sources are useful for ultrafast single-crystal diffraction under shock compression. Here, simulations of X-ray diffraction of shock-compressed single-crystal tantalum with realistic undulator sources are reported, based on large-scale molecular dynamics simulations. Purely elastic deformation, elastic–plastic two-wave structure, and severe plastic deformation under different impact velocities are explored, as well as an edge release case. Transmission-mode diffraction simulations consider crystallographic orientation, loading direction, incident beam direction, X-ray spectrum bandwidth and realistic detector size. Diffraction patterns and reciprocal space nodes are obtained from atomic configurations for different loading (elastic and plastic) and detection conditions, and interpretation of themore » diffraction patterns is discussed.« less

  19. Effect of Spin Multiplicity in O2 Adsorption and Dissociation on Small Bimetallic AuAg Clusters.

    PubMed

    García-Cruz, Raúl; Poulain, Enrique; Hernández-Pérez, Isaías; Reyes-Nava, Juan A; González-Torres, Julio C; Rubio-Ponce, A; Olvera-Neria, Oscar

    2017-08-17

    To dispose of atomic oxygen, it is necessary the O 2 activation; however, an energy barrier must be overcome to break the O-O bond. This work presents theoretical calculations of the O 2 adsorption and dissociation on small pure Au n and Ag m and bimetallic Au n Ag m (n + m ≤ 6) clusters using the density functional theory (DFT) and the zeroth-order regular approximation (ZORA) to explicitly include scalar relativistic effects. The most stable Au n Ag m clusters contain a higher concentration of Au with Ag atoms located in the center of the cluster. The O 2 adsorption energy on pure and bimetallic clusters and the ensuing geometries depend on the spin multiplicity of the system. For a doublet multiplicity, O 2 is adsorbed in a bridge configuration, whereas for a triplet only one O-metal bond is formed. The charge transfer from metal toward O 2 occupies the σ* O-O antibonding natural bond orbital, which weakens the oxygen bond. The Au 3 ( 2 A) cluster presents the lowest activation energy to dissociate O 2 , whereas the opposite applies to the AuAg ( 3 A) system. In the O 2 activation, bimetallic clusters are not as active as pure Au n clusters due to the charge donated by Ag atoms being shared between O 2 and Au atoms.

  20. Aerobic oxidation of alcohols in visible light on Pd-grafted Ti cluster

    EPA Science Inventory

    The titanium cluster with the reduced band gap has been synthesized having the palladium nanoparticles over the surface, which not only binds to the atmospheric oxygen but also catalyzes the oxidation of alcohols under visible light.

  1. Elemental abundances via X-ray observations of galaxy clusters and the InFOCmuS hard X-ray telescope

    NASA Astrophysics Data System (ADS)

    Baumgartner, Wayne H.

    2004-08-01

    The first part of this dissertation deals with the oxygen abundance of the Milky Way interstellar medium. Previous measurements had shown that oxygen in the ISM was depleted compared to its abundance in the sun. This dissertation presents new measurements of the ISM oxygen abundance taken in the X-ray band by observing the oxygen 0.6 keV photoionization K-edge in absorption towards 10 galaxy clusters. These measurements show that the ISM oxygen abundance is 0.9 solar, much greater than earlier depleted values. The oxygen abundance is found to be uniform across our 10 lines of sight, showing that it is not dependent on the depth of the hydrogen column. This implies that the galactic oxygen abundance does not depend on density, and that it is the same in dense clouds and in the more diffuse ISM. The next part of the dissertation measures elemental abundances in the galaxy clusters themselves. The abundances of the elements iron, silicon, sulfur, calcium, argon, and nickel are measured using the strong resonance K-shell emission lines in the X-ray band. Over 300 clusters from the ASCA archives are analyzed with a joint fitting procedure to improve the S/N ratio and provide the first average abundance results for clusters as a function of mass. The α elements silicon, sulfur, argon and calcium are not found to have similar abundances as expected from their supposed common origin. Also, no combination of SN Ia and SN II yields can account for the cluster abundance ratios, perhaps necessitating a contribution from a cosmologically early generation of massive population III stars. The last part of this dissertation details the development of the Cadmium Zinc Telluride (CZT) detectors on the InFOCμS hard X-ray telescope. InFOCμS is a balloon-borne imaging spectrometer that incorporates multi-layer coated grazing-incidence optics and CZT detectors. These detectors are well suited for hard X-ray astronomy because their large bandgap and high atomic number allow for

  2. Fe-S Clusters Emerging as Targets of Therapeutic Drugs

    PubMed Central

    2017-01-01

    Fe-S centers exhibit strong electronic plasticity, which is of importance for insuring fine redox tuning of protein biological properties. In accordance, Fe-S clusters are also highly sensitive to oxidation and can be very easily altered in vivo by different drugs, either directly or indirectly due to catabolic by-products, such as nitric oxide species (NOS) or reactive oxygen species (ROS). In case of metal ions, Fe-S cluster alteration might be the result of metal liganding to the coordinating sulfur atoms, as suggested for copper. Several drugs presented through this review are either capable of direct interaction with Fe-S clusters or of secondary Fe-S clusters alteration following ROS or NOS production. Reactions leading to Fe-S cluster disruption are also reported. Due to the recent interest and progress in Fe-S biology, it is very likely that an increasing number of drugs already used in clinics will emerge as molecules interfering with Fe-S centers in the near future. Targeting Fe-S centers could also become a promising strategy for drug development. PMID:29445445

  3. Molecular growth from a Mo176 to a Mo248 cluster

    NASA Astrophysics Data System (ADS)

    Müller, A.; Shah, Syed Q. N.; Bögge, H.; Schmidtmann, M.

    1999-01-01

    In polyoxometalate chemistry a large variety of compounds, clusters and solid-state structures can be formed by the linking together of well-defined metal-oxygen building blocks, . These species exhibit unusual topological and electronic properties, andfind applications ranging from medicine to industrial processes. The recently reported ring-shaped mixed-valence polyoxomolybdates of the type {Mo154} (refs 5, 6) and {Mo176} (refs 7, 8) represent a new class of giant clusters with nanometre-sized cavities and interesting properties for host-guest chemistry. Here we describe the formation of related clusters of the type {Mo248} formed by addition of further units to the inner surface of the {Mo176 } `wheel'. The additional units arrange themselves into two {Mo36} `hub-caps' on the initial wheel-clusters that are not stable in isolation. These findings reveal a new pathway to the development of complex coordination clusters.

  4. Growth of fluorescence gold clusters using photo-chemically activated ligands

    NASA Astrophysics Data System (ADS)

    Mishra, Dinesh; Aldeek, Fadi; Michael, Serge; Palui, Goutam; Mattoussi, Hedi

    2016-03-01

    Ligands made of lipoic acid (LA) appended with a polyethylene glycol (PEG) chain have been used in the aqueous phase growth of luminescent gold clusters with distinct emission from yellow to near-IR, using two different routes. In the first route, the gold-ligand complex was chemically reduced using sodium borohydride in alkaline medium, which gave near- IR luminescent gold clusters with maximum emission around 745 nm. In the second method, LA-PEG ligand was photochemically modified to a mixture of thiols, oligomers and oxygenated species under UV-irradiation, which was then used as both reducing agent and stabilizing ligand. By adjusting the pH, temperature, and time of the reaction, we were able to obtain clusters with two distinct emission properties. Refluxing the gold-ligand complex in alkaline medium in the presence of excess ligand gave yellow emission within the first two hours and the emission shifted to red after overnight reaction. Mass spectrometry and chemical assay were used to understand the photo-chemical transformation of Lipoic Acid (LA). Mass spectroscopic studies showed the photo-irradiated product contains thiols, oligomers (dimers, trimers and tetramers) as well as oxygenated species. The amount of thiol formed under different conditions of irradiation was estimated using Ellman's assay.

  5. Gradient Nanostructured Tantalum by Thermal-Mechanical Ultrasonic Impact Energy.

    PubMed

    Chae, Jong-Min; Lee, Keun-Oh; Amanov, Auezhan

    2018-03-20

    Microstructural evolution and wear performance of Tantalum (Ta) treated by ultrasonic nanocrystalline surface modification (UNSM) at 25 and 1000 °C were reported. The UNSM treatment modified a surface along with subsurface layer with a thickness in the range of 20 to 150 µm, which depends on the UNSM treatment temperature, via the surface severe plastic deformation (S²PD) method. The cross-sectional microstructure of the specimens was observed by electron backscattered diffraction (EBSD) in order to confirm the microstructural alteration in terms of effective depth and refined grain size. The surface hardness measurement results, including depth profile, revealed that the hardness of the UNSM-treated specimens at both temperatures was increased in comparison with those of the untreated ones. The increase in UNSM treatment temperature led to a further increase in hardness. Moreover, both the UNSM-treated specimens with an increased hardness resulted in a higher resistance to wear in comparison with those of the untreated ones under dry conditions. The increase in hardness and induced compressive residual stress that depend on the formation of severe plastically deformed layer with the refined nano-grains are responsible for the enhancement in wear resistance. The findings of this study may be implemented in response to various industries that are related to strength improvement and wear enhancement issues of Ta.

