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Sample records for acid metallic carbides

  1. Fluorine-Doped and Partially Oxidized Tantalum Carbides as Nonprecious Metal Electrocatalysts for Methanol Oxidation Reaction in Acidic Media.

    PubMed

    Yue, Xin; He, Chunyong; Zhong, Chengyong; Chen, Yuanping; Jiang, San Ping; Shen, Pei Kang

    2016-03-16

    A nonprecious metal electrocatalyst based on fluorine-doped tantalum carbide with an oxidative surface on graphitized carbon (TaCx FyOz/(g)C) is developed by using a simple one-pot in situ ion exchange and adsorption method, and the TaCxFyOz/(g)C shows superior performance and durability for methanol oxidation reaction and extreme tolerance to CO poisoning in acidic media. PMID:26779940

  2. Method of preparing silicon carbide particles dispersed in an electrolytic bath for composite electroplating of metals

    DOEpatents

    Peng, Yu-Min; Wang, Jih-Wen; Liue, Chun-Ying; Yeh, Shinn-Horng

    1994-01-01

    A method for preparing silicon carbide particles dispersed in an electrolytic bath for composite electroplating of metals includes the steps of washing the silicon carbide particles with an organic solvent; washing the silicon carbide particles with an inorganic acid; grinding the silicon carbide particles; and heating the silicon carbide particles in a nickel-containing solution at a boiling temperature for a predetermined period of time.

  3. METHOD FOR COATING GRAPHITE WITH METALLIC CARBIDES

    DOEpatents

    Steinberg, M.A.

    1960-03-22

    A method for producing refractory coatings of metallic carbides on graphite was developed. In particular, the graphite piece to be coated is immersed in a molten solution of 4 to 5% by weight of zirconium, titanium, or niobium dissolved in tin. The solution is heated in an argon atmosphere to above 1400 deg C, whereby the refractory metal reacts with the surface of the graphite to form a layer of metalic carbide. The molten solution is cooled to 300 to 400 deg C, and the graphite piece is removed. Excess tin is wiped from the graphite, which is then heated in vacuum to above 2300 deg C. The tin vaporizes from the graphite surface, leaving the surface coated with a tenacious layer of refractory metallic carbide.

  4. Metal seated ball valves with carbide coatings

    SciTech Connect

    Manuel, R.; Yung, E.

    1994-12-31

    Valvtechnologies valves utilize Alloy Carbide HVOF Sprayed RAM{reg_sign} Hardcoatings such as Chrome Carbide and Tungsten Carbide Coatings. The coatings are applied using a Proprietary Gun combusting Hydrogen and Oxygen. The powders are heated and accelerated toward the valve component forming a tenaciously bonded coating. Each coating is chosen depending upon the environment the valve will operate in. These valves have solved many Petro-Chemical service life problems. Free from the temperature limits of elastomers, the only sealing materials are metal, the carbides and grafoils (carbons). Operating temperatures to 982 C (1,800 F) are typical limits; 649 C (1,200 F) is common. Lower temperatures are also common, even in the cryogenic range. Even though the coatings have low thermal expansion rates, RAM{reg_sign} Hardcoatings can expand and contract with the base material and still maintain a seal.

  5. Method of coating graphite tubes with refractory metal carbides

    DOEpatents

    Wohlberg, C.

    1973-12-11

    A method of coating graphite tubes with a refractory metal carbide is described. An alkali halide is reacted with a metallic oxide, the metallic portion being selected from the IVth or Vth group of the Periodic Table, the resulting salt reacting in turn with the carbon to give the desired refractory metal carbide coating. (Official Gazette)

  6. Chemical vapour deposition: Transition metal carbides go 2D

    NASA Astrophysics Data System (ADS)

    Gogotsi, Yury

    2015-11-01

    The unique properties of 2D materials, such as graphene or transition metal dichalcogenides, have been attracting much attention in the past decade. Now, metallically conductive and even superconducting transition metal carbides are entering the game.

  7. Synthesis of zirconium carbide nanosized powders by pursed wire discharge in oleic acid

    NASA Astrophysics Data System (ADS)

    Sugashima, Kenta; Suzuki, Kazuma; Suzuki, Tsuneo; Nakayama, Tadachika; Suematsu, Hisayuki; Niihara, Koichi

    2016-01-01

    In this study, we propose novel PWD methods in inert gas mixed organic vapor and organic liquid which work as harmless carbon sources. Metal zirconium wire evaporation by PWD in organic vapor or liquid media was investigated. It was confirmed that in the PWD process using oleic acid liquid, single phase zirconium carbide nanopowders were synthesized by a reaction between Zr vapor and oleic acid. A new method for synthesis of carbide nanopowders was developed using the PWD in organic liquid. Therefore, the present result suggested that PWD method in oleic acid liquids is effective for the synthesis of carbide nanopowders.

  8. Tribological properties of silicon carbide in metal removal process

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1980-01-01

    This paper reviews material properties of adhesion, friction and wear of single-crystal silicon carbide in contact with metals and alloys involved in a metal removal process such as grinding. The tribological properties in the metal removal processes are divided into properties which remove metal by adhesion between sliding surfaces, and metal removal by silicon carbide sliding against a metal, indenting it, and plowing a series of grooves or furrows. The paper also deals with fracture and deformation characteristics of the silicon carbide surface; the adhesion, friction and metal transfer to silicon carbide is related to the relative chemical activity of the metals. Atomic size and content of alloying elements play a dominant role in controlling adhesion and friction properties of alloys. The friction and abrasive wear decrease as the shear strength of the bulk metal increases.

  9. METHOD OF COATING GRAPHITE WITH STABLE METAL CARBIDES AND NITRIDES

    DOEpatents

    Gurinsky, D.H.

    1959-10-27

    A method is presented for forming protective stable nitride and carbide compounds on the surface of graphite. This is accomplished by contacting the graphite surface with a fused heavy liquid metal such as bismuth or leadbismuth containing zirconium, titanium, and hafnium dissolved or finely dispersed therein to form a carbide and nitride of at least one of the dissolved metals on the graphite surface.

  10. Metal-ceramics based on nanostructured boron carbide

    NASA Astrophysics Data System (ADS)

    Antadze, M.; Chedia, R.; Tsagareishvili, O.; Mikeladze, A.; Gacheciladze, A.; Margiev, B.; Gabunia, D.; Tsuladze, T.; Khantadze, D.

    2012-11-01

    Boron carbide has unique physicochemical and mechanical properties such as: high modulus of elasticity, high value of a strength-to-density ratio, heightened wear-resistance in unfriendly environment, etc., however dense product of boron carbide is not widely used in the area of engineering due to low impact strength, brittleness and low thermal conductivity of this material. Recent efforts of the scientists working in this area are focused on creating the so-called hetero-modulus metal-ceramic composite materials comprised of high-modulus ceramic and a metallic phase as an elastic binder. Creation of effective boron carbide based hetero-modulus materials is possible when a) boron carbide has a high degree of dispersion; b) metallic binder has a high adhesion ability and low reactivity toward boron carbide. The technology developed for producing boron carbide based metal-ceramic materials provides pyrolysis (900-1100 °C) of the precursors comprised of amorphous boron, carbon-chain polymers and appropriate metal salts. Each particle of the obtained powder contains both - nanostructured components of boron carbide and of a binding metallic phase. The fabricated metal-ceramic product has heightened parameters of impact strength and thermal conductivity in parallel with the retained unique properties of boron carbide.

  11. The diffusion bonding of silicon carbide and boron carbide using refractory metals

    SciTech Connect

    Cockeram, B.V.

    1999-10-01

    Joining is an enabling technology for the application of structural ceramics at high temperatures. Metal foil diffusion bonding is a simple process for joining silicon carbide or boron carbide by solid-state, diffusive conversion of the metal foil into carbide and silicide compounds that produce bonding. Metal diffusion bonding trials were performed using thin foils (5 {micro}m to 100 {micro}m) of refractory metals (niobium, titanium, tungsten, and molybdenum) with plates of silicon carbide (both {alpha}-SiC and {beta}-SiC) or boron carbide that were lapped flat prior to bonding. The influence of bonding temperature, bonding pressure, and foil thickness on bond quality was determined from metallographic inspection of the bonds. The microstructure and phases in the joint region of the diffusion bonds were evaluated using SEM, microprobe, and AES analysis. The use of molybdenum foil appeared to result in the highest quality bond of the metal foils evaluated for the diffusion bonding of silicon carbide and boron carbide. Bonding pressure appeared to have little influence on bond quality. The use of a thinner metal foil improved the bond quality. The microstructure of the bond region produced with either the {alpha}-SiC and {beta}-SiC polytypes were similar.

  12. Electrocatalysis using transition metal carbide and oxide nanocrystals

    NASA Astrophysics Data System (ADS)

    Regmi, Yagya N.

    Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel

  13. Tribological properties of silicon carbide in metal removal process

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1980-01-01

    Material properties are considered as they relate to adhesion, friction, and wear of single crystal silicon carbide in contact with metals and alloys that are likely to be involved in a metal removal process such as grinding. Metal removal from adhesion between sliding surfaces in contact and metal removal as a result of the silicon carbide sliding against a metal, indenting into it, and plowing a series of grooves or furrows are discussed. Fracture and deformation characteristics of the silicon carbide surface are also covered. The adhesion, friction, and metal transfer to silicon carbide is related to the relative chemical activity of the metals. The more active the metal, the higher the adhesion and friction, and the greater the metal transfer to silicon carbide. Atomic size and content of alloying elements play a dominant role in controlling adhesion, friction, and abrasive wear properties of alloys. The friction and abrasive wear (metal removal) decrease linearly as the shear strength of the bulk metal increases. They decrease as the solute to solvent atomic radius ratio increases or decreases linearly from unity, and with an increase of solute content. The surface fracture of silicon carbide is due to cleavages of 0001, 10(-1)0, and/or 11(-2)0 planes.

  14. Radiation damage of transition metal carbides

    SciTech Connect

    Dixon, G.

    1991-01-01

    In this grant period we have investigated electrical properties of transition metal carbides and radiation-induced defects produced by low-temperature electron irradiation in them. Special attention has been given to the composition VC[sub 0.88] in which the vacancies on the carbon sublattice of this fcc crystal order to produce a V[sub 8]C[sub 7] superlattice. The existence of this superlattice structure was found to make the crystal somewhat resistant to radiation damage at low doses and/or at ambient temperature. At larger doses significant changes in the resistivity are produced. Annealing effects were observed which we believe to be connected with the reconstitution of the superlattice structure.

  15. Process for preparing metal-carbide-containing microspheres from metal-loaded resin beads

    DOEpatents

    Beatty, Ronald L.

    1976-01-01

    An improved method for treating metal-loaded resin microspheres is described which comprises heating a metal-loaded resin charge in an inert atmosphere at a pre-carbide-forming temperature under such conditions as to produce a microsphere composition having sufficient carbon as to create a substantially continuous carbon matrix and a metal-carbide or an oxide-carbide mixture as a dispersed phase(s) during carbide-forming conditions, and then heating the thus treated charge to a carbide-forming temperature.

  16. LIQUID PHASE SINTERING OF METALLIC CARBIDES

    DOEpatents

    Hammond, J.; Sease, J.D.

    1964-01-21

    An improved method is given for fabricating uranium carbide composites, The method comprises forming a homogeneous mixture of powdered uranium carbide, a uranium intermetallic compound which wets and forms a eutectic with said carbide and has a non-uranium component which has a relatively high vapor pressure at a temperature in the range 1200 to 1500 deg C, and an organic binder, pressing said mixture to a composite of desired green strength, and then vacuum sintering said composite at the eutectic forming temperature for a period sufficient to remove at least a portion of the non-uranium containing component of said eutectic. (AEC)

  17. Boron-carbide-aluminum and boron-carbide-reactive metal cermets

    DOEpatents

    Halverson, Danny C.; Pyzik, Aleksander J.; Aksay, Ilhan A.

    1986-01-01

    Hard, tough, lightweight boron-carbide-reactive metal composites, particularly boron-carbide-aluminum composites, are produced. These composites have compositions with a plurality of phases. A method is provided, including the steps of wetting and reacting the starting materials, by which the microstructures in the resulting composites can be controllably selected. Starting compositions, reaction temperatures, reaction times, and reaction atmospheres are parameters for controlling the process and resulting compositions. The ceramic phases are homogeneously distributed in the metal phases and adhesive forces at ceramic-metal interfaces are maximized. An initial consolidation step is used to achieve fully dense composites. Microstructures of boron-carbide-aluminum cermets have been produced with modulus of rupture exceeding 110 ksi and fracture toughness exceeding 12 ksi.sqroot.in. These composites and methods can be used to form a variety of structural elements.

  18. Improved adhesion of sputtered refractory carbides to metal substrates

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

    Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited in practice by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium base alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

  19. Process for preparing fine-grain metal carbide powder

    DOEpatents

    Kennedy, C.R.; Jeffers, F.P.

    Fine-grain metal carbide powder suitable for use in the fabrication of heat resistant products is prepared by coating bituminous pitch on SiO/sub 2/ or Ta/sub 2/O/sub 5/ particles, heating the coated particles to convert the bituminous pitch to coke, and then heating the particles to a higher temperature to convert the particles to a carbide by reaction of said coke therewith.

  20. Synthesis of Nanoporous Metals, Oxides, Carbides, and Sulfides: Beyond Nanocasting.

    PubMed

    Luc, Wesley; Jiao, Feng

    2016-07-19

    Nanoporous metal-based solids are of particular interest because they combine a large quantity of surface metal sites, interconnected porous networks, and nanosized crystalline walls, thus exhibiting unique physical and chemical properties compared to other nanostructures and bulk counterparts. Among all of the synthetic approaches, nanocasting has proven to be a highly effective method for the syntheses of metal oxides with three-dimensionally ordered porous structures and crystalline walls. A typical procedure involves a thermal annealing process of a porous silica template filled with an inorganic precursor (often a metal nitrate salt), which converts the precursor into a desired phase within the silica pores. The final step is the selective removal of the silica template in either a strong base or a hydrofluoric acid solution. In the past decade, nanocasting has become a popular synthetic approach and has enabled the syntheses of a variety of nanoporous metal oxides. However, there is still a lack of synthetic methods to fabricate nanoporous materials beyond simple metal oxides. Therefore, the development of new synthetic strategies beyond nanocasting has become an important direction. This Account describes new progress in the preparation of novel nanoporous metal-based solids for heterogeneous catalysis. The discussion begins with a method called dealloying, an effective method to synthesize nanoporous metals. The starting material is a metallic alloy containing two or more elements followed by a selective chemical or electrochemical leaching process that removes one of the preferential elements, resulting in a highly porous structure. Nanoporous metals, such as Cu, Ag, and CuTi, exhibit remarkable electrocatalytic properties in carbon dioxide reduction, oxygen reduction, and hydrogen evolution reactions. In addition, the syntheses of metal oxides with hierarchical porous structures are also discussed. On the basis of the choice of hard template, nanoporous

  1. Phase Behavior of Pseudobinary Precious Metal-Carbide Systems

    SciTech Connect

    Gregoire, John M.; Tague, Michele E.; Smith, Eva H.; Dale, Darren; DiSalvo, Francis J.; Abruña, Héctor D.; Hennig, Richard G.; van Dover, R. Bruce

    2010-11-15

    Transition metal carbides exhibit a variety of interesting material properties, including electrochemical stability. When combined with precious metals, Ta and W carbides have shown promise as fuel cell electrode materials; yet, the phase behavior of these precious metal-carbide systems is largely unexplored. We investigated P-M-C phase behavior with P = Pt, Pd, and Ru and M = Ta and W using composition spread thin films. We attained limited control of the deposited carbide phase through variation of the sputter atmosphere and demonstrated decreased corrosion of W-C materials with increasing C content. A high-throughput X-ray diffraction and X-ray fluorescence experiment was employed for thin film characterization, which revealed solubility of Pt, Pd, and Ru in cubic WC. Density functional calculations of the lattice parameter dependence on carbon concentration enabled the determination of carbon concentration from the X-ray data as a function of transition metal stoichiometry. Our measurement of variations in the C stoichiometry and evolution of thin film texture with transition metal composition yielded surprising results. We detail how the combination of the composition spread technique, the high-throughput thin film characterization, and the density functional modeling of ternary carbide alloys provided a deep understanding of the chemical systems.