  6. Gradient Nanostructured Tantalum by Thermal-Mechanical Ultrasonic Impact Energy

    PubMed Central

    Chae, Jong-Min; Lee, Keun-Oh; Amanov, Auezhan

    2018-01-01

    Microstructural evolution and wear performance of Tantalum (Ta) treated by ultrasonic nanocrystalline surface modification (UNSM) at 25 and 1000 °C were reported. The UNSM treatment modified a surface along with subsurface layer with a thickness in the range of 20 to 150 µm, which depends on the UNSM treatment temperature, via the surface severe plastic deformation (S2PD) method. The cross-sectional microstructure of the specimens was observed by electron backscattered diffraction (EBSD) in order to confirm the microstructural alteration in terms of effective depth and refined grain size. The surface hardness measurement results, including depth profile, revealed that the hardness of the UNSM-treated specimens at both temperatures was increased in comparison with those of the untreated ones. The increase in UNSM treatment temperature led to a further increase in hardness. Moreover, both the UNSM-treated specimens with an increased hardness resulted in a higher resistance to wear in comparison with those of the untreated ones under dry conditions. The increase in hardness and induced compressive residual stress that depend on the formation of severe plastically deformed layer with the refined nano-grains are responsible for the enhancement in wear resistance. The findings of this study may be implemented in response to various industries that are related to strength improvement and wear enhancement issues of Ta. PMID:29558402

  7. Hydrometallurgical Separation of Niobium and Tantalum: A Fundamental Approach

    NASA Astrophysics Data System (ADS)

    Nete, Motlalepula; Purcell, Walter; Nel, Johann T.

    2016-02-01

    A mixture of pure Ta2O5 and Nb2O5 was dissolved using two different fluxes, namely NH4F·HF and Na2HPO4/NaH2PO4·H2O. Selective precipitation and ion exchange were used as separation techniques. Selective precipitation using p-phenylediamine in a fluoride matrix resulted in the isolation of 73(3)% tantalum accompanied by 23(5)% niobium. A separation factor of 11(4) was obtained. A single solvent extraction step using methyl-isobutyl ketone at a 4 M H2SO4 yielded excellent Ta and Nb separation in the fluoride solution with 80% of the Ta and only 2% Nb recovered in the organic layer. A two-step extraction recovered 100% Ta at 0.5-4 M H2SO4 with a separation factor of ~2000. A study of the extraction mechanism indicated that the stability of the protonated compounds such as H2TaF7/H2NbOF5 is in the extraction and separation determining steps in this process. A K' (double de-protonated constant) of approximately 0.2 was calculated for H2TaF7. Only 91.7% Nb and 73.4% Ta were recovered from anion separation using strong Amberlite resin and 96.1% Nb and 52.3% using the weak Dowex Marathon resin from fluoride dissolution.

  8. A Predictive Model of the Oxygen and Heme Regulatory Network in Yeast

    PubMed Central

    Kundaje, Anshul; Xin, Xiantong; Lan, Changgui; Lianoglou, Steve; Zhou, Mei; Zhang, Li; Leslie, Christina

    2008-01-01

    Deciphering gene regulatory mechanisms through the analysis of high-throughput expression data is a challenging computational problem. Previous computational studies have used large expression datasets in order to resolve fine patterns of coexpression, producing clusters or modules of potentially coregulated genes. These methods typically examine promoter sequence information, such as DNA motifs or transcription factor occupancy data, in a separate step after clustering. We needed an alternative and more integrative approach to study the oxygen regulatory network in Saccharomyces cerevisiae using a small dataset of perturbation experiments. Mechanisms of oxygen sensing and regulation underlie many physiological and pathological processes, and only a handful of oxygen regulators have been identified in previous studies. We used a new machine learning algorithm called MEDUSA to uncover detailed information about the oxygen regulatory network using genome-wide expression changes in response to perturbations in the levels of oxygen, heme, Hap1, and Co2+. MEDUSA integrates mRNA expression, promoter sequence, and ChIP-chip occupancy data to learn a model that accurately predicts the differential expression of target genes in held-out data. We used a novel margin-based score to extract significant condition-specific regulators and assemble a global map of the oxygen sensing and regulatory network. This network includes both known oxygen and heme regulators, such as Hap1, Mga2, Hap4, and Upc2, as well as many new candidate regulators. MEDUSA also identified many DNA motifs that are consistent with previous experimentally identified transcription factor binding sites. Because MEDUSA's regulatory program associates regulators to target genes through their promoter sequences, we directly tested the predicted regulators for OLE1, a gene specifically induced under hypoxia, by experimental analysis of the activity of its promoter. In each case, deletion of the candidate

  9. Sol-gel type synthesis of Bi.sub.2 (Sr,Ta.sub.2)O.sub.9 using an acetate based system

    DOEpatents

    Boyle, Timothy J.

    1997-01-01

    A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen.

  10. Aerobic oxidation of alcohols in visible light on Pd-grafted Ti cluster

    EPA Pesticide Factsheets

    The titanium cluster with the reduced band gap has been synthesized having the palladium nanoparticles over the surface, which not only binds to the atmospheric oxygen but also catalyzes the oxidation of alcohols under visible light.This dataset is associated with the following publication:Varma, R., M. Nadagouda, S. Verma, and R.B.N. Baig. Aerobic oxidation of alcohols in visible light on Pd-grafted Ti cluster. TETRAHEDRON. Elsevier Science Ltd, New York, NY, USA, (2016).

  11. Differences in Pedaling Technique in Cycling: A Cluster Analysis.

    PubMed

    Lanferdini, Fábio J; Bini, Rodrigo R; Figueiredo, Pedro; Diefenthaeler, Fernando; Mota, Carlos B; Arndt, Anton; Vaz, Marco A

    2016-10-01

    To employ cluster analysis to assess if cyclists would opt for different strategies in terms of neuromuscular patterns when pedaling at the power output of their second ventilatory threshold (PO VT2 ) compared with cycling at their maximal power output (PO MAX ). Twenty athletes performed an incremental cycling test to determine their power output (PO MAX and PO VT2 ; first session), and pedal forces, muscle activation, muscle-tendon unit length, and vastus lateralis architecture (fascicle length, pennation angle, and muscle thickness) were recorded (second session) in PO MAX and PO VT2 . Athletes were assigned to 2 clusters based on the behavior of outcome variables at PO VT2 and PO MAX using cluster analysis. Clusters 1 (n = 14) and 2 (n = 6) showed similar power output and oxygen uptake. Cluster 1 presented larger increases in pedal force and knee power than cluster 2, without differences for the index of effectiveness. Cluster 1 presented less variation in knee angle, muscle-tendon unit length, pennation angle, and tendon length than cluster 2. However, clusters 1 and 2 showed similar muscle thickness, fascicle length, and muscle activation. When cycling at PO VT2 vs PO MAX , cyclists could opt for keeping a constant knee power and pedal-force production, associated with an increase in tendon excursion and a constant fascicle length. Increases in power output lead to greater variations in knee angle, muscle-tendon unit length, tendon length, and pennation angle of vastus lateralis for a similar knee-extensor activation and smaller pedal-force changes in cyclists from cluster 2 than in cluster 1.

  12. Metal Adatoms and Clusters on Ultrathin Zirconia Films

    PubMed Central

    2016-01-01

    Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces. PMID:27213024

  13. High-resolution spectra of stars in globular clusters. VI - Oxygen-deficient red giant stars in M13

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

    Brown, J.A.; Wallerstein, G.; Oke, J.B.

    From high-resolution, high signal-to-noise spectra, abundances of carbon, nitrogen, and oxygen and the C-12/C-13 ratio for five red giants in M13, including star II-67, which has previously been reported to be deficient in oxygen have been determined. Three of the five stars exhibit substantial oxygen deficiencies; O/Fe values range from +0.5 to less than about 0.3. The sum of the CNO nuclides is the same for all stars, which is interpreted as evidence that mixing of CNO-cycled material into the envelope is the cause of the variations in oxygen abundance. 41 refs.

  14. Conformational Properties, Spectroscopy and Structure of ISATIN-(WATER)_{n=1-3} Clusters

    NASA Astrophysics Data System (ADS)

    Singh, Milind K.; Upadhya, D. M.; Singh, Vipin B.

    2009-06-01

    The structure, stability and vibrational characteristics of Isatin-(Water)_n clusters with n=1=3 have been investigated using second order Moller-Plesset (MP2) perturbation tehory and Density Functional Theory (with B3LYP) methods employing the basis set 6-31+G(d). The vertical excitation energies for these complexes have been also computed using the time-dependent density functional theory. The three stable conformational isomers, each for Isatin-(Water)_1 and Isatin-(Water)_2 clusters were obtained. It is shown that in the most stable isomer of Isatin-(Water)_1 cluster hydrogen bond between amide hydrogen and oxygen of water is found stronger as compared to the H-bond in Indole-(Water)_1 cluster. For a particular position of complexation of water, between the carbonyl oxygen's, results an unusual increase in the dipole moment due to an electronic charge displacement from the N atom to the C atom of the neighboring carbonyl bond. This causes a large separation between the effective charges forming the dipole. The complexes involving this position of water are expected to show a small charge transfer character. The experimentally observed electronic absorption peaks are reasonably reproduced by the TD-DFT calculations and it is found that the longest wavelength absorption peak of isatin at 406 nm is significantly red shifted after addition of a water molecule.

  15. Influence of oxygen on the chemical stage of radiobiological mechanism

    NASA Astrophysics Data System (ADS)

    Barilla, Jiří; Lokajíček, Miloš V.; Pisaková, Hana; Simr, Pavel

    2016-07-01

    The simulation of the chemical stage of radiobiological mechanism may be very helpful in studying the radiobiological effect of ionizing radiation when the water radical clusters formed by the densely ionizing ends of primary or secondary charged particle may form DSBs damaging DNA molecules in living cells. It is possible to study not only the efficiency of individual radicals but also the influence of other species or radiomodifiers (mainly oxygen) being present in water medium during irradiation. The mathematical model based on Continuous Petri nets (proposed by us recently) will be described. It makes it possible to analyze two main processes running at the same time: chemical radical reactions and the diffusion of radical clusters formed during energy transfer. One may study the time change of radical concentrations due to the chemical reactions running during diffusion process. Some orientation results concerning the efficiency of individual radicals in DSB formation (in the case of Co60 radiation) will be presented; the influence of oxygen present in water medium during irradiation will be shown, too.

  16. An efficient laser vaporization source for chemically modified metal clusters characterized by thermodynamics and kinetics

    NASA Astrophysics Data System (ADS)

    Masubuchi, Tsugunosuke; Eckhard, Jan F.; Lange, Kathrin; Visser, Bradley; Tschurl, Martin; Heiz, Ulrich

    2018-02-01

    A laser vaporization cluster source that has a room for cluster aggregation and a reactor volume, each equipped with a pulsed valve, is presented for the efficient gas-phase production of chemically modified metal clusters. The performance of the cluster source is evaluated through the production of Ta and Ta oxide cluster cations, TaxOy+ (y ≥ 0). It is demonstrated that the cluster source produces TaxOy+ over a wide mass range, the metal-to-oxygen ratio of which can easily be controlled by changing the pulse duration that influences the amount of reactant O2 introduced into the cluster source. Reaction kinetic modeling shows that the generation of the oxides takes place under thermalized conditions at less than 300 K, whereas metal cluster cores are presumably created with excess heat. These characteristics are also advantageous to yield "reaction intermediates" of interest via reactions between clusters and reactive molecules in the cluster source, which may subsequently be mass selected for their reactivity measurements.

  17. Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.

    PubMed

    Cox, Nicholas; Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A; Boussac, Alain; Lubitz, Wolfgang

    2014-08-15

    The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S3) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectroscopy reveals that all four manganese ions of the catalyst are structurally and electronically similar immediately before the final oxygen evolution step; they all exhibit a 4+ formal oxidation state and octahedral local geometry. Only one structural model derived from quantum chemical modeling is consistent with all magnetic resonance data; its formation requires the binding of an additional water molecule. O-O bond formation would then proceed by the coupling of two proximal manganese-bound oxygens in the transition state of the cofactor. Copyright © 2014, American Association for the Advancement of Science.

  18. Periodic trends in hexanuclear actinide clusters.

    PubMed

    Diwu, Juan; Wang, Shuao; Albrecht-Schmitt, Thomas E

    2012-04-02

    Four new Th(IV), U(IV), and Np(IV) hexanuclear clusters with 1,2-phenylenediphosphonate as the bridging ligand have been prepared by self-assembly at room temperature. The structures of Th(6)Tl(3)[C(6)H(4)(PO(3))(PO(3)H)](6)(NO(3))(7)(H(2)O)(6)·(NO(3))(2)·4H(2)O (Th6-3), (NH(4))(8.11)Np(12)Rb(3.89)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·15H(2)O (Np6-1), (NH(4))(4)U(12)Cs(8)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·18H(2)O (U6-1), and (NH(4))(4)U(12)Cs(2)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(18)·40H(2)O (U6-2) are described and compared with other clusters of containing An(IV) or Ce(IV). All of the clusters share the common formula M(6)(H(2)O)(m)[C(6)H(3)(PO(3))(PO(3)H)](6)(NO(3))(n)((6-n)) (M = Ce, Th, U, Np, Pu). The metal centers are normally nine-coordinate, with five oxygen atoms from the ligand and an additional four either occupied by NO(3)(-) or H(2)O. It was found that the Ce, U, and Pu clusters favor both C(3i) and C(i) point groups, while Th only yields in C(i), and Np only C(3i). In the C(3i) clusters, there are two NO(3)(-) anions bonded to the metal centers. In the C(i) clusters, the number of NO(3)(-) anions varies from 0 to 2. The change in the ionic radius of the actinide ions tunes the cavity size of the clusters. The thorium clusters were found to accept larger ions including Cs(+) and Tl(+), whereas with uranium and later elements, only NH(4)(+) and/or Rb(+) reside in the center of the clusters.

  19. Degradation and ESR Failures in MnO2 Chip Tantalum Capacitors

    NASA Technical Reports Server (NTRS)

    Teverovsky, Alexander A.

    2017-01-01

    Equivalent series resistance (ESR) of chip tantalum capacitors determines the rate of energy delivery and power dissipation thus affecting temperature and reliability of the parts. Employment of advanced capacitors with reduced ESR decreases power losses and improves efficiency in power systems. Stability of ESR is essential for correct operations of power units and might cause malfunctioning and failures when ESR becomes too high or too low. Several cases with ESR values in CWR29 capacitors exceeding the specified limit that were observed recently raised concerns regarding environmental factors affecting ESR and the adequacy of the existing screening and qualification testing. In this work, results of stress testing of various types of military and commercial capacitors obtained over years by GSFC test lab and NEPP projects that involved ESR measurements are described. Environmental stress tests include testing in humidity and vacuum chambers, temperature cycling, long-term storage at high temperatures, and various soldering simulation tests. Note that in many cases parts failed due to excessive leakage currents or reduced breakdown voltages. However, only ESR-related degradation and failures are discussed. Mechanisms of moisture effect are discussed and recommendations to improve screening and qualification system are suggested.

  20. Tensile strength and failure mechanisms of tantalum at extreme strain rates

    NASA Astrophysics Data System (ADS)

    Hahn, Eric; Fensin, Saryu; Germann, Timothy; Meyers, Marc

    Non-equilibrium molecular dynamics simulations are used to probe the tensile response of monocrystalline, bicrystalline, and nanocrystalline tantalum over six orders of magnitude of strain rate. Our analysis of the strain rate dependence of strength is extended to over nine orders of magnitude by bridging the present simulations to recent laser-driven shock experiments. Tensile strength shows a power-law dependence with strain rate over this wide range, with different relationships depending on the initial microstructure and active deformation mechanism. At high strain rates, multiple spall events occur independently and continue to occur until communication occurs by means of relaxation waves. Temperature plays a significant role in the reduction of spall strength as the initial shock required to achieve such large strain rates also contributes to temperature rise, through pressure-volume work as well as visco-plastic heating, which leads to softening and sometimes melting upon release. At ultra-high strain rates, those approaching or exceeding the atomic vibrational frequency, spall strength saturates at the ultimate cohesive strength of the material. UC Research Laboratories Grant (09-LR-06-118456-MEYM); Department of Energy NNSA/SSAP (DE-NA0002080); DOE ASCR Exascale Co-design Center for Materials in Extreme Environments.

  1. Tantalum-182 Therapy of Vulva Carcinomas. Physical Data, Dosimetry Applications and Techniques, and Results (in German)

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

    Jakob, A.

    1963-04-01

    Experiences with Ta-182 therapy of vulva carcinoma are described. A description is given of the spectrum, the half-value-layer of Ta 182 in water and lead, the dose distribution in tissue, dosimetry, technique of application, and protection of the attending personnel. The results are discussed which were obtained so far on 31 patients since 1955. Radio-tantalum is particularly indicated on old patients or those with heart and circulation troubles, on whom an operation cannot be risked. The strain on the patient is small; the operation is quick, simple and without danger; rest in bed is not always required; no mutilation occurs;more » the costs are low; and the radiation burden for therapist and nursing personnel is small.« less

  2. Thermodynamics of Oxygen Ordering in Yttrium BARIUM(2) COPPER(3) OXYGEN(6+X)

    NASA Astrophysics Data System (ADS)

    Schieger, Paul Richard

    An apparatus has been built to study and manipulate the oxygen in high temperature superconductors. It uses the principle of cryogenically assisted volumetric titration to precisely set changes in the oxygen content of high -T_{c} samples. The apparatus has been used to study the thermodynamics of oxygen in YBa_2Cu_3O _{6 + x} in order to help determine the correct model for oxygen thermodynamics as well as to provide standard curves for materials preparation by other methods. In particular, extensive measurements have been made on the oxygen pressure isotherms as a function of x for temperatures between 450^circ C and 650^circC. The measurement technique also allows one to extract the thermodynamic response function, (partial x/ partialmu)_{T}, ( mu is the chemical potential), which is sensitive to the oxygen configuration and which can be calculated by any candidate theory of the oxygen thermodynamics. Several existing theoretical models for the oxygen ordering thermodynamics are presented and compared to the experimental results. The models considered are classed into two basic approaches: lattice gas models and defect chemical models. It is found that the lattice gas models which assume static effective pair interactions between oxygen atoms, do not fit the experimental data very well, especially in the orthorhombic phase. The defect chemical models, which incorporate additional degrees of freedom (spin and charge) due to the creation of electronic defects, fit significantly better, but make crude assumptions for the configurational entropy of oxygen atoms. Using a commonly accepted picture for the creation of mobile electron holes and unpaired spins on the copper sites, it is possible to relate these quantities in terms of short range cluster probabilities defined in mean field approximations to the 2D lattice gas models. Based upon this connection, a thermodynamical model is developed, which takes into account interactions between oxygen atoms and the

  3. Unraveling the oxygen vacancy structures at the reduced Ce O2(111 ) surface

    NASA Astrophysics Data System (ADS)

    Han, Zhong-Kang; Yang, Yi-Zhou; Zhu, Beien; Ganduglia-Pirovano, M. Verónica; Gao, Yi

    2018-03-01

    Oxygen vacancies at ceria (Ce O2 ) surfaces play an essential role in catalytic applications. However, during the past decade, the near-surface vacancy structures at Ce O2(111 ) have been questioned due to the contradictory results from experiments and theoretical simulations. Whether surface vacancies agglomerate, and which is the most stable vacancy structure for varying vacancy concentration and temperature, are being heatedly debated. By combining density functional theory calculations and Monte Carlo simulations, we proposed a unified model to explain all conflicting experimental observations and theoretical results. We find a novel trimeric vacancy structure which is more stable than any other one previously reported, which perfectly reproduces the characteristics of the double linear surface oxygen vacancy clusters observed by STM. Monte Carlo simulations show that at low temperature and low vacancy concentrations, vacancies prefer subsurface sites with a local (2 × 2) ordering, whereas mostly linear surface vacancy clusters do form with increased temperature and degree of reduction. These results well explain the disputes about the stable vacancy structure and surface vacancy clustering at Ce O2(111 ) , and provide a foundation for the understanding of the redox and catalytic chemistry of metal oxides.