  2. Metallicity of boron carbides at high pressure

    NASA Astrophysics Data System (ADS)

    Dekura, Haruhiko; Shirai, Koun; Yanase, Akira

    2010-03-01

    Electronic structure of semiconducting boron carbide at high pressure has been theoretically investigated, because of interests in the positive pressure dependence of resistivity, in the gap closure, and in the phase transition. The most simplest form B12(CCC) is assumed. Under assumptions of hydrostatic pressure and neglecting finite-temperature effects, boron carbide is quite stable at high pressure. The crystal of boron carbide is stable at least until a pressure higher than previous experiments showed. The gap closure occurs only after p=600 GPa on the assumption of the original crystal symmetry. In the low pressure regime, the pressure dependence of the energy gap almost diminishes, which is an exceptional case for semiconductors, which could be one of reasons for the positive pressure dependence of resistivity. A monotonous increase in the apex angle of rhombohedron suggests that the covalent bond continues to increase. The C chain inserted in the main diagonal of rhombohedral structure is the chief reason of this stability.

  3. Carbide and carbonitride surface treatment method for refractory metals

    DOEpatents

    Meyer, G.A.; Schildbach, M.A.

    1996-12-03

    A carbide and carbonitride surface treatment method for refractory metals is provided, in steps including, heating a part formed of boron, chromium, hafnium, molybdenum, niobium, tantalum, titanium, tungsten or zirconium, or alloys thereof, in an evacuated chamber and then introducing reaction gases including nitrogen and hydrogen, either in elemental or water vapor form, which react with a source of elemental carbon to form carbon-containing gaseous reactants which then react with the metal part to form the desired surface layer. Apparatus for practicing the method is also provided, in the form of a carbide and carbonitride surface treatment system including a reaction chamber, a source of elemental carbon, a heating subassembly and a source of reaction gases. Alternative methods of providing the elemental carbon and the reaction gases are provided, as well as methods of supporting the metal part, evacuating the chamber with a vacuum subassembly and heating all of the components to the desired temperature. 5 figs.

  4. Surface science and electrochemical studies of metal-modified carbides for fuel cells and hydrogen production

    NASA Astrophysics Data System (ADS)

    Kelly, Thomas Glenn

    intermediate on Rh/WC, and that the C-C bond was broken by 200 K. Finally, the suitability of metal-modified molybdenum carbide (Mo2C) as an ethanol decomposition catalyst was studied. A new reaction pathway of partial dehydrogenation to an acetaldehyde product was achieved by using Cu as an admetal. The second section of this dissertation was the study of metal-modified carbides for electrochemical hydrogen evolution. Previously, DFT calculations had predicted a similar hydrogen binding energy (HBE) between Pd-modified carbides and bulk Pd. Linear sweep voltammograms (LSV) demonstrated that Pd-modified WC and Mo2C possessed hydrogen evolution activity orders of magnitude greater than the bare carbides. The long-term stability of these surfaces under operating conditions was also examined. A two-hour chronopotentiometry experiment was performed, after which x-ray photoelectron spectroscopy (XPS) found that negligible loss of the Pd overlayer occurred. As an extension of this work, a DFT study was performed for several admetal/Mo2C combinations. It was shown that the HBE of these surfaces mostly correlated with the pure metal HBE. Some of these combinations were tested experimentally, but were unstable in the acidic electrolyte.

  5. Organic matter formed from hydrolysis of metal carbides of the iron peak of cosmic elemental abundance

    NASA Astrophysics Data System (ADS)

    Cataldo, Franco

    2003-01-01

    inside the iron peak of the cosmic abundances) has been discussed as well. A survey of the hydrolytic behaviour of other carbides has been included so that all lanthanides and actinides are considered as well as carbides of the second and third groups of the periodic table of elements and highly refractory carbides such as those of Ti, Zr, Ta and W have been briefly discussed. Furthermore, the hydrolysis of mixed metal carbides and nitrides is discussed, which gives a mixture of extremely interesting molecules that are considered the raw materials for the formation of the molecules of life: guanidine, methyl hydrazine, formic acid, hydrogen cyanide, urea, cyanamide, methylamine and formaldehyde. The hydrolysis of metal carbides has also been discussed within the framework of other reactions that are well considered in the present day in an astrochemical context: the ion-molecule reaction, the Miller-Urey and the Sagan-Kaare synthesis as well as the catalytic Fischer-Tropsch synthesis and the radiation-driven Fischer-Tropsch synthesis.

  6. Infrared absorption spectra of metal carbides, nitrides and sulfides

    NASA Technical Reports Server (NTRS)

    Kammori, O.; Sato, K.; Kurosawa, F.

    1981-01-01

    The infrared absorption spectra of 12 kinds of metal carbides, 11 kinds of nitrides, and 7 kinds of sulfides, a total of 30 materials, were measured and the application of the infrared spectra of these materials to analytical chemistry was discussed. The measurements were done in the frequency (wave length) range of (1400 to 400/cm (7 to 25 mu). The carbides Al4C3, B4C, the nitrides AlN, BN, Si3N4, WB, and the sulfides Al2S3, FeS2, MnS, NiS and PbS were noted to have specific absorptions in the measured region. The sensitivity of Boron nitride was especially good and could be detected at 2 to 3 micrograms in 300 mg of potassium bromide.

  7. Carbide and carbonitride surface treatment method for refractory metals

    DOEpatents

    Meyer, Glenn A.; Schildbach, Marcus A.

    1996-01-01

    A carbide and carbonitride surface treatment method for refractory metals is provided, in steps including, heating a part formed of boron, chromium, hafnium, molybdenum, niobium, tantalum, titanium, tungsten or zirconium, or alloys thereof, in an evacuated chamber and then introducing reaction gases including nitrogen and hydrogen, either in elemental or water vapor form, which react with a source of elemental carbon to form carbon-containing gaseous reactants which then react with the metal part to form the desired surface layer. Apparatus for practicing the method is also provided, in the form of a carbide and carbonitride surface treatment system (10) including a reaction chamber (14), a source of elemental carbon (17), a heating subassembly (20) and a source of reaction gases (23). Alternative methods of providing the elemental carbon (17) and the reaction gases (23) are provided, as well as methods of supporting the metal part (12), evacuating the chamber (14) with a vacuum subassembly (18) and heating all of the components to the desired temperature.

  8. New method for synthesis of metal carbides, nitrides and carbonitrides

    SciTech Connect

    Koc, R.; Folmer, J.S.; Kodambaka, S.K.

    1997-04-01

    The purpose of this work is to develop a novel synthesis method using a carbothermic reduction reaction of carbon coated precursors for producing high purity, submicron, non-agglomerated powders of metal carbide, metal nitride and metal boride systems. The authors also want to demonstrate the advantages of the process and provide information on the applicability of the process for synthesizing related advanced ceramic powders (e.g. SiC, WC, TiN, TiB{sub 2}, Si{sub 3}N{sub 4}). During the FY96 of the project, steps are taken to investigate the reaction mechanisms and phase evolution during the formation of TiC from carbon coated titania precursors and to produce submicron TiC powders with desired stoichiometries. Depending on the carbon content in the coated titania precursor, TiC powder was produced with different stoichiometries (different amount of oxygen and free carbon).

  9. Metal and Metal Carbide Nanoparticle Synthesis Using Electrical Explosion of Wires Coupled with Epoxide Polymerization Capping.

    PubMed

    Abdelkader, Elseddik M; Jelliss, Paul A; Buckner, Steven W

    2015-06-15

    In this study, metal-containing nanoparticles (NPs) were produced using electrical explosion of wires (EEW) in organic solvents. The explosion chamber was constructed from Teflon to withstand the shockwave, allow growth and reaction of the incipient NPs in various organic solvents containing dissolved ligands, and allow a constant flow of argon to maintain an inert environment. A survey of different transition d-block metals was conducted with metals from groups 4-8, affording metal carbide NPs, while metals from groups 9-12 gave elemental metallic NPs. Tungsten carbide phase WC1-x, which has not been previously isolated as a single-phase material, was exclusively formed during EEW. We used polymerization initiation by electron-rich metallic nanoparticles (PIERMEN) as a capping technique for the nascent NPs with an alkyl epoxide employed as the monomers. Transmission electron microscopy showed spherical particles with the metallic core embedded in a polymer matrix with predominantly smaller particles (<50 nm), but also a broad size distribution with some larger particles (>100 nm). Powder X-ray diffraction (PXRD) was used to confirm the identity of the metallic NPs. The capping agents were characterized using ATR-FTIR spectroscopy. No evidence is observed for the formation of crystalline oxides during EEW for any metals used. Differential scanning calorimetry/thermal gravimetric analysis was used to study the NP's behavior upon heating under an air flow up to 800 °C with the product oxides characterized by PXRD. The bifurcation between metal-carbide NPs and metal NPs correlates with the enthalpy of formation of the product carbides. We observed PIERMEN capping of elemental metal NPs only when the metal has negative standard electrode potentials (relative to a bis(biphenyl) chromium(I)/(0) reference electrode). PMID:26011064

  10. Steam Reforming on Transition-metal Carbides from Density-functional Theory

    SciTech Connect

    Vojvodic, Aleksandra

    2012-05-11

    A screening study of the steam reforming reaction on clean and oxygen covered early transition-metal carbides surfaces is performed by means of density-functional theory calculations. It is found that carbides provide a wide spectrum of reactivities, from too reactive via suitable to too inert. Several molybdenum-based systems are identified as possible steam reforming catalysts. The findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.

  11. Boron-carbide-aluminum and boron-carbide-reactive metal cermets. [B/sub 4/C-Al

    DOEpatents

    Halverson, D.C.; Pyzik, A.J.; Aksay, I.A.

    1985-05-06

    Hard, tough, lighweight boron-carbide-reactive metal composites, particularly boron-carbide-aluminum composites, are produced. These composites have compositions with a plurality of phases. A method is provided, including the steps of wetting and reacting the starting materials, by which the microstructures in the resulting composites can be controllably selected. Starting compositions, reaction temperatures, reaction times, and reaction atmospheres are parameters for controlling the process and resulting compositions. The ceramic phases are homogeneously distributed in the metal phases and adhesive forces at ceramic-metal interfaces are maximized. An initial consolidated step is used to achieve fully dense composites. Microstructures of boron-carbide-aluminum cermets have been produced with modules of rupture exceeding 110 ksi and fracture toughness exceeding 12 ksi..sqrt..in. These composites and methods can be used to form a variety of structural elements.

  12. Friction and wear behavior of single-crystal silicon carbide in sliding contact with various metals

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1978-01-01

    Sliding friction experiments were conducted with single-crystal silicon carbide in contact with various metals. Results indicate the coefficient of friction is related to the relative chemical activity of the metals. The more active the metal, the higher the coefficient of friction. All the metals examined transferred to silicon carbide. The chemical activity of the metal and its shear modulus may play important roles in metal transfer, the form of the wear debris and the surface roughness of the metal wear scar. The more active the metal, and the less resistance to shear, the greater the transfer to silicon carbide and the rougher the wear scar on the surface of the metal. Hexagon shaped cracking and fracturing formed by cleavage of both prismatic and basal planes is observed on the silicon carbide surface.

  13. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production

    PubMed Central

    Wu, Hao Bin; Xia, Bao Yu; Yu, Le; Yu, Xin-Yao; Lou, Xiong Wen (David)

    2015-01-01

    Electrochemical water splitting has been considered as a promising approach to produce clean and sustainable hydrogen fuel. However, the lack of high-performance and low-cost electrocatalysts for hydrogen evolution reaction hinders the large-scale application. As a new class of porous materials with tunable structure and composition, metal-organic frameworks have been considered as promising candidates to synthesize various functional materials. Here we demonstrate a metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbides based on the confined carburization in metal-organic frameworks matrix. Starting from a compound consisting of copper-based metal-organic frameworks host and molybdenum-based polyoxometalates guest, mesoporous molybdenum carbide nano-octahedrons composed of ultrafine nanocrystallites are successfully prepared as a proof of concept, which exhibit remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions. The present study provides some guidelines for the design and synthesis of nanostructured electrocatalysts. PMID:25758159

  14. Porous molybdenum carbide nano-octahedrons synthesized via confined carburization in metal-organic frameworks for efficient hydrogen production

    NASA Astrophysics Data System (ADS)

    Wu, Hao Bin; Xia, Bao Yu; Yu, Le; Yu, Xin-Yao; Lou, Xiong Wen (David)

    2015-03-01

    Electrochemical water splitting has been considered as a promising approach to produce clean and sustainable hydrogen fuel. However, the lack of high-performance and low-cost electrocatalysts for hydrogen evolution reaction hinders the large-scale application. As a new class of porous materials with tunable structure and composition, metal-organic frameworks have been considered as promising candidates to synthesize various functional materials. Here we demonstrate a metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbides based on the confined carburization in metal-organic frameworks matrix. Starting from a compound consisting of copper-based metal-organic frameworks host and molybdenum-based polyoxometalates guest, mesoporous molybdenum carbide nano-octahedrons composed of ultrafine nanocrystallites are successfully prepared as a proof of concept, which exhibit remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions. The present study provides some guidelines for the design and synthesis of nanostructured electrocatalysts.

  15. Friction and metal transfer for single-crystal silicon carbide in contact with various metals in vacuum

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1978-01-01

    Sliding friction experiments were conducted with single-crystal silicon carbide in contact with transition metals (tungsten, iron, rhodium, nickel, titanium, and cobalt), copper, and aluminum. Results indicate the coefficient of friction for a silicon carbide-metal system is related to the d bond character and relative chemical activity of the metal. The more active the metal, the higher the coefficient of friction. All the metals examined transferred to the surface of silicon carbide in sliding. The chemical activity of metal to silicon and carbon and shear modulus of the metal may play important roles in metal transfer and the form of the wear debris. The less active and greater resistance to shear the metal has, with the exception of rhodium and tungsten, the less transfer to silicon carbide.