  4. Effects of a Tantalum Addition on the Morphological and Compositional Evolutions of a Model Ni-AL-Cr Superalloy

    NASA Technical Reports Server (NTRS)

    Booth-Morrison, Christopher; Seidman, David N.; Noebe, Ronald D.

    2008-01-01

    The effects of a 2.0 at.% addition of Ta to a model Ni-Al-Cr superalloy aged at 1073 K are assessed using scanning electron microscopy and atom-probe tomography. The addition of Ta results in appreciable strengthening, and the morphology is found to evolve from a bimodal distribution of spheroidal precipitates, to cuboidal precipitates aligned along the elastically soft <001>-type directions. Tantalum is observed to partition preferentially to the gamma -precipitate phase and decreases the mobility of Ni in the gamma- matrix sufficiently to cause an accumulation of Ni on the gamma-matrix side of the gamma -precipitate/gamma-matrix heterophase interface.

  5. Low oxygen tension enhances endothelial fate of human pluripotent stem cells.

    PubMed

    Kusuma, Sravanti; Peijnenburg, Elizabeth; Patel, Parth; Gerecht, Sharon

    2014-04-01

    A critical regulator of the developing or regenerating vasculature is low oxygen tension. Precise elucidation of the role of low oxygen environments on endothelial commitment from human pluripotent stem cells necessitates controlled in vitro differentiation environments. We used a feeder-free, 2-dimensional differentiation system in which we could monitor accurately dissolved oxygen levels during human pluripotent stem cell differentiation toward early vascular cells (EVCs). We found that oxygen uptake rate of differentiating human pluripotent stem cells is lower in 5% O2 compared with atmospheric conditions. EVCs differentiated in 5% O2 had an increased vascular endothelial cadherin expression with clusters of vascular endothelial cadherin+ cells surrounded by platelet-derived growth factor β+ cells. When we assessed the temporal effects of low oxygen differentiation environments, we determined that low oxygen environments during the early stages of EVC differentiation enhance endothelial lineage commitment. EVCs differentiated in 5% O2 exhibited an increased expression of vascular endothelial cadherin and CD31 along with their localization to the membrane, enhanced lectin binding and acetylated low-density lipoprotein uptake, rapid cord-like structure formation, and increased expression of arterial endothelial cell markers. Inhibition of reactive oxygen species generation during the early stages of differentiation abrogated the endothelial inductive effects of the low oxygen environments. Low oxygen tension during early stages of EVC derivation induces endothelial commitment and maturation through the accumulation of reactive oxygen species, highlighting the importance of regulating oxygen tensions during human pluripotent stem cell-vascular differentiation.

  6. High-Resolution CCD Spectra of Stars in Globular Clusters. IX. The "Young" Clusters Ruprecht 106 and PAL 12

    NASA Astrophysics Data System (ADS)

    Brown, Jeffrey A.; Wallerstein, George; Zucker, Daniel

    1997-07-01

    We have performed a spectroscopic abundance analysis of two stars each in the anomalously young globular clusters Rup 106 and Pal 12. We find [Fe/H] =~ -1.45 for Rup 106 and -1.0 for Pal 12. The abundance ratios in both clusters are peculiar in comparison to other globulars: the alpha -elements are not enhanced over the solar ratio. We find that oxygen in Rup 106 is also relatively low, with [O/Fe] =~ 0.0 - +0.1. The similarity of the ratio of the alpha-elements to iron to the solar ratio shows that species contributed by supernovae of type Ia have ``caught up" with species produced by SN II's. The similar contributions of the alpha - and Fe-peak species to disk stars shows that age, not metallicity, is the determining factor in the ratio of SN II/SN Ia nucleosynthesis. Galactic enrichment models show that these abundance ratios can be understood as being the result of these two clusters coming from an environment with multiple discontinuous star formation events.

  7. Diversity and Spatial Distribution of Hydrazine Oxidoreductase (hzo) Gene in the Oxygen Minimum Zone Off Costa Rica

    PubMed Central

    Kong, Liangliang; Jing, Hongmei; Kataoka, Takafumi; Buchwald, Carolyn; Liu, Hongbin

    2013-01-01

    Anaerobic ammonia oxidation (anammox) as an important nitrogen loss pathway has been reported in marine oxygen minimum zones (OMZs), but the community composition and spatial distribution of anammox bacteria in the eastern tropical North Pacific (ETNP) OMZ are poorly determined. In this study, anammox bacterial communities in the OMZ off Costa Rica (CRD-OMZ) were analyzed based on both hydrazine oxidoreductase (hzo) genes and their transcripts assigned to cluster 1 and 2. The anammox communities revealed by hzo genes and proteins in CRD-OMZ showed a low diversity. Gene quantification results showed that hzo gene abundances peaked in the upper OMZs, associated with the peaks of nitrite concentration. Nitrite and oxygen concentrations may therefore colimit the distribution of anammox bacteria in this area. Furthermore, transcriptional activity of anammox bacteria was confirmed by obtaining abundant hzo mRNA transcripts through qRT-PCR. A novel hzo cluster 2x clade was identified by the phylogenetic analysis and these novel sequences were abundant and widely distributed in this environment. Our study demonstrated that both cluster 1 and 2 anammox bacteria play an active role in the CRD-OMZ, and the cluster 1 abundance and transcriptional activity were higher than cluster 2 in both free-living and particle-attached fractions at both gene and transcriptional levels. PMID:24205176

  8. Diversity and spatial distribution of hydrazine oxidoreductase (hzo) gene in the oxygen minimum zone off Costa Rica.

    PubMed

    Kong, Liangliang; Jing, Hongmei; Kataoka, Takafumi; Buchwald, Carolyn; Liu, Hongbin

    2013-01-01

    Anaerobic ammonia oxidation (anammox) as an important nitrogen loss pathway has been reported in marine oxygen minimum zones (OMZs), but the community composition and spatial distribution of anammox bacteria in the eastern tropical North Pacific (ETNP) OMZ are poorly determined. In this study, anammox bacterial communities in the OMZ off Costa Rica (CRD-OMZ) were analyzed based on both hydrazine oxidoreductase (hzo) genes and their transcripts assigned to cluster 1 and 2. The anammox communities revealed by hzo genes and proteins in CRD-OMZ showed a low diversity. Gene quantification results showed that hzo gene abundances peaked in the upper OMZs, associated with the peaks of nitrite concentration. Nitrite and oxygen concentrations may therefore colimit the distribution of anammox bacteria in this area. Furthermore, transcriptional activity of anammox bacteria was confirmed by obtaining abundant hzo mRNA transcripts through qRT-PCR. A novel hzo cluster 2x clade was identified by the phylogenetic analysis and these novel sequences were abundant and widely distributed in this environment. Our study demonstrated that both cluster 1 and 2 anammox bacteria play an active role in the CRD-OMZ, and the cluster 1 abundance and transcriptional activity were higher than cluster 2 in both free-living and particle-attached fractions at both gene and transcriptional levels.

  9. Ammonia-Oxidizing β-Proteobacteria from the Oxygen Minimum Zone off Northern Chile▿

    PubMed Central

    Molina, Verónica; Ulloa, Osvaldo; Farías, Laura; Urrutia, Homero; Ramírez, Salvador; Junier, Pilar; Witzel, Karl-Paul

    2007-01-01

    The composition of ammonia-oxidizing bacteria from the β-Proteobacteria subclass (βAOB) was studied in the surface and upper-oxycline oxic waters (2- to 50-m depth, ∼200 to 44 μM O2) and within the oxygen minimum zone (OMZ) suboxic waters (50- to 400-m depth, ≤10 μM O2) of the eastern South Pacific off northern Chile. This study was carried out through cloning and sequencing of genes coding for 16S rRNA and the ammonia monooxygenase enzyme active subunit (amoA). Sequences affiliated with Nitrosospira-like cluster 1 dominated the 16S rRNA gene clone libraries constructed from both oxic and suboxic waters. Cluster 1 consists exclusively of yet-uncultivated βAOB from marine environments. However, a single clone, out of 224 obtained from the OMZ, was found to belong to Nitrosospira lineage cluster 0. To our knowledge, cluster 0 sequences have been derived from βAOB isolated only from sand, soil, and freshwater environments. Sequences in clone libraries of the amoA gene from the surface and upper oxycline could be grouped in a marine subcluster, also containing no cultured representatives. In contrast, all 74 amoA sequences originating from the OMZ were either closely affiliated with cultured Nitrosospira spp. from clusters 0 and 2 or with other yet-uncultured βAOB from soil and an aerated-anoxic Orbal process waste treatment plant. Our results reveal the presence of Nitrosospira-like βAOB in both oxic and suboxic waters associated with the OMZ but with a clear community shift at the functional level (amoA) along the strong oxygen gradient. PMID:17416686

  10. Ammonia-oxidizing beta-proteobacteria from the oxygen minimum zone off northern Chile.

    PubMed

    Molina, Verónica; Ulloa, Osvaldo; Farías, Laura; Urrutia, Homero; Ramírez, Salvador; Junier, Pilar; Witzel, Karl-Paul

    2007-06-01

    The composition of ammonia-oxidizing bacteria from the beta-Proteobacteria subclass (betaAOB) was studied in the surface and upper-oxycline oxic waters (2- to 50-m depth, approximately 200 to 44 microM O(2)) and within the oxygen minimum zone (OMZ) suboxic waters (50- to 400-m depth, < or =10 microM O(2)) of the eastern South Pacific off northern Chile. This study was carried out through cloning and sequencing of genes coding for 16S rRNA and the ammonia monooxygenase enzyme active subunit (amoA). Sequences affiliated with Nitrosospira-like cluster 1 dominated the 16S rRNA gene clone libraries constructed from both oxic and suboxic waters. Cluster 1 consists exclusively of yet-uncultivated betaAOB from marine environments. However, a single clone, out of 224 obtained from the OMZ, was found to belong to Nitrosospira lineage cluster 0. To our knowledge, cluster 0 sequences have been derived from betaAOB isolated only from sand, soil, and freshwater environments. Sequences in clone libraries of the amoA gene from the surface and upper oxycline could be grouped in a marine subcluster, also containing no cultured representatives. In contrast, all 74 amoA sequences originating from the OMZ were either closely affiliated with cultured Nitrosospira spp. from clusters 0 and 2 or with other yet-uncultured betaAOB from soil and an aerated-anoxic Orbal process waste treatment plant. Our results reveal the presence of Nitrosospira-like betaAOB in both oxic and suboxic waters associated with the OMZ but with a clear community shift at the functional level (amoA) along the strong oxygen gradient.

  11. Electronic structure of trioxide, oxoperoxide, oxosuperoxide, and ozonide clusters of the 3d elements: density functional theory study.

    PubMed

    Uzunova, Ellie L

    2011-03-03

    The trioxide clusters with stoichiometry MO3, and the structural isomers with side-on and end-on bonded oxygen atoms, are studied by DFT with the B1LYP functional. For the first half of the 3d elements row (Sc to Cr), pyramidal or distorted pyramidal structures dominate among the trioxide and oxoperoxide ground states, while the remaining elements form planar trioxides, oxoperoxides, oxosuperoxides, and ozonides. Low-lying trioxide clusters are formed by Ti, V, Cr, and Mn, among which the distorted pyramidal VO3 in the (2)A'' state, the pyramidal CrO3 in the (1)A1 state, and the planar MnO3 in the (2)A1' state are global minima. With the exception of the middle-row elements Mn, Fe, and Co, the magnetic moment of the ground-state clusters is formed with a major contribution from unpaired electrons located at the oxygen atoms. The stability of trioxides and oxoperoxides toward release of molecular oxygen is significantly higher for Sc, Ti, and V than for the remaining elements of the row. A trend of increasing the capability to dissociate one oxygen molecule is observed from Cr to Cu, with the exception of OFe(O2) being more reactive than OCo(O2). A gradual increase of reactivity from Ti to Cu is observed for the complete fragmentation reaction M + O + O2.

  12. The Relationship of Sodium and Oxygen in Galactic Field RR Lyrae Stars

    NASA Astrophysics Data System (ADS)

    Andrievsky, S.; Wallerstein, G.; Korotin, S.; Lyashko, D.; Kovtyukh, V.; Tsymbal, V.; Davis, C. E.; Gomez, T.; Huang, W.; Farrell, E. M.

    2018-02-01

    We analyzed 62 high-resolution spectra of 30 Galactic Field RR Lyrae-type stars with the aim of deriving their atmospheric parameters (T eff , {log}g, V t ), metallicity ([Fe/H]), radial velocities, and NLTE abundances of oxygen and sodium. We found that there is no clear anti-correlation between [O/Fe] and [Na/Fe] as is seen in globular clusters. On this basis, we conclude that the majority of field RR Lyrae-type stars should hardly be considered to be remnants of the dissolution of globular clusters.

  13. Intra-cluster Globular Clusters in a Simulated Galaxy Cluster

    NASA Astrophysics Data System (ADS)

    Ramos-Almendares, Felipe; Abadi, Mario; Muriel, Hernán; Coenda, Valeria

    2018-01-01

    Using a cosmological dark matter simulation of a galaxy-cluster halo, we follow the temporal evolution of its globular cluster population. To mimic the red and blue globular cluster populations, we select at high redshift (z∼ 1) two sets of particles from individual galactic halos constrained by the fact that, at redshift z = 0, they have density profiles similar to observed ones. At redshift z = 0, approximately 60% of our selected globular clusters were removed from their original halos building up the intra-cluster globular cluster population, while the remaining 40% are still gravitationally bound to their original galactic halos. As the blue population is more extended than the red one, the intra-cluster globular cluster population is dominated by blue globular clusters, with a relative fraction that grows from 60% at redshift z = 0 up to 83% for redshift z∼ 2. In agreement with observational results for the Virgo galaxy cluster, the blue intra-cluster globular cluster population is more spatially extended than the red one, pointing to a tidally disrupted origin.

  14. British Thoracic Society guidelines for home oxygen use in adults.

    PubMed

    Hardinge, Maxine; Annandale, Joe; Bourne, Simon; Cooper, Brendan; Evans, Angela; Freeman, Daryl; Green, Angela; Hippolyte, Sabrine; Knowles, Vikki; MacNee, William; McDonnell, Lynn; Pye, Kathy; Suntharalingam, Jay; Vora, Vandana; Wilkinson, Tom

    2015-06-01

    The British Thoracic Society (BTS) Home Oxygen Guideline provides detailed evidence-based guidance for the use of home oxygen for patients out of hospital. Although the majority of evidence comes from the use of oxygen in patients with chronic obstructive pulmonary disease, the scope of the guidance includes patients with a variety of long-term respiratory illnesses and other groups in whom oxygen is currently ordered, such as those with cardiac failure, cancer and end-stage cardiorespiratory disease, terminal illness or cluster headache. It explores the evidence base for the use of different modalities of oxygen therapy and patient-related outcomes such as mortality, symptoms and quality of life. The guideline also makes recommendations for assessment and follow-up protocols, and risk assessments, particularly in the clinically challenging area of home oxygen users who smoke. The guideline development group is aware of the potential for confusion sometimes caused by the current nomenclature for different types of home oxygen, and rather than renaming them, has adopted the approach of clarifying those definitions, and in particular emphasising what is meant by long-term oxygen therapy and palliative oxygen therapy. The home oxygen guideline provides expert consensus opinion in areas where clinical evidence is lacking, and seeks to deliver improved prescribing practice, leading to improved compliance and improved patient outcomes, with consequent increased value to the health service. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

  15. Globular Cluster Star Classification: Application to M13

    NASA Astrophysics Data System (ADS)

    Caimmi, R.

    2013-06-01

    Starting from recent determination of Fe, O, Na abundances on a restricted sample (N=67) of halo and thick disk stars, a natural and well motivated selection criterion is defined for the classification globular cluster stars. An application is performed to M13 using a sample (N=113) for which Fe, O, Na abundances have been recently inferred from observations. A comparison is made between the current and earlier M13 star classifications. Both O and Na empirical differential abundance distributions are determined for each class and for the whole sample (with the addition of Fe in the last case) and compared with their theoretical counterparts due to cosmic scatter obeying a Gaussian distribution whose parameters are inferred from related subsamples. The occurrence of an agreement between the empirical and theoretical distributions is interpreted as absence of significant chemical evolution and vice versa. The procedure is repeated with regard to four additional classes depending on whether oxygen and sodium abundance is above (stage CE) or below (stage AF) a selected threshold. Both O and Na empirical differential abundance distributions, related to the whole sample, exhibit a linear fit for the AF and CE stage. Within the errors, the oxygen slope for the CE stage is equal and of opposite sign with respect to the sodium slope for AF stage, while the contrary holds when dealing with the oxygen slope for the AF stage with respect to the sodium slope for the CE stage. In the light of simple models of chemical evolution applied to M13, oxygen depletion appears to be mainly turned into sodium enrichment for [O/H]≥-1.35 and [Na/H]≤-1.45, while one or more largely preferred channels occur for [O/H]<-1.35 and [Na/H]>-1.45. In addition, the primordial to the current M13 mass ratio can be inferred from the true sodium yield in units of the sodium solar abundance. Though the above results are mainly qualitative due to large (∓.5 dex) uncertainties in abundance

  16. Redistribution of oxygen ions in single crystal YBa2Cu3O7-x owing to external hydrostatic pressure

    NASA Astrophysics Data System (ADS)

    Boiko, Yu. I.; Bogdanov, V. V.; Vovk, R. V.; Khadzhai, G. Ya.; Savich, S. V.

    2018-01-01

    The effect of high hydrostatic pressure on the temperature dependences of the electrical resistance in the basal plane of single crystal YBa2Cu3O7-x with an oxygen deficit is studied. It is found that an external hydrostatic pressure P ≈ 7 kbar substantially intensifies the diffusive coalescence of oxygen clusters, i.e., causes an increase in their average size. This, in turn, produces an increased number of negative U-centers whose presence leads to the appearance of a phase capable of generating paired carriers of electrical charge and is, therefore, characterized by a higher transition temperature Tc. Changes in the form of the temperature and time dependences of the electrical resistivity under external hydrostatic pressure are discussed in terms of this same hypothesis regarding the mechanism of diffusive coalescence of oxygen clusters.