  16. Reaction-Forming Method for Producing Near Net-Shape Refractory Metal Carbides

    SciTech Connect

    Palmisiano, Marc N.; Jakubenas, Kevin J.; Baranwal, Rita

    2004-07-20

    A method for reaction forming refractory metal carbides. The method involves the fabrication of a glassy carbon preform by casting an organic, resin-based liquid mixture into a mold and subsequently heat treating it in two steps, which cures and pyrolizes the resin resulting in a porous carbon preform. By varying the amounts of the constituents in the organic, resin-based liquid mixture, control over the density of the carbon preform is obtained. Control of the density and microstructure of the carbon preform allows for determination of the microstructure and properties of the refractory metal carbide material produced. The glassy carbon preform is placed on a bed of refractory metal or refractory metal--silicon alloy. The pieces are heated above the melting point of the metal or alloy. The molten metal wicks inside the porous carbon preform and reacts, forming the refractory metal carbide or refractory metal carbide plus a minor secondary phase.

  17. New catalysts for coal processing: Metal carbides and nitrides

    SciTech Connect

    S. Ted Oyama; David F. Cox

    1999-12-03

    The subject of this research project was to investigate the catalytic properties of a new class of materials, transition metal carbides and nitrides, for treatment of coal liquid and petroleum feedstocks. The main objectives were: (1) preparation of catalysts in unsupported and supported form; (2) characterization of the materials; (3) evaluation of their catalytic properties in HDS and HDN; (4) measurement of the surface properties; and (5) observation of adsorbed species. All of the objectives were substantially carried out and the results will be described in detail below. The catalysts were transition metal carbides and nitrides spanning Groups 4--6 in the Periodic Table. They were chosen for study because initial work had shown they were promising materials for hydrotreating. The basic strategy was first to prepare the materials in unsupported form to identify the most promising catalyst, and then to synthesize a supported form of the material. Already work had been carried out on the synthesis of the Group VI compounds Mo{sub 2}C, Mo{sub 2}N, and WC, and new methods were developed for the Group V compounds VC and NbC. All the catalysts were then evaluated in a hydrotreating test at realistic conditions. It was found that the most active catalyst was Mo{sub 2}C, and further investigations of the material were carried out in supported form. A new technique was employed for the study of the bulk and surface properties of the catalysts, near edge x-ray absorption spectroscopy (NEXAFS), that fingerprinted the electronic structure of the materials. Finally, two new research direction were explored. Bimetallic alloys formed between two transition metals were prepared, resulting in catalysts having even higher activity than Mo{sub 2}C. The performance of the catalysts in hydrodechloration was also investigated.

  18. Replacing precious metals with carbide catalysts for hydrogenation reactions

    DOE PAGESBeta

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Nimore » modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.« less

  19. Replacing precious metals with carbide catalysts for hydrogenation reactions

    SciTech Connect

    Ruijun, Hou; Chen, Jingguang G.; Chang, Kuan; Wang, Tiefeng

    2015-03-03

    Molybdenum carbide (Mo₂C and Ni/Mo₂C) catalysts were compared with Pd/SiO₂ for the hydrogenation of several diene molecules, 1,3- butadiene, 1,3- and 1,4-cyclohexadiene (CHD). Compared to Pd/SiO₂, Mo₂C showed similar hydrogenation rate for 1,3-butadiene and 1,3-CHD and even higher rate for 1,4-CHD, but with significant deactivation rate for 1,3-CHD hydrogenation. However, the hydrogenation activity of Mo₂C could be completely regenerated by H₂ treatment at 723 K for the three molecules. The Ni modified Mo₂C catalysts retained similar activity for 1,3-butadiene hydrogenation with significantly enhanced selectivity for 1-butene production. The 1-butene selectivity increased with increasing Ni loading below 15%. Among the Ni modified Mo₂C catalysts, 8.6%Ni/Mo₂C showed the highest selectivity to 1-butene, which was even higher selectivity than that over Pd/SiO₂. Compared to Pd/SiO₂, both Mo₂C and Ni/Mo₂C showed combined advantages in hydrogenation activity and catalyst cost reduction, demonstrating the potential to use less expensive carbide catalysts to replace precious metals for hydrogenation reactions.

  20. Study of Metallic Carbide (MC) in a Ni-Co-Cr-Based Powder Metallurgy Superalloy

    NASA Astrophysics Data System (ADS)

    Ma, Wen-Bin; Liu, Guo-Quan; Hu, Ben-Fu; Hu, Peng-Hui; Zhang, Yi-Wen

    2014-01-01

    The evolution of carbides in a Ni-Cr-Co-based powder metallurgy (PM) superalloy in the as-atomized, as-atomized + annealed, hot isostatic pressed (HIPed) and HIPed + annealed conditions were systematically analyzed to understand the formation of blocky metallic carbide (MC) along the previous particle boundary (PPB). The results show that the carbides both on the powder surfaces and in the bulk of the powder particles are mainly fan-shaped MC whose decomposition temperatures are in the range of 1473 K to 1493 K (1200 °C to 1220 °C). PPB carbides in the HIPed alloy are mainly block-shaped MC, and the fan-shaped MC densely distributed in the area that have not been consumed by the recrystallized grains. The formation mechanism of PPB carbides can be described as follows: When the powders are HIPed at 1453 K (1180 °C), the fan-shaped carbides are decomposed at the migrating boundaries of recrystallized grains, and the preferential precipitation of block-shaped MC at PPB is promoted by the carbide-forming elements released by the fan-shaped carbides. When the HIPed alloy is annealed at 1453 K (1180 °C), the area fraction of PPB carbides increases with an increase in annealing time but that of the fan-shaped carbides exhibits opposite behavior. This proves the above formation mechanism of PPB carbides.

  1. Two-dimensional, ordered, double transition metals carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Kent, Paul; Anasori, Babak; Xie, Yu; Beidaghi, Majid; Lu, Jun; Hosler, Brian; Hultman, Lars; Gogotsi, Yury; Barsoum, Michel

    We use density functional theory to predict the existence of two new families of 2D ordered carbides (MXenes), M'2M''C2 and M'2M''2C3, where each M is a different early transition metal. Synthesizing Mo2TiC2Tx, Mo2Ti2C3Tx, and Cr2TiC2Tx (where T is a surface termination), we validated the DFT predictions. Since the Mo and Cr atoms are on the outside, they control the 2D flakes' chemical and electrochemical properties. The latter was proven by showing quite different electrochemical behavior of Mo2TiC2Tx and Ti3C2Tx. This work further expands the family of 2D materials, offering additional choices of structures, chemistries, and ultimately useful properties.

  2. Analysis of powdered tungsten carbide hard-metal precursors and cemented compact tungsten carbides using laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Novotný, K.; Staňková, A.; Häkkänen, H.; Korppi-Tommola, J.; Otruba, V.; Kanický, V.

    2007-12-01

    Laser-induced breakdown spectroscopy (LIBS) has been applied to the direct analysis of powdered tungsten carbide hard-metal precursors and cemented tungsten carbides. The aim of this work was to examine the possibility of quantitative determination of the niobium, titanium, tantalum and cobalt. The investigated samples were in the form of pellets, pressed with and without binder (powdered silver) and in the form of cemented tungsten carbides. The pellets were prepared by pressing the powdered material in a hydraulic press. Cemented tungsten carbides were embedded in resin for easier manipulation. Several lasers and detection systems were utilized. The Nd:YAG laser working at a basic wavelength of 1064 nm and fourth-harmonic frequency of 266 nm with a gated photomultiplier or ICCD detector HORIBA JY was used for the determination of niobium which was chosen as a model element. Different types of surrounding gases (air, He, Ar) were investigated for analysis. The ICCD detector DICAM PRO with Mechelle 7500 spectrometer with ArF laser (193 nm) and KrF laser (248 nm) were employed for the determination of niobium, titanium, tantalum and cobalt in samples under air atmosphere. Good calibration curves were obtained for Nb, Ti, and Ta (coefficients of determination r2 > 0.96). Acceptable calibration curves were acquired for the determination of cobalt (coefficient of determination r2 = 0.7994) but only for the cemented samples. In the case of powdered carbide precursors, the calibration for cobalt was found to be problematic.

  3. Electromagnetic interference shielding with 2D transition metal carbides (MXenes).

    PubMed

    Shahzad, Faisal; Alhabeb, Mohamed; Hatter, Christine B; Anasori, Babak; Man Hong, Soon; Koo, Chong Min; Gogotsi, Yury

    2016-09-01

    Materials with good flexibility and high conductivity that can provide electromagnetic interference (EMI) shielding with minimal thickness are highly desirable, especially if they can be easily processed into films. Two-dimensional metal carbides and nitrides, known as MXenes, combine metallic conductivity and hydrophilic surfaces. Here, we demonstrate the potential of several MXenes and their polymer composites for EMI shielding. A 45-micrometer-thick Ti3C2Tx film exhibited EMI shielding effectiveness of 92 decibels (>50 decibels for a 2.5-micrometer film), which is the highest among synthetic materials of comparable thickness produced to date. This performance originates from the excellent electrical conductivity of Ti3C2Tx films (4600 Siemens per centimeter) and multiple internal reflections from Ti3C2Tx flakes in free-standing films. The mechanical flexibility and easy coating capability offered by MXenes and their composites enable them to shield surfaces of any shape while providing high EMI shielding efficiency. PMID:27609888

  4. Wear of single-crystal silicon carbide in contact with various metals in vacuum

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1978-01-01

    Sliding friction experiments were conducted in vacuum with single crystal silicon carbide (0001) surface in contact with transition metals (tungsten, iron, rhodium, nickel, titanium, and cobalt), copper, and aluminum. The hexagon shaped cracking and fracturing of silicon carbide that occurred is believed to be due to cleavages of both the prismatic and basal planes. The silicon carbide wear debris, which was produced by brittle fracture, slides or rolls on both the metal and silicon carbide and produces grooves and indentations on these surfaces. The wear scars of aluminum and titanium, which have much stronger chemical affinity for silicon and carbon, are generally rougher than those of the other metals. Fracturing and cracking along the grain boundary of rhodium and tungsten were observed. These may be primarily due to the greater shear moduli of the metals.

  5. Generic trend of work functions in transition-metal carbides and nitrides

    SciTech Connect

    Yoshitake, Michiko

    2014-11-15

    Transition-metal carbides and nitrides (TMCs and TMNs) are promising electrode materials for various electronic devices such as metal-oxide-semiconductor field-effect transistors and metal-insulator-metal capacitors. In this paper, the work functions of TMCs and TMNs are discussed systematically. Based upon the origin of the work function, the effect upon transition metal species by different periodic table groups is explained, carbides are compared with nitrides for the same transition metal, and the effect of carbon or nitrogen vacancies is discussed. In addition, a method to estimate the generic trend of the work function is proposed for TMC{sub x}, TMN{sub x}, TMC{sub 1−y}N{sub y} (transition metal carbonitrides), and TM{sub 1−z}TM′{sub z}C (alloy carbides)

  6. An expeditious synthesis of early transition metal carbide nanoparticles on graphitic carbons.

    PubMed

    Ressnig, Debora; Moldovan, Simona; Ersen, Ovidiu; Beaunier, Patricia; Portehault, David; Sanchez, Clément; Carenco, Sophie

    2016-08-01

    An expeditious synthesis of metal carbide nanoparticles onto various carbon supports is demonstrated. The procedure is versatile and readily yields TiC, VC, Mo2C and W2C nanoparticles on different types of carbons. The reaction is initiated at room temperature and proceeds within seconds. This novel synthetic route paves the way for a large variety of metal carbide-carbon nanocomposites that may be implemented in emerging nanotechnology fields. PMID:27383864

  7. Chemistry of Two-Dimensional Transition Metal Carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Mashtalir, Olha

    With consumer trends pushing toward smaller, faster, more flexible, multitasking devices, researchers striving to meet these needs have targeted two-dimensional (2D) materials---and graphene in particular---as holding the most promise for use in advanced applications. But in 2011, a significant interest has been triggered by a newly discovered family of novel 2D materials---layered transitional metal carbides and carbonitrides, named MXenes. Those compounds were of general formula Mn+1 XnTx, where M stands for metal atom, X is C and/or N, n = 1, 2 or 3, and Tx represents surface groups. Being initially suggested as a material for electrical energy storage systems, MXenes' properties and their potential applications have not been explored. This work is the first complete study of MXenes' chemistry that sheds light on the chemical composition, structure and properties of these novel materials and possible routes of its modification. The research was focused on 2D titanium carbide, Ti3C2Tx, chosen as the representative of the MXene family. The kinetic study of Ti 3C2Tx synthesis discovered the main synthesis parameters, viz. temperature, time and particle size, that affect the etching process and define the quality of final product. MXenes were found to be able to spontaneously accommodate various ions and small organic molecules between the layers leading to preopening of the structure. A major challenge of large scale production of delaminated, atomically thin 2D MXene layers was solved with two delamination techniques involving dimethyl sulfoxide and isopropyl amine pre-intercalation followed by sonication in water. Ti3C2Tx was also found to possess adsorptive and photocatalytic properties, revealing its potential for environmental applications. It also showed limited stability in water and in the presence of oxygen, providing important practical information on proper handling and storage of MXene materials. Completion of this work allowed the performance of energy

  8. Magnetic Behavior of 3d Transition Metals in Silicon Carbide

    NASA Astrophysics Data System (ADS)

    Miao, Maosheng; Lambrecht, Walter R. L.

    2002-03-01

    The magnetic properties of cubic silicon carbide (SiC) doped by first row transition metals (TM) are studied within the local spin density functional approach using the linearized muffin-tin orbital method in the atomic sphere approximation. It is found that the couplings between the TM d orbitals and the dangling bond states are stronger for the Si site doping, which gives a larger e-t2 splitting. The stronger coupling also delocalizes the t2 states and hence reduces the spin polarization. As a result the TMs tend to have a low spin configuration at the Si site and a high spin one at the C site. On the other hand, the strong couplings lower the formation energy at the Si site and TMs prefer to dope the Si site in both the Si-rich and C-rich limits. For Si site doping, Cr and Mn exhibit the most pronounced magnetic behavior with Cr favoring ferromagnetic and Mn antiferromagnetic nearest neighbor coupling.

  9. Characterization of silicon carbide metal oxide semiconductor capacitors

    NASA Astrophysics Data System (ADS)

    Marinella, Matthew J.