  17. CHROMOSPHERIC MODELS AND THE OXYGEN ABUNDANCE IN GIANT STARS

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

    Dupree, A. K.; Avrett, E. H.; Kurucz, R. L., E-mail: dupree@cfa.harvard.edu

    Realistic stellar atmospheric models of two typical metal-poor giant stars in Omega Centauri, which include a chromosphere (CHR), influence the formation of optical lines of O i: the forbidden lines (λ6300, λ6363) and the infrared triplet (λλ7771−7775). One-dimensional semi-empirical non-local thermodynamic equilibrium (LTE) models are constructed based on observed Balmer lines. A full non-LTE formulation is applied for evaluating the line strengths of O i, including photoionization by the Lyman continuum and photoexcitation by Lyα and Lyβ. Chromospheric models (CHR) yield forbidden oxygen transitions that are stronger than those in radiative/convective equilibrium (RCE) models. The triplet oxygen lines from highmore » levels also appear stronger than those produced in an RCE model. The inferred oxygen abundance from realistic CHR models for these two stars is decreased by factors of ∼3 as compared to values derived from RCE models. A lower oxygen abundance suggests that intermediate-mass AGB stars contribute to the observed abundance pattern in globular clusters. A change in the oxygen abundance of metal-poor field giants could affect models of deep mixing episodes on the red giant branch. Changes in the oxygen abundance can impact other abundance determinations that are critical to astrophysics, including chemical tagging techniques and galactic chemical evolution.« less

  18. Influence of temperature on the molecular composition of ions and charged clusters during pure biogenic nucleation

    NASA Astrophysics Data System (ADS)

    Frege, Carla; Ortega, Ismael K.; Rissanen, Matti P.; Praplan, Arnaud P.; Steiner, Gerhard; Heinritzi, Martin; Ahonen, Lauri; Amorim, António; Bernhammer, Anne-Kathrin; Bianchi, Federico; Brilke, Sophia; Breitenlechner, Martin; Dada, Lubna; Dias, António; Duplissy, Jonathan; Ehrhart, Sebastian; El-Haddad, Imad; Fischer, Lukas; Fuchs, Claudia; Garmash, Olga; Gonin, Marc; Hansel, Armin; Hoyle, Christopher R.; Jokinen, Tuija; Junninen, Heikki; Kirkby, Jasper; Kürten, Andreas; Lehtipalo, Katrianne; Leiminger, Markus; Mauldin, Roy Lee; Molteni, Ugo; Nichman, Leonid; Petäjä, Tuukka; Sarnela, Nina; Schobesberger, Siegfried; Simon, Mario; Sipilä, Mikko; Stolzenburg, Dominik; Tomé, António; Vogel, Alexander L.; Wagner, Andrea C.; Wagner, Robert; Xiao, Mao; Yan, Chao; Ye, Penglin; Curtius, Joachim; Donahue, Neil M.; Flagan, Richard C.; Kulmala, Markku; Worsnop, Douglas R.; Winkler, Paul M.; Dommen, Josef; Baltensperger, Urs

    2018-01-01

    It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1-2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α-pinene at 5 °C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and -25 °C). Most negative HOM clusters include a nitrate (NO3-) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH4+) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ˜ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (-25 °C), the presence of C30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.

  19. Spectroscopic insights into the oxygen-tolerant membrane-associated [NiFe] hydrogenase of Ralstonia eutropha H16.

    PubMed

    Saggu, Miguel; Zebger, Ingo; Ludwig, Marcus; Lenz, Oliver; Friedrich, Bärbel; Hildebrandt, Peter; Lendzian, Friedhelm

    2009-06-12

    This study provides the first spectroscopic characterization of the membrane-bound oxygen-tolerant [NiFe] hydrogenase (MBH) from Ralstonia eutropha H16 in its natural environment, the cytoplasmic membrane. The H2-converting MBH is composed of a large subunit, harboring the [NiFe] active site, and a small subunit, capable in coordinating one [3Fe4S] and two [4Fe4S] clusters. The hydrogenase dimer is electronically connected to a membrane-integral cytochrome b. EPR and Fourier transform infrared spectroscopy revealed a strong similarity of the MBH active site with known [NiFe] centers from strictly anaerobic hydrogenases. Most redox states characteristic for anaerobic [NiFe] hydrogenases were identified except for one remarkable difference. The formation of the oxygen-inhibited Niu-A state was never observed. Furthermore, EPR data showed the presence of an additional paramagnetic center at high redox potential (+290 mV), which couples magnetically to the [3Fe4S] center and indicates a structural and/or redox modification at or near the proximal [4Fe4S] cluster. Additionally, significant differences regarding the magnetic coupling between the Nia-C state and [4Fe4S] clusters were observed in the reduced form of the MBH. The spectroscopic properties are discussed with regard to the unusual oxygen tolerance of this hydrogenase and in comparison with those of the solubilized, dimeric form of the MBH.

  20. Sol-gel type synthesis of Bi{sub 2}(Sr,Ta{sub 2})O{sub 9} using an acetate based system

    DOEpatents

    Boyle, T.J.

    1997-11-04

    A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen. 6 figs.

  1. Characterization of [4Fe-4S]-containing and cluster-free forms of Streptomyces WhiD

    PubMed Central

    Crack, Jason C.; den Hengst, Chris D.; Jakimowicz, Piotr; Subramanian, Sowmya; Johnson, Michael K.; Buttner, Mark J.; Thomson, Andrew J.; Le Brun, Nick E.

    2009-01-01

    WhiD, a member of the WhiB-like (Wbl) family of iron-sulfur proteins found exclusively within the actinomycetes, is required for the late stages of sporulation in Streptomyces coelicolor. Like all other Wbl proteins, WhiD has not so far been purified in a soluble form that contains a significant amount of cluster and characterization has relied on cluster-reconstituted protein. Thus, a major goal in Wbl research is to obtain and characterize native protein containing iron-sulfur clusters. Here we report the analysis of S. coelicolor WhiD purified anaerobically from E. coli as a soluble protein containing a single [4Fe-4S]2+ cluster ligated by four cysteines. Upon exposure to oxygen, spectral features associated with the [4Fe-4S] cluster were lost in a slow reaction that unusually yielded apo-WhiD directly without significant concentrations of cluster intermediates. This process was found to be highly pH dependent with an optimal stability observed between pH 7.0 and 8.0. Low molecular weight thiols, including a mycothiol analogue and thioredoxin, exerted a small but significant protective effect against WhiD cluster loss, an activity that could be of physiological importance. [4Fe-4S]2+ WhiD was found to react much more rapidly with superoxide than with either oxygen or hydrogen peroxide, which may also be of physiological significance. Loss of the [4Fe-4S] cluster to form apo-protein destabilized the protein fold significantly, but did not lead to complete unfolding. Finally, apo-WhiD exhibited negligible activity in an insulin-based disulfide reductase assay demonstrating that it does not function as a general protein disulfide reductase. PMID:19954209

  2. Effect of aging at 1040 C (1900 F) on the ductility and structure of a tantalum alloy, T-111

    NASA Technical Reports Server (NTRS)

    Watson, G. K.; Stephens, J. R.

    1972-01-01

    The post-aging embrittlement of T-111 (tantalum - 8-percent tungsten - 2-percent hafnium) following exposure for up to about 10,000 hours at 1040 C in either vacuum or liquid lithium was investigated for sheet and tubing samples. This thermal aging was shown to greatly increase the sensitivity of T-111 to hydrogen embrittlement during subsequent room temperature specimen processing or testing. The hydrogen embrittlement problem can be avoided by preventing exposure to the T-111 to moisture during post-aging processing or testing. Aging at 1040 C also resulted in formation of HfO2 particles at grain boundaries, which may contribute to the observed embrittlement.

  3. Oxygen-related vacancy-type defects in ion-implanted silicon

    NASA Astrophysics Data System (ADS)

    Pi, X. D.; Burrows, C. P.; Coleman, P. G.; Gwilliam, R. M.; Sealy, B. J.

    2003-10-01

    Czochralski silicon samples implanted to a dose of 5 × 1015 cm-2 with 0.5 MeV O and to a dose of 1016 cm-2 with 1 MeV Si, respectively, have been studied by positron annihilation spectroscopy. The evolution of divacancies to vacancy (V)-O complexes is out-competed by V-interstitial (I) recombination at 400 and 500 °C in the Si- and O-implanted samples; the higher oxygen concentration makes the latter temperature higher. The defective region shrinks as the annealing temperature increases as interstitials are injected from the end of the implantation range (Rp). VmOn (m> n) are formed in the shallow region most effectively at 700 °C for both Si and O implantation. VxOy (x< y) are produced near Rp by the annealing. At 800 °C, implanted Si ions diffuse and reduce m and implanted O ions diffuse and increase n in VmOn. All oxygen-related vacancy-type defects appear to begin to dissociate at 950 °C, with the probable formation of oxygen clusters. At 1100 °C, oxygen precipitates appear to form just before Rp in O-implanted silicon.