    Only a few years after the invention of the transistor, William Shockley considered silicon carbide (SiC) an excellent material for high temperature semiconductor devices. Over a half century later, SiC technology is nearly mature enough that it may be considered for use in commercial electronic devices. Furthermore, since SiC has the ability to grow thermal silicon dioxide, significant research has been directed toward the creation of a commercial SiC metal oxide semiconductor field effect transistor (MOSFET). However, a number of significant hurdles still must be overcome before SiC devices can become commercially competitive, including the relatively high cost and low quality of materials. Another significant problem is the lack of understanding of factors which limit the minority carrier lifetime. The primary purpose of this work was to use the pulsed metal oxide semiconductor capacitor (MOS-C) technique to measure generation lifetime in SiC materials. It was found that many nonidealities corrupt the results obtained by this technique. One very interesting nonideality was negative bias temperature instability (NBTI), which has also been widely studied by the silicon industry in recent years. Methods to understand and minimize the effect of these nonidealities were developed. Furthermore, these methods allowed for further study of the oxide properties, such as leakage current. Even after accounting for nonidealities, generation lifetimes showed several peculiarities, such as a variation of as much as a factor of 1000 within a square cm area. In addition, the ratio of generation to recombination lifetime is less than unity, which is not predicted by classic theory, nor typically observed in silicon devices. Possible explanations are put forth to explain these observations. In addition, to further investigate these abnormalities, Schottky diodes were fabricated and characterized. When applied to the SiC MOS capacitor, the pulsed MOS-C technique involves

  10. Structure-Property Relationship in Metal Carbides and Bimetallic Alloys

    SciTech Connect

    Chen, Jingguan

    2014-03-04

    The primary objective of our DOE/BES sponsored research is to use carbide and bimetallic catalysts as model systems to demonstrate the feasibility of tuning the catalytic activity, selectivity and stability. Our efforts involve three parallel approaches, with the aim at studying single crystal model surfaces and bridging the “materials gap” and “pressure gap” between fundamental surface science studies and real world catalysis. The utilization of the three parallel approaches has led to the discovery of many intriguing catalytic properties of carbide and bimetallic surfaces and catalysts. During the past funding period we have utilized these combined research approaches to explore the possibility of predicting and verifying bimetallic and carbide combinations with enhanced catalytic activity, selectivity and stability.

  11. Interface reactions between silicon carbide and interlayers in silicon carbide copper metal matrix composites

    NASA Astrophysics Data System (ADS)

    Köck, T.; Brendel, A.; Bolt, H.

    2007-05-01

    Novel copper matrix composites reinforced with silicon carbide fibres are considered as a new generation of heat sink materials for the divertor of future fusion reactors. The divertor is exposed to intense particle bombardment and heat loads of up to 15 MW m-2. This component consists of the plasma-facing material which is bonded to the actively cooled heat sink. Due to its high thermal conductivity of about 400 W m-1 K-1 copper is a promising material for the heat sink. To increase the mechanical properties of copper at working temperature (823 K), silicon carbide fibres with a diameter of 140 μm are used to reinforce the interface area between the plasma-facing material and the heat sink. Push-out tests show that the adhesion between SiC fibre and Cu matrix without any interlayer is very low. To increase the fibre-matrix bonding the fibres are coated with Cr and W with a thickness of 300-400 nm before Cu deposition by magnetron sputtering. Push-out tests on these modified fibres show a significant increase in adhesion compared to the fibres without interlayer. XRD investigations after a heat treatment at 923 K show a chromium carbide (Cr23C6, Cr3C2) formation and the absence of chromium silicides. In the case of a W interlayer a W2C formation is detected and also no tungsten silicides. Single-fibre tensile tests were performed to investigate the influence of the reaction zone on the ultimate tensile strength of the fibres. The ultimate tensile strength for fibres without interlayer remains constant at about 2200 MPa after annealing at 923 K. The fibres with chromium and tungsten interlayers, respectively, show a decrease of about 30% of the ultimate tensile strength after the heat treatment at 923 K.

  12. Solid oxide membrane-assisted controllable electrolytic fabrication of metal carbides in molten salt.

    PubMed

    Zou, Xingli; Zheng, Kai; Lu, Xionggang; Xu, Qian; Zhou, Zhongfu

    2016-08-15

    Silicon carbide (SiC), titanium carbide (TiC), zirconium carbide (ZrC), and tantalum carbide (TaC) have been electrochemically produced directly from their corresponding stoichiometric metal oxides/carbon (MOx/C) precursors by electrodeoxidation in molten calcium chloride (CaCl2). An assembled yttria stabilized zirconia solid oxide membrane (SOM)-based anode was employed to control the electrodeoxidation process. The SOM-assisted controllable electrochemical process was carried out in molten CaCl2 at 1000 °C with a potential of 3.5 to 4.0 V. The reaction mechanism of the electrochemical production process and the characteristics of these produced metal carbides (MCs) were systematically investigated. X-ray diffraction, scanning electron microscopy, and transmission electron microscopy analyses clearly identify that SiC, TiC, ZrC, and TaC carbides can be facilely fabricated. SiC carbide can be controlled to form a homogeneous nanowire structure, while the morphologies of TiC, ZrC, and TaC carbides exhibit porous nodular structures with micro/nanoscale particles. The complex chemical/electrochemical reaction processes including the compounding, electrodeoxidation, dissolution-electrodeposition, and in situ carbonization processes in molten CaCl2 are also discussed. The present results preliminarily demonstrate that the molten salt-based SOM-assisted electrodeoxidation process has the potential to be used for the facile and controllable electrodeoxidation of MOx/C precursors to micro/nanostructured MCs, which can potentially be used for various applications. PMID:27195950

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

    DOEpatents

    Halverson, Danny C.; Landingham, Richard L.

    1988-01-01

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

  14. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Howard, J.B.; Peters, W.A.

    1993-02-01

    Light hydrocarbon gases could be reacted with low cost alkaline earth metal oxide (CaO, MgO) in high-temperature plasma reactor to achieve very high ([le]100%) gas conversion to H[sub 2], CO, and the corresponding metal carbides. These carbides could be stored, transported, and hydrolyzed to acetylene or methyl acetylene, which in turn could be upgraded to a wide range of chemicals and premium liquid hydrocarbon fuels. An electric arc discharge reactor was built for converting methane. Literature reviews were made.

  15. Correlation between volatility of rare-earth metals and encapsulation of their carbides in carbon nanocapsules

    SciTech Connect

    Saito, Yahachi; Okuda, Mitsumasa; Yoshikawa, Tadanobu ); Kasuya, Atsuo; Nishina, Yuichiro )

    1994-07-07

    Encapsulation of metals in multilayered graphitic capsules has been studied for all the rare-earth elements (Sc, Y, and Ln = La, Ce, ..., Lu) excluding Pm by using electric arc discharge. Electron microscopy and X-ray diffraction of carbonaceous products revealed that most of rare-earth metals (Sc, Y, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu) were encapsulated in the form of carbides, but the others, Sm, Eu, and Yb, were not. The metals in the former group that were encapsulated had vapor pressures definitely lower than those in the latter group. In the case of thulium (Tm), whose vapor pressure is intermediate between the two groups, only a trace amount of encapsulated carbide was formed. Correlation of volatility of metals with encapsulation was clearly found, suggesting that the volatility of a metal plays an important role in a process of the metal encapsulation. 25 refs., 4 figs., 1 tab.

  16. Carbide-Free Bainitic Weld Metal: A New Concept in Welding of Armor Steels

    NASA Astrophysics Data System (ADS)

    Krishna Murthy, N.; Janaki Ram, G. D.; Murty, B. S.; Reddy, G. M.; Rao, T. J. P.

    2014-12-01

    Carbide-free bainite, a fine mixture of bainitic ferrite and austenite, is a relatively recent development in steel microstructures. Apart from being very strong and tough, the microstructure is hydrogen-tolerant. These characteristics make it well-suited for weld metals. In the current work, an armor-grade quenched and tempered steel was welded such that the fusion zone developed a carbide-free bainitic microstructure. These welds showed very high joint efficiency and ballistic performance compared to those produced, as per the current industrial practice, using austenitic stainless steel fillers. Importantly, these welds showed no vulnerability to cold cracking, as verified using oblique Y-groove tests. The concept of carbide-free bainitic weld metal thus promises many useful new developments in welding of high-strength steels.

  17. Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

    DOE PAGESBeta

    Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.; Nash, Connor; Steirer, K. Xerxes; Clark, Jared; Robichaud, David J.; Ruddy, Daniel A.

    2016-01-21

    Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo2C) for the deoxygenation of acetic acid, anmore » abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

  18. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction

    PubMed Central

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-01-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (−0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm−2 at −0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries. PMID:25997590

  19. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction.

    PubMed

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-01-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (-0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm(-2) at -0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries. PMID:25997590

  20. Nitrogen-doped Graphene-Supported Transition-metals Carbide Electrocatalysts for Oxygen Reduction Reaction

    NASA Astrophysics Data System (ADS)

    Chen, Minghua; Liu, Jilei; Zhou, Weijiang; Lin, Jianyi; Shen, Zexiang

    2015-05-01

    A novel and facile two-step strategy has been designed to prepare high performance bi-transition-metals (Fe- and Mo-) carbide supported on nitrogen-doped graphene (FeMo-NG) as electrocatalysts for oxygen reduction reactions (ORR). The as-synthesized FeMo carbide -NG catalysts exhibit excellent electrocatalytic activities for ORR in alkaline solution, with high onset potential (-0.09 V vs. saturated KCl Ag/AgCl), nearly four electron transfer number (nearly 4) and high kinetic-limiting current density (up to 3.5 mA cm-2 at -0.8 V vs. Ag/AgCl). Furthermore, FeMo carbide -NG composites show good cycle stability and much better toxicity tolerance durability than the commercial Pt/C catalyst, paving their application in high-performance fuel cell and lithium-air batteries.

  1. Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts

    DOEpatents

    Choi, Jae Soon; Armstrong, Beth L; Schwartz, Viviane

    2015-04-21

    A method for synthesizing catalyst beads of bulk transmission metal carbides, nitrides and phosphides is provided. The method includes providing an aqueous suspension of transition metal oxide particles in a gel forming base, dropping the suspension into an aqueous solution to form a gel bead matrix, heating the bead to remove the binder, and carburizing, nitriding or phosphiding the bead to form a transition metal carbide, nitride, or phosphide catalyst bead. The method can be tuned for control of porosity, mechanical strength, and dopant content of the beads. The produced catalyst beads are catalytically active, mechanically robust, and suitable for packed-bed reactor applications. The produced catalyst beads are suitable for biomass conversion, petrochemistry, petroleum refining, electrocatalysis, and other applications.

  2. Structural evolution of molybdenum carbides in hot aqueous environments and impact on low-temperature hydroprocessing of acetic acid

    SciTech Connect

    Choi, Jae -Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo; Crocker, Mark; Lewis, Sr., Samuel A.; Lance, Michael J.; Meyer, III, Harry M.; More, Karren L.

    2015-03-13

    In this paper, we investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. Finally, the results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.

  3. Structural evolution of molybdenum carbides in hot aqueous environments and impact on low-temperature hydroprocessing of acetic acid

    DOE PAGESBeta

    Choi, Jae -Soon; Schwartz, Viviane; Santillan-Jimenez, Eduardo; Crocker, Mark; Lewis, Sr., Samuel A.; Lance, Michael J.; Meyer, III, Harry M.; More, Karren L.

    2015-03-13

    In this paper, we investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating themore » possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. Finally, the results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.« less

  4. Friction and wear of metals with a single-crystal abrasive grit of silicon carbide: Effect of shear strength of metal

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1978-01-01

    Sliding friction experiments were conducted with spherical, single-crystal silicon carbide riders in contact with various metals and with metal riders in contact with silicon carbide flats. Results indicate that: (1) the friction force in the plowing of metal and (2) the groove height (corresponding to the volume of the groove) are related to the shear strength of the metal. That is, they decrease linearly as the shear strength of the bulk metal increases. Grooves are formed in metals primarily from plastic deformation, with occasional metal removal. The relation between the groove width D and the load W can be expressed by W = kD, superscript n which satisfies Meyer's law.

  5. Transition metals and their carbides and nitrides: Trends in electronic and structural properties

    NASA Astrophysics Data System (ADS)

    Grossman, Jeffrey C.; Mizel, Ari; Côté, Michel; Cohen, Marvin L.; Louie, Steven G.

    1999-09-01

    A study of the structural and electronic properties of selected transition metals and their carbides and nitrides is presented. We focus on assessing trends of possible importance for understanding their hardness. Lattice constants, bulk moduli (Bo), and charge densities are calculated using the local density approximation with a pseudopotential plane wave approach. An fcc lattice is employed for the transition metal elements in order to make comparisons and study trends relateable to their carbides and nitrides. Our results show that both increasing the number of valence d electrons and the presence of f electrons in the core lead to larger (Bo). Charge density plots and histograms enable us to explain the nature of the charge distribution in the interstitial region for the different compounds considered. In addition, we include the heavier elements seaborgium, bohrium, and hasnium in order to test further trends. Surprisingly, the calculated Bo for Hs is comparable to that of diamond.

  6. Magnetic composites based on metallic nickel and molybdenum carbide: a potential material for pollutants removal.

    PubMed

    Mambrini, Raquel V; Fonseca, Thales L; Dias, Anderson; Oliveira, Luiz C A; Araujo, Maria Helena; Moura, Flávia C C

    2012-11-30

    New magnetic composites based on metallic nickel and molybdenum carbide, Ni/Mo(2)C, have been produced via catalytic chemical vapor deposition from ethanol. Scanning electron microscopy, thermal analysis, Raman spectroscopy and X-ray diffraction studies suggest that the CVD process occurs in a single step. This process involves the reduction of NiMo oxides at different temperatures (700, 800 and 900°C) with catalytic deposition of carbon from ethanol producing molybdenum carbide on Ni surface. In the absence of molybdenum the formation of Ni/C was observed. The magnetic molybdenum carbide was successfully used as pollutants removal by adsorption of sulfur and nitrogen compounds from liquid fuels and model dyes such as methylene blue and indigo carmine. The dibenzothiofene adsorption process over Ni/Mo(2)C reached approximately 20 mg g(-1), notably higher than other materials described in the literature and also removed almost all methylene blue dye. The great advantage of these carbide composites is that they may be easily recovered magnetically and reused. PMID:23036701

  7. In vitro genotoxic effects of different combinations of cobalt and metallic carbide particles.

    PubMed

    De Boeck, Marlies; Lombaert, Noömi; De Backer, Sofie; Finsy, Robert; Lison, Dominique; Kirsch-Volders, Micheline

    2003-03-01

    Occupational exposure to hard metal dust, consisting of tungsten carbide (WC) and metallic cobalt particles (Co), is associated with an increased risk of lung cancer, while no increased risk was observed in workers exposed to Co alone. In vitro, in human peripheral blood mononucleated cells (PBMC), we previously demonstrated that WC-Co is more genotoxic than Co and WC alone. A possible mechanism underlying this higher genotoxicity is a specific physicochemical interaction between Co and WC particles leading to the enhanced short-term formation of active oxygen species. The aim of this study was to evaluate the in vitro genotoxicity of other combinations of Co with metal carbide particles in comparison with WC-Co. The ability of Cr(3)C(2), Mo(2)C and NbC and of their powder mixtures with Co to induce DNA strand breaks and alkali-labile sites was assessed by the alkaline Comet assay and their potential to induce chromosome(/genome) mutations by the cytokinesis-block micronucleus test on human PBMC from two donors. PBMC were treated in vitro for 15 min, 24 h after the onset of PHA stimulation. In the micronucleus test, while the metal carbides alone did not increase the micronucleus frequency, Co alone and the four tested carbide-Co mixtures induced a statistically significant concentration-dependent increase in micronucleated binucleates. In addition to WC, NbC and Cr(3)C(2) particles were able to interact with Co, producing a higher mutagenic effect than the individual metal particles. Mo(2)C particles did not display interactive mutagenicity with Co in the micronucleus test, possibly related to their small specific surface area, compactness and/or spherical shape. With the Comet assay, applied directly at the end of the treatment, less clear results, due to inter-experimental and inter-donor variation, were obtained. These data indicate that particular interaction of a metal carbide with Co leading to enhanced mutagenicity is not specific for WC. PMID:12621074

  8. A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides.

    PubMed

    Esposito, Daniel V; Hunt, Sean T; Kimmel, Yannick C; Chen, Jingguang G

    2012-02-15

    This work explores the opportunity to substantially reduce the cost of hydrogen evolution reaction (HER) catalysts by supporting monolayer (ML) amounts of precious metals on transition metal carbide substrates. The metal component includes platinum (Pt), palladium (Pd), and gold (Au); the low-cost carbide substrate includes tungsten carbides (WC and W(2)C) and molybdenum carbide (Mo(2)C). As a platform for these studies, single-phase carbide thin films with well-characterized surfaces have been synthesized, allowing for a direct comparison of the intrinsic HER activity of bare and Pt-modified carbide surfaces. It is found that WC and W(2)C are both excellent cathode support materials for ML Pt, exhibiting HER activities that are comparable to bulk Pt while displaying stable HER activity during chronopotentiometric HER measurements. The findings of excellent stability and HER activity of the ML Pt-WC and Pt-W(2)C surfaces may be explained by the similar bulk electronic properties of tungsten carbides to Pt, as is supported by density functional theory calculations. These results are further extended to other metal overlayers (Pd and Au) and supports (Mo(2)C), which demonstrate that the metal ML-supported transition metal carbide surfaces exhibit HER activity that is consistent with the well-known volcano relationship between activity and hydrogen binding energy. This work highlights the potential of using carbide materials to reduce the costs of hydrogen production from water electrolysis by serving as stable, low-cost supports for ML amounts of precious metals. PMID:22280370

  9. Electronic structure and Fermi surfaces of transition metal carbides with rocksalt structure

    NASA Astrophysics Data System (ADS)

    Paduani, C.

    2008-06-01

    First-principles calculations were carried out to investigate the structural and electronic properties of the metal carbides FeC, CoC, NiC, and PtC in the rocksalt structure. The full-potential linearized augmented-plane wave (FP-LAPW) method was used in the framework of the density-functional theory with the generalized gradient approximation (GGA) for the exchange-correlation potential. Ground state properties are determined and compared with available experimental data. The energy band structures, densities of states, and Fermi surface structures are obtained, which show that these compounds are metallic like the conventional transition metal carbides. There is an extensive hybridization between the metal-d and C-2p states for all the studied carbides, which can form bonding and antibonding states. From FeC to PtC a band narrowing for the hybridized metal-d and C-2p states near to the Fermi level takes place, which is expected to lead to smaller interactions between adjacent atoms. The largest bulk modulus of FeC is expected to be associated with the behavior of valence electrons near the Fermi level, i.e. a higher degree of hybridization between p-d states that are responsible for the chemical bonding results in strengthened interactions. The decrease in the number of bonding orbitals or decrease in metallic valence with the increase in number of 3d electrons from FeC to PtC provides a mechanism for weaker interactions due to the filling of antibonding bands.

  10. Determination of micro amounts of iron, aluminum, and alkaline earth metals in silicon carbide

    NASA Technical Reports Server (NTRS)

    Hirata, H.; Arai, M.

    1978-01-01

    A colorimetric method for analysis of micro components in silicon carbide used as the raw material for varistors is described. The microcomponents analyzed included iron soluble in hydrochloric acid, iron, aluminum, calcium and magnesium. Samples were analyzed by the method, and the results for iron and aluminum agreed well with the N.B.S. standard values and the values obtained by the other company. The method can therefore be applied to the analysis of actual samples.

  11. Processing of solid solution, mixed uranium/refractory metal carbides for advanced space nuclear power and propulsion systems

    NASA Astrophysics Data System (ADS)

    Knight, Travis Warren

    Nuclear thermal propulsion (NTP) and space nuclear power are two enabling technologies for the manned exploration of space and the development of research outposts in space and on other planets such as Mars. Advanced carbide nuclear fuels have been proposed for application in space nuclear power and propulsion systems. This study examined the processing technologies and optimal parameters necessary to fabricate samples of single phase, solid solution, mixed uranium/refractory metal carbides. In particular, the pseudo-ternary carbide, UC-ZrC-NbC, system was examined with uranium metal mole fractions of 5% and 10% and corresponding uranium densities of 0.8 to 1.8 gU/cc. Efforts were directed to those methods that could produce simple geometry fuel elements or wafers such as those used to fabricate a Square Lattice Honeycomb (SLHC) fuel element and reactor core. Methods of cold uniaxial pressing, sintering by induction heating, and hot pressing by self-resistance heating were investigated. Solid solution, high density (low porosity) samples greater than 95% TD were processed by cold pressing at 150 MPa and sintering above 2600 K for times longer than 90 min. Some impurity oxide phases were noted in some samples attributed to residual gases in the furnace during processing. Also, some samples noted secondary phases of carbon and UC2 due to some hyperstoichiometric powder mixtures having carbon-to-metal ratios greater than one. In all, 33 mixed carbide samples were processed and analyzed with half bearing uranium as ternary carbides of UC-ZrC-NbC. Scanning electron microscopy, x-ray diffraction, and density measurements were used to characterize samples. Samples were processed from powders of the refractory mono-carbides and UC/UC 2 or from powders of uranium hydride (UH3), graphite, and refractory metal carbides to produce hypostoichiometric mixed carbides. Samples processed from the constituent carbide powders and sintered at temperatures above the melting point of UC

  12. High-temperature mass spectrometry - Vaporization of group 4-B metal carbides. [using Knudsen effusion

    NASA Technical Reports Server (NTRS)

    Stearns, C. A.; Kohl, F. J.

    1974-01-01

    The high temperature vaporization of the metal-carbon systems TiC, ZrC, HfC, and ThC was studied by the Knudsen effusion - mass spectrometric method. For each system the metal dicarbide and tetracarbide molecular species were identified in the gas phase. Relative ion currents of the carbides and metals were measured as a function of temperature. Second- and third-law methods were used to determine enthalpies. Maximum values were established for the dissociation energies of the metal monocarbide molecules TiC, ZrC, HfC, and ThC. Thermodynamic functions used in the calculations are discussed in terms of assumed molecular structures and electronic contributions to the partition functions. The trends shown by the dissociation energies of the carbides of Group 4B are compared with those of neighboring groups and discussed in relation to the corresponding oxides and chemical bonding. The high temperature molecular beam inlet system and double focusing mass spectrometer are described.

  13. Metal modified tungsten carbide (WC) for catalytic and electrocatalytic applications

    NASA Astrophysics Data System (ADS)

    Mellinger, Zachary J.

    One of the major challenges in the commercialization of proton exchange membrane fuel cells (PEMFC) is the cost, and low CO tolerance of the anode electrocatalyst material. The anode typically requires a high loading of precious metal electrocatalyst (Pt or Pt--Ru) to obtain a useful amount of electrical energy from the electrooxidation of methanol (CH3OH) or ethanol (C2H5OH). The complete electro--oxidation of methanol or ethanol on these catalysts produces strongly adsorbed CO on the surface, which reduces the activity of the Pt or Pt--Ru catalysts. Another major disadvantage of these electrocatalyst components is the scarcity and consequently high price of both Pt and Ru. Tungsten monocarbide (WC) has shown similar catalytic properties to Pt, leading to the utilization of WC and metal modified WC as replacements to Pt and Pt--Ru. In this thesis we investigated WC and Pt--modified WC as a potentially more CO--tolerant electrocatalysts as compared to pure Pt. These catalysts would reduce or remove the high loading of Pt used industrially. The binding energy of CO, estimated using temperature programmed desorption, is weaker on WC and Pt/WC than on Pt, suggesting that it should be easier to oxidize CO on WC and Pt/WC. This hypothesis was verified using cyclic voltammetry to compare the electro--oxidation of CO on WC, Pt/WC, and Pt supported on carbon substrates, which showed a lower voltage for the onset of oxidation of CO on WC and Pt/WC than on Pt. After observing these improved properties on the Pt/WC catalysts, we decided to expand our studies to investigate Pd--modified WC as Pd is less expensive than Pt and has shown more ideal properties for alcohol electrocatalysis in alkaline media. Pd/WC showed a lower binding energy of CO than both its parent metal Pd as well as Pt. Then, density functional theory (DFT) calculations were performed to determine how the presence of Pd affected the bonding of methanol and ethanol on the WC surface. The DFT studies showed

  14. Processing and mechanical properties of aluminium-silicon carbide metal matrix composites

    NASA Astrophysics Data System (ADS)

    Nuruzzaman, D. M.; Kamaruzaman, F. F. B.

    2016-02-01

    In this study, aluminium-silicon carbide (Al-SiC) metal matrix composites (MMCs) of different compositions were prepared under different compaction loads. Three different types Al-SiC composite specimens having 10%, 20% and 30% volume fractions of silicon carbide were fabricated using conventional powder metallurgy (PM) route. The specimens of different compositions were prepared under different compaction loads 10 ton and 15 ton. The effect of volume fraction of SiC particulates and compaction load on the properties of Al/SiC composites were investigated. The obtained results show that density and hardness of the composites are greatly influenced by volume fraction of silicon carbide particulates. Results also show that density, hardness and microstructure of Al-SiC composites are significantly influenced depending on the compaction load. The increase in the volume fraction of SiC enhances the density and hardness of the Al/SiC composites. For 15 ton compaction load, the composites show increased density and hardness as well as improved microstructure than the composites prepared under 10 ton compaction load. Furthermore, optical micrographs reveal that SiC particulates are uniformly distributed in the Al matrix.

  15. Evaluation of the apoptogenic potential of hard metal dust (WC-Co), tungsten carbide and metallic cobalt.

    PubMed

    Lombaert, Noömi; De Boeck, Marlies; Decordier, Ilse; Cundari, Enrico; Lison, Dominique; Kirsch-Volders, Micheline

    2004-12-01

    The present study aimed at comparing in vitro the apoptogenic properties of metallic cobalt (Co), tungsten carbide (WC) and tungsten carbide-cobalt (WC-Co) in conditions known to cause genotoxicity. Human peripheral blood mononucleated cells were incubated with 2.0-6.0 microg/ml of Co alone or mixed with WC particles and 33.3-100.0 microg/ml WC alone for up to 24 h. Under these culture conditions the majority (60%) of the cobalt metal particles were almost immediately solubilised in the culture medium, while WC remained under the form of particles that were progressively phagocytosed by monocytes. Apoptosis was assessed by Annexin-V staining, flow cytometry and analysis of DNA fragmentation by ELISA. Metallic Co-particles induced apoptosis in vitro. Furthermore, although so far considered as biologically inert, WC particles also induced apoptosis. When compared with its individual components WC-Co displayed an additive apoptotic effect in the DNA fragmentation assay. Apoptosis induced by WC particles was found largely dependent on caspase-9 activation and occurred presumably in monocytes, while that induced by Co involved both caspase-9 and -8 activation. The data suggest that apoptosis induced by the tested WC-Co mixture results from the additive effects of WC apoptosis induced in monocytes and Co-specific apoptosis in both monocytes and lymphocytes. The apoptogenic properties of these metals may be important in the mechanism of lung pathologies induced by the cobalt-containing particles. PMID:15475175

  16. Analytical and experimental evaluation of joining silicon nitride to metal and silicon carbide to metal for advanced heat engine applications

    SciTech Connect

    Kang, S.; Selverian, J.H.; Kim, H.; O'Niel, D.; Kim, K. )

    1990-04-01

    This report summarizes the results of Phase I of Analytical and Experimental Evaluation of Joining Silicon Nitride to Metal and Silicon Carbide to Metal and Silicon Carbide to Metal for Advanced Heat Engine Applications. A general methodology was developed to optimize the joint geometry and material systems for 650 and 950{degree}C applications. Failure criteria were derived to predict the fracture of the braze and ceramic. Extensive finite element analyses (FEA), using ABAQUS code, were performed to examine various joint geometries and to evaluate the affect of different interlayers on the residual stress state. Also, material systems composed of coating materials, interlayers, and braze alloys were developed for the program based on the chemical stability and strength of the joints during processing and service. Finally, the FEA results were compared with experiments using an idealized strength relationship. The results showed that the measured strength of the joint reached 30--90% of the strength by predicted by FEA. Overall results demonstrated that FEA is an effective tool for designing the geometries of ceramic-metal joints and that joining by brazing is a relevant method for advanced heat engine applications. 33 refs., 54 figs., 36 tabs.

  17. Size versus electronic factors in transition metal carbide and TCP phase stability

    NASA Astrophysics Data System (ADS)

    Pettifor, D. G.; Seiser, B.; Margine, E. R.; Kolmogorov, A. N.; Drautz, R.

    2013-09-01

    The contributions of atomic size and electronic factors to the structural stability of transition metal carbides and topologically close-packed (TCP) phases are investigated. The hard-sphere model that has been used by Cottrell to rationalize the occurrence of the octahedral and trigonal local coordination polyhedra within the transition metal carbides is shown to have limitations in TiC since density functional theory (DFT) predicts that the second most metastable phase closest to the B1 (NaCl) ground state takes the B? (BN) structure type with 5-atom local coordination polyhedra with very short Ti-C bond lengths. The importance of electronic factors in the TCP phases is demonstrated by DFT predictions that the A15, ? and ? phases are stabilized between groups VI and VII of the elemental transition metals, whereas the ? and Laves phases are destabilized. The origin of this difference is related to the bimodal shape parameter of the electronic density of states by using the bond-order potential expansion of the structural energy within a canonical tight-binding model. The importance of the size factor in the TCP phases is illustrated by the DFT heats of formation for the binary systems Mo-Re, Mo-Ru, Nb-Re and Nb-Ru which show that the ? and Laves phases become more and more stable compared to A15, ? and ? as the size factor increases from Mo-Re through to Nb-Ru.