  4. Mammalian Fe-S cluster biogenesis and its implication in disease.

    PubMed

    Beilschmidt, Lena K; Puccio, Hélène M

    2014-05-01

    Iron-sulfur (Fe-S) clusters are inorganic cofactors that are ubiquitous and essential. Due to their chemical versatility, Fe-S clusters are implicated in a wide range of protein functions including mitochondrial respiration and DNA repair. Composed of iron and sulfur, they are sensible to oxygen and their biogenesis requires a highly conserved protein machinery that facilitates assembly of the cluster as well as its insertion into apoproteins. Mitochondria are the central cellular compartment for Fe-S cluster biogenesis in eukaryotic cells and the importance of proper function of this biogenesis for life is highlighted by a constantly increasing number of human genetic diseases that are associated with dysfunction of this Fe-S cluster biogenesis pathway. Although these disorders are rare and appear dissimilar, common aspects are found among them. This review will give an overview on what is known on mammalian Fe-S cluster biogenesis today, by putting it into the context of what is known from studies from lower model organisms, and focuses on the associated diseases, by drawing attention to the respective mutations. Finally, it outlines the importance of adequate cellular and murine models to uncover not only each protein function, but to resolve their role and requirement throughout the mammalian organism. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

  5. Deuterium desorption from ion-irradiated tantalum and effects on surface morphology

    NASA Astrophysics Data System (ADS)

    Novakowski, T. J.; Sundaram, A.; Tripathi, J. K.; Gonderman, S.; Hassanein, A.

    2018-06-01

    Compared to tungsten (W), tantalum (Ta) has shown superior resistance to helium (He)-induced surface morphology changes under fusion-relevant irradiation conditions. However, Ta is also expected to have a stronger interaction with hydrogen isotopes, potentially limiting its use as a plasma-facing material. Despite these concerns, detailed investigations on hydrogen irradiation effects on Ta are scarce. In this study, pristine and fuzzy (He+ ion-irradiated) Ta samples are irradiated with 120 eV deuterium (D) ions at various temperatures and examined with a combination of thermal desorption spectroscopy (TDS), scanning electron microscopy (SEM), and optical reflectivity. TDS reveals discrete D desorption temperatures at 660 and 760 K, corresponding to trapping energies of 1.82 and 2.11 eV, respectively. Although D is retained in Ta both in higher quantities and at higher temperatures compared to W, extreme surface temperatures expected in tokamak divertors may exceed these desorption temperatures and counteract retention. Furthermore, this study indicates that Ta is relatively resistant to adverse surface structuring under D+ ion irradiation. In fact, D+ is shown to prevent and suppress Ta fuzz formation in sequential D+/He+ ion irradiation experiments. While further investigations are needed to elucidate this behavior, these initial investigations show a strong potential for the use of Ta as a PFC material.

  6. Low emissivity high-temperature tantalum thin film coatings for silicon devices

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

    Rinnerbauer, Veronika; Senkevich, Jay J.; Joannopoulos, John D.

    The authors study the use of thin ( ~230 nm ) tantalum (Ta) layers on silicon (Si) as a low emissivity (high reflectivity) coating for high-temperature Si devices. Such coatings are critical to reduce parasitic radiation loss, which is one of the dominant loss mechanisms at high temperatures (above 700 °C ). The key factors to achieve such a coating are low emissivity in the near infrared and superior thermal stability at high operating temperatures. The authors investigated the emissivity of Ta coatings deposited on Si with respect to deposition parameters, and annealing conditions, and temperature. The authors found thatmore » after annealing at temperatures ≥900 °C the emissivity in the near infrared ( 1–3 μm ) was reduced by a factor of 2 as compared to bare Si. In addition, the authors measured thermal emission at temperatures from 700 to 1000 °C , which is stable up to a heater temperature equal to the annealing temperature. Furthermore, Auger electron spectroscopy profiles of the coatings before and after annealing were taken to evaluate thermal stability. A thin (about 70 nm) Ta₂O₅ layer was found to act as an efficient diffusion barrier between the Si substrate and the Ta layer to prevent Si diffusion.« less

  7. Modeling of grain size strengthening in tantalum at high pressures and strain rates

    DOE PAGES

    Rudd, Robert E.; Park, H. -S.; Cavallo, R. M.; ...

    2017-01-01

    Laser-driven ramp wave compression experiments have been used to investigate the strength (flow stress) of tantalum and other metals at high pressures and high strain rates. Recently this kind of experiment has been used to assess the dependence of the strength on the average grain size of the material, finding no detectable variation with grain size. The insensitivity to grain size has been understood theoretically to result from the dominant effect of the high dislocation density generated at the extremely high strain rates of the experiment. Here we review the experiments and describe in detail the multiscale strength model usedmore » to simulate them. The multiscale strength model has been extended to include the effect of geometrically necessary dislocations generated at the grain boundaries during compatible plastic flow in the polycrystalline metal. Lastly, we use the extended model to make predictions of the threshold strain rates and grain sizes below which grain size strengthening would be observed in the laser-driven Rayleigh-Taylor experiments.« less

  8. Why did Nature choose manganese to make oxygen?

    PubMed Central

    Armstrong, Fraser A

    2007-01-01

    This paper discusses the suitability of manganese for its function in catalysing the formation of molecular oxygen from water. Manganese is an abundant element. In terms of its inherent properties, Mn has a particularly rich redox chemistry compared with other d-block elements, with several oxidizing states accessible. The most stable-state Mn2+ behaves like a Group 2 element—it is mobile, weakly complexing, easily taken up by cells and redox-inactive in simple aqueous media. Only in the presence of suitable ligands does Mn2+ become oxidized, so it provides an uncomplicated building unit for the oxygen-evolving centre (OEC). The intermediate oxidation states Mn(III) and Mn(IV) are strongly complexed by O2− and form robust mixed-valence poly-oxo clusters in which the Mn(IV)/Mn(III) ratio can be elevated, one electron at a time, accumulating oxidizing potential and capacity. The OEC is a Mn4CaOx cluster that undergoes sequential oxidations by P680+ at potentials above 1 V, ultimately to a super-oxidized level that includes one Mn(V) or a Mn(IV)-oxyl radical. The latter is powerfully oxidizing and provides the crucial ‘power stroke’ necessary to generate an O–O bond. This leaves a centre still rich in Mn(IV), ensuring a rapid follow-through to O2. PMID:17971329

  9. Structural basis for a [4Fe-3S] cluster in the oxygen-tolerant membrane-bound [NiFe]-hydrogenase.

    PubMed

    Shomura, Yasuhito; Yoon, Ki-Seok; Nishihara, Hirofumi; Higuchi, Yoshiki

    2011-10-16

    Membrane-bound respiratory [NiFe]-hydrogenase (MBH), a H(2)-uptake enzyme found in the periplasmic space of bacteria, catalyses the oxidation of dihydrogen: H(2) → 2H(+) + 2e(-) (ref. 1). In contrast to the well-studied O(2)-sensitive [NiFe]-hydrogenases (referred to as the standard enzymes), MBH has an O(2)-tolerant H(2) oxidation activity; however, the mechanism of O(2) tolerance is unclear. Here we report the crystal structures of Hydrogenovibrio marinus MBH in three different redox conditions at resolutions between 1.18 and 1.32 Å. We find that the proximal iron-sulphur (Fe-S) cluster of MBH has a [4Fe-3S] structure coordinated by six cysteine residues--in contrast to the [4Fe-4S] cubane structure coordinated by four cysteine residues found in the proximal Fe-S cluster of the standard enzymes--and that an amide nitrogen of the polypeptide backbone is deprotonated and additionally coordinates the cluster when chemically oxidized, thus stabilizing the superoxidized state of the cluster. The structure of MBH is very similar to that of the O(2)-sensitive standard enzymes except for the proximal Fe-S cluster. Our results give a reasonable explanation why the O(2) tolerance of MBH is attributable to the unique proximal Fe-S cluster; we propose that the cluster is not only a component of the electron transfer for the catalytic cycle, but that it also donates two electrons and one proton crucial for the appropriate reduction of O(2) in preventing the formation of an unready, inactive state of the enzyme.

  10. Thermal O-H Bond Activation of Water as Mediated by Heteronuclear [Al2Mg2O5]•+: Evidence for Oxygen-Atom Scrambling.

    PubMed

    Geng, Caiyun; Li, Jilai; Weiske, Thomas; Schwarz, Helmut

    2018-06-25

    Mechanistic insight into the thermal O-H bond activation of water by the cubane-like, prototypical heteronuclear oxide cluster [Al 2 Mg 2 O 5 ] •+ has been derived from a combined experimental/computational study. Experiments in the highly diluted gas phase using Fourier transform ion-cyclotron resonance mass spectrometry show that hydrogen-atom abstraction from water by the cluster cation [Al 2 Mg 2 O 5 ] •+ occurs at ambient conditions accompanied by the liberation of an OH • radical. Due to a complete randomization of all oxygen atoms prior to fragmentation about 83% of the oxygen atoms of the hydroxyl radical released originate from the oxide cluster itself. The experimental findings are supported by detailed high-level quantum chemical calculations. The theoretical analysis reveals that the transfer of a formal hydrogen atom from water to the metal-oxide cation can proceed mechanistically via proton- or hydrogen-atom transfer exploiting different active sites of the cluster oxide. In addition to the unprecedented oxygen-atom scrambling, one of the more general and quite unexpected findings concerns the role of spin density at the hydrogen-acceptor oxide atom. While this feature is so crucial for [M-O] + /CH 4 couples, it is much less important in the O-H bond activation of water.

  11. Thermal transport in tantalum oxide films for memristive applications

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

    Landon, Colin D.; Wilke, Rudeger H. T.; Brumbach, Michael T.