  18. Study of Early Transition Metal Carbides for Energy Storage Applications

    NASA Astrophysics Data System (ADS)

    Dall'Agnese, Yohan

    An increase in energy and power density is needed to match the growing energy storage demands linked with the development of renewable energy production, and portable electronics. Several energy storage technologies exist including lithium-ion batteries, sodium-ion batteries, fuel cells and supercapacitors. These systems are mutually complementary. For example, supercapacitors can deliver high power densities whereas batteries can be used for high energy density applications. The first objective of this work was to investigate the electrochemical performances of a new family of 2-D materials called MXenes by cyclic voltammetry and galvanostatic charge-discharge measurements and to propose new solutions to tackle the energy storage concern. To achieve this goal, several directions have been explored. The first part of the research focused on Ti3C 2-based MXenes behavior as electrode materials for supercapacitors in aqueous electrolytes. The charge storage mechanisms in basic and neutral aqueous electrolytes, investigated by X-ray diffraction, were demonstrated to be attributed to cations intercalation between Ti3C2 layers. X-ray photoelectron spectroscopy highlighted the contribution of oxygenated functional groups on surface redox reactions in sulfuric acid. High capacitances were achieved, up to 520 F/cm3 and 325 F/g. Then the electrochemical behaviors of MXenes in sodium-based organic electrolytes were explored. A new hybrid system of sodium-ion capacitor was proposed. It was demonstrated that V2C-based MXene electrodes were suitable to be used as positive electrodes with an operating potential from 1 V to 3.5 V vs. Na+/Na. Continuous intercalation and de-intercalation of sodium ions between the V2C layers during sodiation and desodiation were showed by X-ray diffraction. An asymmetric sodium-ion capacitor full cell was assembled using hard carbon as negative electrode and showed promising results, with a capacity of 50 mAh/g. The last part was focused on the

  19. Carbide-forming groups IVB-VIB metals: a new territory in the periodic table for CVD growth of graphene.

    PubMed

    Zou, Zhiyu; Fu, Lei; Song, Xiuju; Zhang, Yanfeng; Liu, Zhongfan

    2014-07-01

    Early transition metals, especially groups IVB-VIB metals, can form stable carbides, which are known to exhibit excellent "noble-metal-like" catalytic activities. We demonstrate herein the applications of groups IVB-VIB metals in graphene growth using atmospheric pressure chemical vapor deposition technique. Similar to the extensively studied Cu, Ni, and noble metals, these transition-metal foils facilitate the catalytic growth of single- to few-layer graphene. The most attractive advantage over the existing catalysts is their perfect control of layer thickness and uniformity with highly flexible experimental conditions by in situ converting the dissolved carbons into stable carbides to fully suppress the upward segregation/precipitation effect. The growth performance of graphene on these transition metals can be well explained by the periodic physicochemical properties of elements. Our work has disclosed a new territory of catalysts in the periodic table for graphene growth and is expected to trigger more interest in graphene research. PMID:24873697

  20. A model for understanding the formation energies of nanolamellar phases in transition metal carbides and nitrides

    NASA Astrophysics Data System (ADS)

    Yu, Hang; Guziewski, Matthew; Thompson, Gregory B.; Weinberger, Christopher R.

    2016-06-01

    In this paper we introduce a stacking-fault based model to understand the energetics of formation of the nanolamellar-based metal carbide and nitride structures. The model is able to reproduce the cohesive energies of the stacking fault phases from density functional theory calculations by fitting the energy of different stacking sequences of metal layers. The model demonstrates that the first and second nearest metal-metal neighbor interactions and the nearest metal-carbon/nitrogen interaction are the dominant terms in determining the cohesive energy of these structures. The model further demonstrates that above a metal to non-metal ratio of 75%, there is no energetic favorability for the stacking faults to form a long-range ordered structure. The model’s applicability is demonstrated using the Ta-C system as its case study from which we report that the interfacial energy between ζ-Ta4C3 and TaC or Ta2C is negligible. Our results suggest that the closed packed planes of these phases should be aligned and that precipitated phases should be thin, which is in agreement with experiments.

  1. Phonon related properties of transition metals, their carbides, and nitrides: A first-principles study

    NASA Astrophysics Data System (ADS)

    Isaev, E. I.; Simak, S. I.; Abrikosov, I. A.; Ahuja, R.; Vekilov, Yu. Kh.; Katsnelson, M. I.; Lichtenstein, A. I.; Johansson, B.

    2007-06-01

    Lattice dynamics of body-centered cubic (bcc) Vb-VIb group transition metals (TM), and B1-type monocarbides and mononitrides of IIIb-VIb transition metals are studied by means of first-principles density functional perturbation theory, ultra soft pseudopotentials, and generalized gradient approximation to the exchange-correlation functional. Ground state parameters of transition metals and their compounds are correctly reproduced with the generated ultrasoft pseudopotentials. The calculated phonon spectra of the bcc metals are in excellent agreement with results of inelastic neutron scattering experiments. We show that the superconductivity of transition metal carbides (TMC) and transition metal nitrides (TMN) is related to peculiarities of the phonon spectra, and the anomalies of the spectra are connected to the number of valence electrons in crystals. The calculated electron-phonon interaction constants for TM, TMC, and TMN are in excellent agreement with experimentally determined values. Phonon spectra for a number of monocarbides and mononitrides of transition metals within the cubic NaCl- and hexagonal WC-type structures are predicted. Ideal stoichiometric B1 crystals of ScC, YC, and VC are predicted to be dynamically stable and superconducting materials. We also conclude that YN is a semiconductor.

  2. Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Stottlemyer, Alan L.; Kelly, Thomas G.; Meng, Qinghe; Chen, Jingguang G.

    2012-09-01

    Historically the interest in the catalytic properties of transition metal carbides (TMC) has been inspired by their "Pt-like" properties in the transformation reactions of hydrocarbon molecules. Recent studies, however, have revealed that the reaction pathways of oxygen-containing molecules are significantly different between TMCs and Pt-group metals. Nonetheless, TMCs demonstrate intriguing catalytic properties toward oxygen-containing molecules, either as the catalyst or as the catalytically active substrate to support metal catalysts, in several important catalytic and electrocatalytic applications, including water electrolysis, alcohol electrooxidation, biomass conversion, and water gas shift reactions. In the current review we provide a summary of theoretical and experimental studies of the interaction of TMC surfaces with oxygen-containing molecules, including both inorganic (O2, H2O, CO and CO2) and organic (alcohols, aldehydes, acids and esters) molecules. We will discuss the general trends in the reaction pathways, as well as future research opportunities in surface science studies that would facilitate the utilization of TMCs as catalysts and electrocatalysts.

  3. Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

    NASA Astrophysics Data System (ADS)

    Stottlemyer, Alan L.; Kelly, Thomas G.; Meng, Qinghe; Chen, Jingguang G.

    2012-09-01

    Historically the interest in the catalytic properties of transition metal carbides (TMC) has been inspired by their “Pt-like” properties in the transformation reactions of hydrocarbon molecules. Recent studies, however, have revealed that the reaction pathways of oxygen-containing molecules are significantly different between TMCs and Pt-group metals. Nonetheless, TMCs demonstrate intriguing catalytic properties toward oxygen-containing molecules, either as the catalyst or as the catalytically active substrate to support metal catalysts, in several important catalytic and electrocatalytic applications, including water electrolysis, alcohol electrooxidation, biomass conversion, and water gas shift reactions. In the current review we provide a summary of theoretical and experimental studies of the interaction of TMC surfaces with oxygen-containing molecules, including both inorganic (O2, H2O, CO and CO2) and organic (alcohols, aldehydes, acids and esters) molecules. We will discuss the general trends in the reaction pathways, as well as future research opportunities in surface science studies that would facilitate the utilization of TMCs as catalysts and electrocatalysts.

  4. Transition metals and their carbides and nitrides: Trends in electronic and structural properties

    SciTech Connect

    Grossman, J.C.; Mizel, A.; Cote, M.; Cohen, M.L.; Louie, S.G. Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 )

    1999-09-01

    A study of the structural and electronic properties of selected transition metals and their carbides and nitrides is presented. We focus on assessing trends of possible importance for understanding their hardness. Lattice constants, bulk moduli (B[sub o]), and charge densities are calculated using the local density approximation with a pseudopotential plane wave approach. An fcc lattice is employed for the transition metal elements in order to make comparisons and study trends relateable to their carbides and nitrides. Our results show that both increasing the number of valence d electrons and the presence of f electrons in the core lead to larger (B[sub o]). Charge density plots and histograms enable us to explain the nature of the charge distribution in the interstitial region for the different compounds considered. In addition, we include the heavier elements seaborgium, bohrium, and hasnium in order to test further trends. Surprisingly, the calculated B[sub o] for Hs is comparable to that of diamond. [copyright] [ital 1999] [ital The American Physical Society

  5. Structural and electronic studies of metal carbide clusterfullerene Sc2C2@Cs-C72

    NASA Astrophysics Data System (ADS)

    Feng, Yongqiang; Wang, Taishan; Wu, Jingyi; Feng, Lai; Xiang, Junfeng; Ma, Yihan; Zhang, Zhuxia; Jiang, Li; Shu, Chunying; Wang, Chunru

    2013-07-01

    We present a metal carbide clusterfullerene Sc2C2@Cs(10528)-C72, whose structure has been baffling for many years. A motional endohedral Sc2C2 cluster, special molecule geometry and electronic structure were found in Sc2C2@Cs(10528)-C72. The paramagnetic Sc2C2@Cs-C72 anion radical was successfully prepared by a chemical reduction method and hyperfine couplings in the ESR spectrum were observed.We present a metal carbide clusterfullerene Sc2C2@Cs(10528)-C72, whose structure has been baffling for many years. A motional endohedral Sc2C2 cluster, special molecule geometry and electronic structure were found in Sc2C2@Cs(10528)-C72. The paramagnetic Sc2C2@Cs-C72 anion radical was successfully prepared by a chemical reduction method and hyperfine couplings in the ESR spectrum were observed. Electronic supplementary information (ESI) available: Experimental details, HPLC chromatogram, and DFT calculations. CCDC 917712. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3nr01739g

  6. Optical and Spin Signatures of Transition Metal Impurities in Silicon Carbide

    NASA Astrophysics Data System (ADS)

    Koehl, William; Whitely, Samuel J.; Diler, Berk; Bourassa, Alexandre; Awschalom, David D.; Son, Nguyen Tien

    Point defects and impurities are increasingly viewed as an important resource for solid-state implementations of quantum information technologies. Electronic spins bound to point defects like the nitrogen vacancy center in diamond and divacancy in silicon carbide are especially attractive because they function as long-lived qubit states that can be controlled optically at the single-site level. These capabilities have generated a growing interest in identifying other classes of point defect with similar properties, since discovery of such systems might allow for new ranges of functionality in solid-state quantum device design. Transition metal ions are a promising area for exploration, since they often introduce isolated electronic levels within the bandgaps of semiconductors and possess a wide variety of magnetic and optical properties. Here we describe recent experimental studies of the optical and spin properties of transition metal impurities in silicon carbide. Using ensemble spectroscopies, we evaluate their potential for use as optically-controllable spin states within this industrially-important, wide-bandgap, optoelectronic material. This work supported by the AFOSR, NSF MRSEC, and Argonne LDRD Program.

  7. Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers

    DOE PAGESBeta

    Anasori, Babak; Shi, Chenyang; Moon, Eun Ju; Xie, Yu; Voigt, Cooper A.; Kent, Paul R. C.; May, Steven J.; Billinge, Simon J. L.; Barsoum, Michel W.; Gogotsi, Yury

    2016-02-24

    In this paper, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M3C2 and M4C3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX]nM arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M'2M"C2 and M'2M"2C3 – where M' and M" are two different early transition metals, such as Mo, Cr, Ta, Nb, V, andmore » Ti. The M' atoms only occupy the outer layers and the M" atoms fill the middle layers. In other words, M' atomic layers sandwich the middle M"–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo2TiC2 and Mo2Ti2C3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC]nM structures. The electronic properties of these Mo-containing MXenes are compared with their Ti3C2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo2TiC2Tx exhibits semiconductor-like transport behavior, while Ti3C2Tx is a metal. Finally, this finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.« less

  8. C-H Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3 (-).

    PubMed

    Li, Zi-Yu; Hu, Lianrui; Liu, Qing-Yu; Ning, Chuan-Gang; Chen, Hui; He, Sheng-Gui; Yao, Jiannian

    2015-12-01

    Although early transition metal (ETM) carbides can activate CH bonds in condensed-phase systems, the electronic-level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, CH activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3 (-) ) under thermal-collision conditions has been identified by using high-resolution mass spectrometry, photoelectron imaging spectroscopy, and high-level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3 (-) with C2 H6 . The CH activation follows a mechanism of oxidative addition that is much more favorable in the carbon-stabilized low-spin ground electronic state than in the high-spin excited state. The reaction efficiency between the MoC3 (-) anion and C2 H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt(+) +C2 H6 ) was made. It turned out that the potential-energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different. PMID:26490554

  9. Ion-plasma erosion-resistant nanocoatings based on metal carbides and nitrides

    NASA Astrophysics Data System (ADS)

    Muboyadzhyan, S. A.; Aleksandrov, D. A.; Gorlov, D. S.

    2010-09-01

    The erosion, corrosion, and heat resistance of alloy/ion-plasma nanolayer coating compositions based on TiC and CrC carbides and TiN, CrN, ZrN, and AlN nitrides are studied. The effect of the nanolayer thickness, composition, and structure of the coatings based on the metal nitrides and carbides on the relative erosion resistance of alloy/coating compositions in a gas-abrasive quartz sand flux is studied at a sand grain size of 300-350 μm, abrasive supply rate of 200 g/min, and an angle of flux incidence of 20° (tangential flow) and 70° (near-head-on attack flow). It is shown that high erosion resistance is characteristic of 15-22 μm thick coatings that are produced by assisted deposition and consist of alternating TiN (70 nm) and CrN (70 nm) layers on a VT1-0 titanium alloy or TiC (70 nm) and CrC (70 nm) layers on an EP866 compressor steel.

  10. New catalysts for coal processing: Metal carbides and nitrides. Final report, September 11, 1991--September 10, 1994

    SciTech Connect

    Oyama, S.T.

    1994-06-08

    The main objective of this project was to study transition metal carbides and nitrides as catalysts for hydroprocessing. In particular, the goals were to study the solid-state transformations that occur during synthesis of the compounds using a temperature-programmed method, and to investigate the catalytic properties of the materials for the upgrading of model coal liquids at realistic process conditions.

  11. Preparation and sintering of refractory metal borides, carbides and nitrides of high purity

    SciTech Connect

    Sane, A.Y.

    1987-09-15

    The method of preparing a consolidated and purified Group IVb, Vb, or VIb refractory metal boride, carbide, nitride, or mixture, combination or cermet thereof by means of aided, reduced pressure and elevated temperature conditions is described. It consists of: (a) establishing a composition for a second stage reaction step of reaction sintering and adapted for enhanced production of desired product; (b) providing sintering aid at least in part together with the composition and resting the composition upon the sintering aid, which aid is solid at normal pressure and temperatures and aids via the vapor phase at the pressure and temperature conditions of the second stage reaction step; (c) reducing the pressure around the composition; (d) heating the composition at a temperature for sintering; while (e) establishing sintering aid atmosphere in contact with the composition; and (f) maintaining the heating for a time sufficient to consolidate the composition, and thereby prepare a consolidate and purified product.

  12. Clean and metal-doped bundles of boron-carbide nanotubes: A density functional study

    NASA Astrophysics Data System (ADS)

    Ponomarenko, O.; Radny, M. W.; Smith, P. V.

    2007-07-01

    Carbon nanotubes and many types of inorganic nanotubes can be produced in the form of hexagonal arrays or bundles. In this paper, we discuss results of ab initio density functional theory calculations on the stability, and atomic and electronic structure, of bundles of narrow, clean, and Li- and Cu-doped, boron-carbide nanotubes related to LiBC and CuBC layered compounds. We find that covalent bonding arises between neighboring tubes in the bundles which results in the formation of complex structures. We show that a high concentration of dopant Li atoms in the bundles can be achieved by a combination of in-tube and interstitial doping. A high concentration of Li atoms involving only in-tube doping is energetically unfavorable due to repulsive interaction between the Li atoms. By contrast, increased doping with Cu atoms can produce a metallic wirelike structure along the longitudinal axis of each tube within the bundle.

  13. Low loadings of platinum on transition metal carbides for hydrogen oxidation and evolution reactions in alkaline electrolytes.

    PubMed

    Wang, Lu; Mahoney, Elizabeth G; Zhao, Shen; Yang, Bolun; Chen, Jingguang G

    2016-03-01

    Low-loadings of Pt supported over six transition metal carbide (Pt/TMC) powder catalysts were synthesized and evaluated for hydrogen oxidation and evolution reactions in an alkaline electrolyte. The roughness factor of each Pt/TMC catalyst was different, indicating that the carbide supports affect the dispersion of Pt. Furthermore, when normalized by the corresponding roughness factors, all Pt/TMC catalysts were found to have similar intrinsic activities that were comparable to the state-of-the-art commercial Pt/C electrocatalysts. PMID:26862592

  14. A new electrothermal-chemical method for metals, carbides, and ceramics hard coating: Experiment and theory

    SciTech Connect

    Zoler, D.; Bruma, C.; Cuperman, S.

    1999-07-01

    A new method and an experimental device for powders of metals, carbides and ceramics coating of various substrates are presented. The powder-particles are accelerated and heated by a mixture of plasma and gases resulted from the burning of an energetic (propellant). The operating prototype already allows one to obtain coatings of metals, carbides and ceramics. Some of the coatings obtained, especially those by carbides powders, indicate even at the present stage of research, properties (as hardness, porosity) which are comparable to those provided by the presently industrial methods in use. The accelerating-heating agent in the device (the plasma-gas mixture) is characterized by very high densities (up to 120 kg/m{sup 3}), temperatures (up to 20,000 K) and velocities (more than 1,500 m/s). Due to these characteristics, the powder particles are accelerated to velocities significantly higher than those reached in other coating devices as, for example, the detonation (D) gun. Some preliminary experimental data show that the accelerated particle can reach velocities higher than 1,000 m/s. In parallel, in order to better understand the phenomena taking place inside the device and to determine the optimal process parameters leading to high quality coatings an appropriate theoretical model was developed. The model is able to describe the complex processes of plasma-gas-propellant interaction, gas flow and powder particles heating and acceleration. The model gives a detailed description of the gas, propellant and accelerated particle parameters, their spatial distribution and temporal evolution; predicts their dependence on the values of some input quantities such as: the plasma energy, propellant characteristics and accelerated particles type and geometry. The computational results the authors obtained show that, indeed, during the acceleration process the particles are heated, melted and eventually vaporized. One of the most interesting theoretical results is that the

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

    NASA Astrophysics Data System (ADS)

    Johnston, Jamin M.; Catledge, Shane A.

    2016-02-01

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

  16. Effect of Catalytic Graphitization on the Thermo-Mechanical Properties of Isotropic Graphite Doped with Metallic Carbides

    NASA Astrophysics Data System (ADS)

    OrdA~¡s, N.; GarcA~­-Rosales, C.; Lindig, S.; Balden, M.; Wang, H.

    The influence of several graphitization parameters (temperature, dwell time, HIPing subsequent to graphitization) on the final properties of doped isotropic graphite has been investigated. The aim of this work is to obtain doped isotropic graphite with reduced chemical erosion by hydrogen bombardment, high thermal conductivity and large thermal shock resistance. As starting material, a self-sintering mesophase carbon powder and different metallic carbides (TiC, VC, ZrC and WC) as dopants has been used. Longer dwell time results in a remarkable increase of thermal conductivity, depending on the dopant and on the graphitization temperature. However, it leads also to carbide coarsening and local carbide agglomeration and thus to degradation of the mechanical properties. HIPing subsequent to graphitization leads to a significant reduction of porosity for the materials doped with VC and WC and thus to an improvement of their mechanical properties. A solid–liquid–solid model for metal catalysts can be applied to our experimental observations of graphitization in the presence of metallic carbides.

  17. CuCl2 for the isolation of a broad array of endohedral fullerenes containing metallic, metallic carbide, metallic nitride, and metallic oxide clusters, and separation of their structural isomers.

    PubMed

    Stevenson, Steven; Rottinger, Khristina A

    2013-08-19

    A typical arc-synthesis generates many types of fullerenes and endohedrals. Resulting soot extracts contain a complex mixture of >50 types of fullerenes, metallofullerenes, and their structural isomers. Prior to application development, novel separation methods are required to fractionate this rich array of metallic, metallic carbide, metallic nitride, and metallic oxide endohedrals, all of which can be present in a single, soot extract. Herein, we report the discovery of CuCl2 as a Lewis acid that will selectively precipitate only the more reactive members of each of these endohedral families. The more reactive Sc4O2@Ih-C80, Sc3C2@Ih-C80, and Sc3N@D3h-C78 endohedrals are quickly removed from extracts to greatly decrease the number of endohedrals present in a sample. Experiments indicate that enrichment factors of several orders of magnitude can be achieved within minutes of reaction time. CuCl2 also has sufficient selectivity to resolve and separate structural isomers, as demonstrated with Er2@C82 (isomer I, Cs(6)-C82 versus isomer III). The selective complexation of CuCl2 with fullerenes can be correlated to their first oxidation potential. We estimate a significantly lower threshold of precipitation for CuCl2 (<0.19 V) compared to stronger Lewis acids. Fullerenes and metallofullerenes having first oxidation potentials above 0.19 V tend to remain unreacted in solution. In contrast, species with first oxidation potentials below 0.19 V (vs Fc/Fc(+)) precipitate via complexation, and are easily decomplexed. CuCl2 is compared to Lewis acids having higher precipitation thresholds (e.g., FeCl3) in our goal to predict a priori which endohedrals would remain in solution versus which endohedral species would complex and precipitate. The ability to predict endohedral precipitation a priori is beneficial to the design of purification strategies for metallofullerenes. PMID:23952569

  18. Effect of initial composition on boron carbide production by SHS process followed by acid leaching

    NASA Astrophysics Data System (ADS)

    Alkan, Murat; Sonmez, M. Seref; Derin, Bora; Yücel, Onuralp

    2012-11-01

    In this study, iron-free boron carbide powders (B4C) were produced from the milled SHS (self-propagating high temperature synthesis) products followed by leaching in an aqueous hydrochloric acid (HCl) media. The SHS mixtures were composed of boron oxide (B2O3), carbon black and magnesium. Thermochemical simulations were performed to estimate the effect of initial composition on the SHS process. In the SHS experiments, it was found that the formations of boron carbide and magnesium borates were directly related with B2O3 and carbon black contents in the initial SHS mixture. The aqueous HCl leaching of the SHS products did not only eliminate the unwanted byproducts (i.e. MgO, Mg3B2O6 and Mg2B2O5) but also enhanced substantially the pore structure of the particles. Even though the leached SHS particles (d0.5 = 7.96 μm) were much coarser than that of the commercial powder (d0.5 = 1.73 μm), the surface area of the leached product (15.56 m2/g) was found to be larger than that of commercial one (4.92 m2/g).

  19. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    SciTech Connect

    Ebbinghaus, B.B.

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF[sub 2], ThO[sub 2], YDT(0.85ThO[sub 2]-0.15YO[sub 1.5]), and LDT(0.85ThO[sub 2]- 0.15LaO[sub 1.5]) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  20. The strong reactions of Lewis-base noble-metals with vanadium and other acidic transition metals

    SciTech Connect

    Ebbinghaus, B.B.

    1991-05-01

    The noble metals often thought of as unreactive solids,react strongly with nearly 40% of the elements in the periodictable: group IIIB-VB transition metals, lanthanides, theactinides, and group IIIA-IVA non-transition metals. These strong reactions arise from increased bonding/electron transfer fromnonbonding electrons d electron pairs on the noble metal tovacant orbitals on V, etc. This effect is a generalized Lewis acid-base interaction. The partial Gibbs energy of V in the noblemetals has been measured as a function of concentration at a temperature near 1000C. Thermodynamics of the intermetallics are determined by ternary oxide equilibria, ternary carbide equilibria, and the high-temperature galvanic cell technique. These experimental methods use equilibrated solid composite mixtures in which grains of V oxides or of V carbides are interspersed with grains of V-NM(noble-metal) alloys. In equilibrium the activity of V in the oxide or the carbide equals the activity in the alloy. Consequently, the thermodynamics available in the literature for the V oxides and V carbides are reviewed. Test runs on the galvanic cell were attempted. The V oxide electrode reacts with CaF{sub 2}, ThO{sub 2}, YDT(0.85ThO{sub 2}-0.15YO{sub 1.5}), and LDT(0.85ThO{sub 2}- 0.15LaO{sub 1.5}) to interfere with the measured data observed toward the beginning of a galvanic cell experiment are the most accurate. The interaction of vanadium at infinite dilution in the noble-metals was determined.

  1. An efficient hydrogenation catalyst in sulfuric acid for the conversion of nitrobenzene to p-aminophenol: N-doped carbon with encapsulated molybdenum carbide.

    PubMed

    Wang, Tao; Dong, Zhen; Cai, Weimeng; Wang, Yongzheng; Fu, Teng; Zhao, Bin; Peng, Luming; Ding, Weiping; Chen, Yi

    2016-08-23

    The transfer of catalytic function from molybdenum carbide to N-doped carbon has been tested by encapsulating molybdenum carbide with N-doped carbon using a one-pot preparation process. The outer layer of N-doped carbon, inert itself, exhibits high activity and excellent selectivity with molybdenum carbide as the catalyst for the hydrogenation of nitrobenzene to p-aminophenol in sulfuric acid. PMID:27506592

  2. EPR investigations of silicon carbide nanoparticles functionalized by acid doped polyaniline

    NASA Astrophysics Data System (ADS)

    Karray, Fekri; Kassiba, Abdelhadi

    2012-06-01

    Nanocomposites (SiC-PANI) based on silicon carbide nanoparticles (SiC) encapsulated in conducting polyaniline (PANI) are synthesized by direct polymerization of PANI on the nanoparticle surfaces. The conductivity of PANI and the nanocomposites was modulated by several doping levels of camphor sulfonic acid (CSA). Electron paramagnetic resonance (EPR) investigations were carried out on representative SiC-PANI samples over the temperature range [100-300 K]. The features of the EPR spectra were analyzed taking into account the paramagnetic species such as polarons with spin S=1/2 involved in two main environments realized in the composites as well as their thermal activation. A critical temperature range 200-225 K was revealed through crossover changes in the thermal behavior of the EPR spectral parameters. Insights on the electronic transport properties and their thermal evolutions were inferred from polarons species probed by EPR and the electrical conductivity in doped nanocomposites.

  3. Nanosized Borides and Carbides for Electroplating. Metal-Matrix Coatings: Specifications, Performance Evaluation

    NASA Astrophysics Data System (ADS)

    Galevskiy, G. V.; Rudneva, V. V.; Galevskiy, S. G.; Il’yashchenko, D. P.; Kartsev, D. S.

    2016-04-01

    This paper summarizes experience of application of nano-sized carbides and borides of titanium and chromium, silicon carbide as components of electro-depositable coating compositions based on nickel, zinc, and chromium. Basic physical and mechanical properties of the coatings are determined. Technological and economic evaluation is completed; practicability of high-cost nano-diamonds substitution for nano-sized borides and carbides is justified.

  4. Monitoring the formation of carbide crystal phases during the thermal decomposition of 3d transition metal dicarboxylate complexes

    SciTech Connect

    Huba, ZJ; Carpenter, EE

    2014-06-06

    Single molecule precursors can help to simplify the synthesis of complex alloys by minimizing the amount of necessary starting reagents. However, single molecule precursors are time consuming to prepare with very few being commercially available. In this study, a simple precipitation method is used to prepare Fe, Co, and Ni fumarate and succinate complexes. These complexes were then thermally decomposed in an inert atmosphere to test their efficiency as single molecule precursors for the formation of metal carbide phases. Elevated temperature X-ray diffraction was used to identify the crystal phases produced upon decomposition of the metal dicarboxylate complexes. Thermogravimetric analysis coupled with an infrared detector was used to identify the developed gaseous decomposition products. All complexes tested showed a reduction from the starting M2+ oxidation state to the M oxidation state, upon decomposition. Also, each complex tested showed CO2 and H2O as gaseous decomposition products. Nickel succinate, iron succinate, and iron fumarate complexes were found to form carbide phases upon decomposition. This proves that transition metal dicarboxylate salts can be employed as efficient single molecule precursors for the formation of metal carbide crystal phases.

  5. ROLE OF C AND P SITES ON THE CHEMICAL ACTIVITY OF METAL CARBIDE AND PHOSPHIDES: FROM CLUSTERS TO SINGLE-CRYSTAL SURFACES

    SciTech Connect

    RODRIGUEZ,J.A.; VINES, F.; LIU, P.; ILLAS, F.

    2007-07-01

    Transition metal carbides and phosphides have shown tremendous potential as highly active catalysts. At a microscopic level, it is not well understood how these new catalysts work. Their high activity is usually attributed to ligand or/and ensemble effects. Here, we review recent studies that examine the chemical activity of metal carbide and phosphides as a function of size, from clusters to extended surfaces, and metal/carbon or metal/phosphorous ratio. These studies reveal that the C and P sites in these compounds cannot be considered as simple spectators. They moderate the reactivity of the metal centers and provide bonding sites for adsorbates.

  6. A Study of the Metal Carbide-Carbon Peritectic Phase Transition for the Cr-C System

    NASA Astrophysics Data System (ADS)

    Yamada, Y.; Wang, Y.; Zheng, W.; Sasajima, N.

    2007-12-01

    The authors recently reported the very first radiometric plateau observation of high-temperature fixed points of metal-carbide carbon peritectics. These act in a similar way to the metal (carbide)-carbon eutectic points in the sense that they can be used at high temperature without being contaminated by their graphite crucibles. The performance seems similar in terms of repeatability and plateau shape. The peritectic transition temperatures are close to the transition temperatures of some of the metal (carbide)-carbon eutectics. In this article, results of further study to understand the melting and freezing involved in these fixed points are reported, with the focus on the Cr3C2-C peritectic point. Difficulty in producing an ingot without voids was encountered. To overcome this, a filling technique that takes advantage of the capillary effect was devised. Plateau shapes and microstructures observed with electron-probe microanalysis (EPMA) and back-scattered electron imaging (BSE) for various filling methods were compared. The observation of two fixed-point plateaux, one at the Cr3C2-C peritectic point and the other at a lower temperature of the Cr7C3-Cr3C2 eutectic point, correlates to the presence of two kinds of domains in the observed microstructure. The graphite crucible is shown to play an essential role in realizing peritectic plateaux of good quality.