    2015-07-13

    The thermal conductivity of amorphous TaO{sub x} memristive films having variable oxygen content is measured using time domain thermoreflectance. Thermal transport is described by a two-part model where the electrical contribution is quantified via the Wiedemann-Franz relation and the vibrational contribution by the minimum thermal conductivity limit for amorphous solids. The vibrational contribution remains constant near 0.9 W/mK regardless of oxygen concentration, while the electrical contribution varies from 0 to 3.3 W/mK. Thus, the dominant thermal carrier in TaO{sub x} switches between vibrations and charge carriers and is controllable either by oxygen content during deposition, or dynamically by field-induced charge state migration.

  12. Molecular dynamics simulations of oxygen vacancy diffusion in SrTiO3.

    PubMed

    Schie, Marcel; Marchewka, Astrid; Müller, Thomas; De Souza, Roger A; Waser, Rainer

    2012-12-05

    A classical force-field model with partial ionic charges was applied to study the behaviour of oxygen vacancies in the perovskite oxide strontium titanate (SrTiO(3)). The dynamical behaviour of these point defects was investigated as a function of temperature and defect concentration by means of molecular dynamics (MD) simulations. The interaction between oxygen vacancies and an extended defect, here a Σ3(111) grain boundary, was also examined by means of MD simulations. Analysis of the vacancy distribution revealed considerable accumulation of vacancies in the envelope of the grain boundary. The possible clustering of oxygen vacancies in bulk SrTiO(3) was studied by means of static lattice calculations within the Mott-Littleton approach. All binary vacancy-vacancy configurations were found to be energetically unfavourable.

  13. Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol.

    PubMed

    Grundner, Sebastian; Markovits, Monica A C; Li, Guanna; Tromp, Moniek; Pidko, Evgeny A; Hensen, Emiel J M; Jentys, Andreas; Sanchez-Sanchez, Maricruz; Lercher, Johannes A

    2015-06-25

    Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon-hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite.

  14. Phasing and structure of bestrophin-1: a case study in the use of heavy-atom cluster compounds with multi-subunit transmembrane proteins

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

    Kane Dickson, Veronica

    The purification and three-dimensional crystallization of membrane proteins are commonly affected by a cumulation of pathologies that are less prevalent in their soluble counterparts. This may include severe anisotropy, poor spot shape, poor to moderate-resolution diffraction, crystal twinning, translational pseudo-symmetry and poor uptake of heavy atoms for derivatization. Such challenges must be circumvented by adaptations in the approach to crystallization and/or phasing. Here, an example of a protein that exhibited all of the above-mentioned complications is presented. Bestrophin-1 is a eukaryotic calcium-activated chloride channel, the structure of which was recently determined in complex with monoclonal antibody fragments using SAD phasingmore » with tantalum bromide clusters (Ta 6Br 12·Br 2). Some of the obstacles to obtaining improved diffraction and phasing for this particular channel are discussed, as well as the approach and adaptations that were key to determining the structure.« less

  15. Cluster headache: clinical features and therapeutic options.

    PubMed

    Gaul, Charly; Diener, Hans-Christoph; Müller, Oliver M

    2011-08-01

    Cluster headache is the most common type of trigemino-autonomic headache, affecting ca. 120 000 persons in Germany alone. The attacks of pain are in the periorbital area on one side, last 90 minutes on average, and are accompanied by trigemino-autonomic manifestations and restlessness. Most patients have episodic cluster headache; about 15% have chronic cluster headache, with greater impairment of their quality of life. The attacks often possess a circadian and seasonal rhythm. Selective literature review Oxygen inhalation and triptans are effective acute treatment for cluster attacks. First-line drugs for attack prophylaxis include verapamil and cortisone; alternatively, lithium and topiramate can be given. Short-term relief can be obtained by the subcutaneous infiltration of local anesthetics and steroids along the course of the greater occipital nerve, although most of the evidence in favor of this is not derived from randomized clinical trials. Patients whose pain is inadequately relieved by drug treatment can be offered newer, invasive treatments, such as deep brain stimulation in the hypothalamus (DBS) and bilateral occipital nerve stimulation (ONS). Pharmacotherapy for the treatment of acute attacks and for attack prophylaxis is effective in most patients. For the minority who do not gain adequate relief, newer invasive techniques are available in some referral centers. Definitive conclusions as to their value cannot yet be drawn from the available data.

  16. Thermal transport in tantalum oxide films for memristive applications

    DOE PAGES

    Landon, Colin Donald; Wilke, Rudeger H. T.; Brumbach, Michael T.; ...

    2015-07-15

    The thermal conductivity of amorphous TaO x memristive films having variable oxygen content is measured using time domain thermoreflectance. Furthermore, the thermal transport is described by a two-partmodel where the electrical contribution is quantified via the Wiedemann-Franz relation and the vibrational contribution by the minimum thermal conductivity limit for amorphous solids. Additionally, the vibrational contribution remains constant near 0.9 W/mK regardless of oxygen concentration, while the electrical contribution varies from 0 to 3.3 W/mK. Thus, the dominant thermal carrier in TaO x switches between vibrations and charge carriers and is controllable either by oxygen content during deposition, or dynamically bymore » field-induced charge state migration.« less

  17. The mitochondrial outer membrane protein mitoNEET is a redox enzyme catalyzing electron transfer from FMNH2 to oxygen or ubiquinone.

    PubMed

    Wang, Yiming; Landry, Aaron P; Ding, Huangen

    2017-06-16

    Increasing evidence suggests that mitoNEET, a target of the type II diabetes drug pioglitazone, is a key regulator of energy metabolism in mitochondria. MitoNEET is anchored to the mitochondrial outer membrane via its N-terminal α helix domain and hosts a redox-active [2Fe-2S] cluster in its C-terminal cytosolic region. The mechanism by which mitoNEET regulates energy metabolism in mitochondria, however, is not fully understood. Previous studies have shown that mitoNEET specifically interacts with the reduced flavin mononucleotide (FMNH 2 ) and that FMNH 2 can quickly reduce the mitoNEET [2Fe-2S] clusters. Here we report that the reduced mitoNEET [2Fe-2S] clusters can be readily oxidized by oxygen. In the presence of FMN, NADH, and flavin reductase, which reduces FMN to FMNH 2 using NADH as the electron donor, mitoNEET mediates oxidation of NADH with a concomitant reduction of oxygen. Ubiquinone-2, an analog of ubiquinone-10, can also oxidize the reduced mitoNEET [2Fe-2S] clusters under anaerobic or aerobic conditions. Compared with oxygen, ubiquinone-2 is more efficient in oxidizing the mitoNEET [2Fe-2S] clusters, suggesting that ubiquinone could be an intrinsic electron acceptor of the reduced mitoNEET [2Fe-2S] clusters in mitochondria. Pioglitazone or its analog NL-1 appears to inhibit the electron transfer activity of mitoNEET by forming a unique complex with mitoNEET and FMNH 2 The results suggest that mitoNEET is a redox enzyme that may promote oxidation of NADH to facilitate enhanced glycolysis in the cytosol and that pioglitazone may regulate energy metabolism in mitochondria by inhibiting the electron transfer activity of mitoNEET. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

  18. Separation of no-carrier-added rhenium from bulk tantalum by the sodium malonate-PEG aqueous biphasic system.

    PubMed

    Dutta, Binita; Lahiri, Susanta; Tomar, B S

    2014-02-01

    The aqueous biphasic system (ABS) involving sodium malonate-polyethylene glycol (PEG) phases has been applied for the first time for separation of no-carrier-added (183)Re (T1/2=70 d) from α-particle irradiated bulk tantalum target. The various ABS conditions were applied for investigating the separation by varying pH, temperature, PEG-molecular weight, concentration of salt. The extraction pattern was hardly affected by change in pH and the molecular weight of PEG. One step separation of nca (183)Re from Ta was achieved at the optimal conditions of (i) 50% (w/w) PEG-4000-2 M sodium malonate, 40 °C and (ii) 50% (w/w) PEG-4000-3 M sodium malonate, room temperature (27 °C). © 2013 Published by Elsevier Ltd.

  19. Density functional theory study of ethylene partial oxidation on Ag 7 clusters

    NASA Astrophysics Data System (ADS)

    Yu, Hua-Gen

    2006-11-01

    The partial oxidation reaction of ethylene on neutral and anionic Ag 7 clusters has been studied using the BPW91 hybrid DFT method with the Stuttgart RSC97 relativistic pseudopotential for the 28-electron ionic core of Ag. The atomic oxygen reaction mechanism is mainly addressed. Results show that the reaction occurs via a stable oxametallacycle intermediate ( AgOCH4p, p = 0 or -1), but it involves small reaction barriers along the reaction path. The ZPE-corrected barrier heights are obtained as 0.7-6.5 kcal/mole. In addition, the structure and anionic effects of Ag 7 clusters are also discussed.

  20. Crystallization of carbon-oxygen mixtures in white dwarf stars.

    PubMed

    Horowitz, C J; Schneider, A S; Berry, D K

    2010-06-11

    We determine the phase diagram for dense carbon-oxygen mixtures in white dwarf (WD) star interiors using molecular dynamics simulations involving liquid and solid phases. Our phase diagram agrees well with predictions from Ogata et al. and from Medin and Cumming and gives lower melting temperatures than Segretain et al. Observations of WD crystallization in the globular cluster NGC 6397 by Winget et al. suggest that the melting temperature of WD cores is close to that for pure carbon. If this is true, our phase diagram implies that the central oxygen abundance in these stars is less than about 60%. This constraint, along with assumptions about convection in stellar evolution models, limits the effective S factor for the 12C(α,γ)16O reaction to S(300)≤170  keV b.