  7. BIORECOVERY OF METALS FROM ACID MINE DRAINAGE

    EPA Science Inventory

    Acid mine water is an acidic, metal-bearing wastewater generated by the oxidation of metallic sulfides by certain bacteria in both active and abandoned mining operations. The wastewaters contain substantial quantities of dissolved solids with the particular pollutants dependant u...

  8. Catalytic hydrodechlorination of chloroarenes over novel transition metal and carbide catalysts

    NASA Astrophysics Data System (ADS)

    Jujjuri, Satyakrishna T. H.

    -Cl bond activation for hydrogen scission. HDC kinetics have been studied in detail for reaction over Pd/SiO2 where the effects of altering hydrogen partial pressure and temperature on HDC activity/selectivity have been considered with a view to process optimization. The feasibility of applying Group VI transition metal (Mo and W) carbides and nitrides as HDC catalysts has also been addressed where HDC performance is correlated with critical catalyst characterization results.

  9. Silicon carbide: A unique platform for metal-oxide-semiconductor physics

    SciTech Connect

    Liu, Gang; Tuttle, Blair R.; Dhar, Sarit

    2015-06-15

    A sustainable energy future requires power electronics that can enable significantly higher efficiencies in the generation, distribution, and usage of electrical energy. Silicon carbide (4H-SiC) is one of the most technologically advanced wide bandgap semiconductor that can outperform conventional silicon in terms of power handling, maximum operating temperature, and power conversion efficiency in power modules. While SiC Schottky diode is a mature technology, SiC power Metal Oxide Semiconductor Field Effect Transistors are relatively novel and there is large room for performance improvement. Specifically, major initiatives are under way to improve the inversion channel mobility and gate oxide stability in order to further reduce the on-resistance and enhance the gate reliability. Both problems relate to the defects near the SiO{sub 2}/SiC interface, which have been the focus of intensive studies for more than a decade. Here we review research on the SiC MOS physics and technology, including its brief history, the state-of-art, and the latest progress in this field. We focus on the two main scientific problems, namely, low channel mobility and bias temperature instability. The possible mechanisms behind these issues are discussed at the device physics level as well as the atomic scale, with the support of published physical analysis and theoretical studies results. Some of the most exciting recent progress in interface engineering for improving the channel mobility and fundamental understanding of channel transport is reviewed.

  10. Electronic structure and optical properties of layered ternary transition-metal carbides and nitrides

    NASA Astrophysics Data System (ADS)

    Mo, Yuxiang

    2011-12-01

    The electronic structure and optical properties of Ti3AC 2 (A=Al, Si, Ge), Ti2AC (A=Al, Ga, In; Si, Ge, Sn; P, As; S), Ti2AlN, M2AlC (M=V, Nb, Cr) and Tan+1AlC n (n=1˜4) have been studied using first--principles orthogonalized linear combination of atomic orbitals (OLCAO) method. These layered ternary transition--metal carbides and nitrides are also commonly referred to as "MAX phases". Trends were observed for the calculated density of states (DOS) at Fermi--level, with respect to elemental variations and number of M and X layers. A local minimum of DOS(Ef) was found for Ti3AlC2, Ti2InC and Cr2AlC, predicting relatively high intrinsic structural stability. While a local maximum or an incline was discovered for Ti3GeC2, Ti2GeC, Ti2SnC, Ti 2PC, Nb2AlC, Ta2AlC, Ta4AlC3 and Ta5AlC4, indicating their lower intrinsic structural stability. Inter-band optical conductivities showed anisotropy, but not considerable. The reflectance and colors of the MAX phase compounds were also obtained.

  11. Rovibronically Selected and Resolved Laser Photoionization and Photoelectron Studies of Transition Metal Carbides, Nitrides, and Oxides.

    NASA Astrophysics Data System (ADS)

    Luo, Zhihong; Chang, Yih-Chung; Huang, Huang; Ng, Cheuk-Yiu

    2014-06-01

    Transition metal (M) carbides, nitrides, and oxides (MX, X = C, N, and O) are important molecules in astrophysics, catalysis, and organometallic chemistry. The measurements of the ionization energies (IEs), bond energies, and spectroscopic constants for MX/MX+ in the gas phase by high-resolution photoelectron methods represent challenging but profitable approaches to gain fundamental understandings of the electronic structures and bonding properties of these compounds and their cations. We have developed a two-color laser excitation scheme for high-resolution pulse field ionization photoelectron (PFI-PE) measurements of MX species. By exciting the neutral MX species to a single rovibronic state using a visible laser prior to photoionization by a UV laser, we have obtained fully rotational resolved PFI-PE spectra for TiC+, TiO+, VCH+, VN+, CoC+, ZrO+, and NbC+. The unambiguous rotational assignments of these spectra have provided highly accurate IE values for TiC, TiO, VCH, VN, CoC, ZrO, and NbC, and spectroscopic constants for their cations.

  12. Enhancement of Wettability of Aluminum Based Silicon Carbide Reinforced Particulate Metal Matrix Composite

    NASA Astrophysics Data System (ADS)

    Singh, V. K.; Chauhan, Sakshi; Gope, P. C.; Chaudhary, A. K.

    2015-04-01

    Lately, materials research has shifted to composite materials from monolithic, adjusting to the global need for light weight, low cost, quality, and high performance in structural materials. Every effort aims to develop a material which can be appropriate for various industry and machinery purpose. In the present study, a modest attempt has been made to develop cast aluminum based silicon carbide (SiC) particulate metal matrix composite (MMC) and worked upon to raise the wettability factor between the matrix and dispersion phase. Magnesium (Mg) is used as wetting agent. It works by scavenging the oxygen from dispersoids surface and thinning the gas layer around dispersoids and this is done by forming MgO or MgAl2O4 or both according to concentration of Magnesium added. Mg2Si is the compound responsible for strengthening. The combination of aluminum and magnesium seems to have synergetic effect on wetting and give appropriate strength. All mechanical properties obtained are well correlated with microstructure obtained by Scanning electron micrograph. Differential thermal analysis (DTA) and thermo gravimetric analysis (TGA) also justified the results obtained in present investigations.

  13. Silicon carbide: A unique platform for metal-oxide-semiconductor physics

    NASA Astrophysics Data System (ADS)

    Liu, Gang; Tuttle, Blair R.; Dhar, Sarit

    2015-06-01

    A sustainable energy future requires power electronics that can enable significantly higher efficiencies in the generation, distribution, and usage of electrical energy. Silicon carbide (4H-SiC) is one of the most technologically advanced wide bandgap semiconductor that can outperform conventional silicon in terms of power handling, maximum operating temperature, and power conversion efficiency in power modules. While SiC Schottky diode is a mature technology, SiC power Metal Oxide Semiconductor Field Effect Transistors are relatively novel and there is large room for performance improvement. Specifically, major initiatives are under way to improve the inversion channel mobility and gate oxide stability in order to further reduce the on-resistance and enhance the gate reliability. Both problems relate to the defects near the SiO2/SiC interface, which have been the focus of intensive studies for more than a decade. Here we review research on the SiC MOS physics and technology, including its brief history, the state-of-art, and the latest progress in this field. We focus on the two main scientific problems, namely, low channel mobility and bias temperature instability. The possible mechanisms behind these issues are discussed at the device physics level as well as the atomic scale, with the support of published physical analysis and theoretical studies results. Some of the most exciting recent progress in interface engineering for improving the channel mobility and fundamental understanding of channel transport is reviewed.

  14. Trends in bulk electron-structural features of rocksalt early transition-metal carbides

    NASA Astrophysics Data System (ADS)

    Vojvodic, Aleksandra; Ruberto, Carlo

    2010-09-01

    A detailed and systematic density-functional theory (DFT) study of a series of early transition-metal carbides (TMCs) in the NaCl structure is presented. The focus is on the trends in the electronic structure and nature of bonding, which are essential for the understanding of the reactivity of TMCs. The employed approach is based on a thorough complementary analysis of the electron density differences, the density of states (DOS), the band structure and the real-space wavefunctions to gain an insight into the bonding of this class of materials and get a more detailed picture of it than previously achieved, as the trend study allows for a systematic identification of the bond character along the different bands. Our approach confirms the presence of both the well-known TM-C and TM-TM bonds and, more importantly, it shows the existence and significance of direct C-C bonds in all investigated TMCs, which are frequently neglected but have been identified in some cases (Zhang et al 2002 Solid State Commun. 121 411; Ruberto et al 2007 Phys. Rev. B 75 235438). New information on the spatial extent of the bonds, their k-space location within the band structure and their importance for the bulk cohesion is provided. Trends in covalency and ionicity are presented. The resulting electron-structural trends are analyzed and discussed within a two-level model.

  15. Self-lubricating aluminum metal-matrix composites dispersed with tungsten disulfide and silicon carbide

    SciTech Connect

    Prasad, S.V.; Mecklenburg, K.R.

    1994-07-01

    This paper describes the synthesis and tribological behavior of self-lubricating aluminum alloy metal-matrix composites (MMCs). The formulations of MMCs comprised of tungsten disulfide (WS{sub 2}) and silicon carbide (SiC) particles dispersed in a commercial aluminum alloy (Al-0.40Si-0.75Mg) matrix. Composites were fabricated by a conventional powder metallurgy route involving blending, compacting and sintering. Friction and wear tests (up to a duration of one million cycles) were performed in a ball-on-disk configuration against a steel counterface. Wear scars on MMC disks and steel balls were analyzed in SEM/EDXS. In a dry nitrogen environment, the steady state friction coefficient of an Al-0.10SiC-0.03WS{sub 2}MMC was 0.05, whereas in laboratory air with relative humidity at approximately 65 percent it was 0.10. In both environments, transfer of aluminum to the steel counterface was absent. 20 refs., 12 figs., 2 tabs.

  16. Nanoporous, Metal Carbide, Surface Diffusion Membranes for High Temperature Hydrogen Separations

    SciTech Connect

    Way, J.; Wolden, Colin

    2013-09-30

    Colorado School of Mines (CSM) developed high temperature, hydrogen permeable membranes that contain no platinum group metals with the goal of separating hydrogen from gas mixtures representative of gasification of carbon feedstocks such as coal or biomass in order to meet DOE NETL 2015 hydrogen membrane performance targets. We employed a dual synthesis strategy centered on transition metal carbides. In the first approach, novel, high temperature, surface diffusion membranes based on nanoporous Mo{sub 2}C were fabricated on ceramic supports. These were produced in a two step process that consisted of molybdenum oxide deposition followed by thermal carburization. Our best Mo{sub 2}C surface diffusion membrane achieved a pure hydrogen flux of 367 SCFH/ft{sup 2} at a feed pressure of only 20 psig. The highest H{sub 2}/N{sub 2} selectivity obtained with this approach was 4.9. A transport model using “dusty gas” theory was derived to describe the hydrogen transport in the Mo{sub 2}C coated, surface diffusion membranes. The second class of membranes developed were dense metal foils of BCC metals such as vanadium coated with thin (< 60 nm) Mo{sub 2}C catalyst layers. We have fabricated a Mo{sub 2}C/V composite membrane that in pure gas testing delivered a H{sub 2} flux of 238 SCFH/ft{sup 2} at 600 °C and 100 psig, with no detectable He permeance. This exceeds the 2010 DOE Target flux. This flux is 2.8 times that of pure Pd at the same membrane thickness and test conditions and over 79% of the 2015 flux target. In mixed gas testing we achieved a permeate purity of ≥99.99%, satisfying the permeate purity milestone, but the hydrogen permeance was low, ~0.2 SCFH/ft{sup 2}.psi. However, during testing of a Mo{sub 2}C coated Pd alloy membrane with DOE 1 feed gas mixture a hydrogen permeance of >2 SCFH/ft{sup 2}.psi was obtained which was stable during the entire test, meeting the permeance associated with the 2010 DOE target flux. Lastly, the Mo{sub 2}C/V composite

  17. Nanostructured metal carbides for aprotic Li-O2 batteries. New insights into interfacial reactions and cathode stability

    DOE PAGESBeta

    Kundu, Dipan; Black, Robert; Adams, Brian; Harrison, Katharine; Zavadil, Kevin R.; Nazar, Linda F.

    2015-05-01

    The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O2 to give lithium peroxide (Li2O2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li2O2 oxidation on a passivated nanostructured metallic carbide (Mo2C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the LixMoO3-passivated conductive interface formed on the carbide, owing to their close redoxmore » potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing LixMoO3 into the electrolyte, explaining the low charging potential.« less

  18. Nanostructured Metal Carbides for Aprotic Li-O2 Batteries: New Insights into Interfacial Reactions and Cathode Stability.

    PubMed

    Kundu, Dipan; Black, Robert; Adams, Brian; Harrison, Katharine; Zavadil, Kevin; Nazar, Linda F

    2015-06-18

    The development of nonaqueous Li-oxygen batteries, which relies on the reversible reaction of Li + O2 to give lithium peroxide (Li2O2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li2O2 oxidation on a passivated nanostructured metallic carbide (Mo2C), carbon-free cathode host. Online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the Li(x)MoO3-passivated conductive interface formed on the carbide, owing to their close redox potentials. The process rejuvenates the surface on each cycle upon electrochemical charge by releasing Li(x)MoO3 into the electrolyte, explaining the low charging potential. PMID:26266600

  19. Characterization of Interface State in Silicon Carbide Metal Oxide Semiconductor Capacitors

    NASA Astrophysics Data System (ADS)

    Kao, Wei-Chieh

    Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system.

  20. Surface group modification and carrier transport properties of layered transition metal carbides (Ti2CTx, T: -OH, -F and -O)

    NASA Astrophysics Data System (ADS)

    Lai, Shen; Jeon, Jaeho; Jang, Sung Kyu; Xu, Jiao; Choi, Young Jin; Park, Jin-Hong; Hwang, Euyheon; Lee, Sungjoo

    2015-11-01

    In spite of recent significant research into various two-dimensional (2D) materials after the emergence of graphene, the development of a new 2D material that provides both high mobility and an appropriate energy band gap (which are crucial for various device applications) remains elusive. In this report, we demonstrate that the carrier transport behaviour of 2D Ti2CTx, which belongs to the family of 2D transition metal carbides and nitrides, can be tuned by modifying the surface group Tx (-OH, -F, and -O). Our results show that 2D Ti2C(OH)xFy and Ti2COx films can be obtained via simple chemical treatment, thermal annealing, and mechanical exfoliation processes. For the first time, we study the carrier transport properties of 2D Ti2CTx field effect transistors (FETs), obtaining the high field effect carrier mobilities of 104 cm2 V-1 s-1 at room temperature. The temperature dependent resistivity of the Ti2COx film exhibits semiconductor like Arrhenius behaviour at zero gate voltage, from which we estimate the energy gap of 80 meV. One interesting feature of the FETs based on transition metal carbides is that the field effect mobility at room temperature is less sensitive to the measured transport gaps, which may arise from the dominant charge transport of activated carriers over the narrow energy gaps of the transition metal carbides. Our results open up the possibility that new 2D materials with high mobilities and appropriate band gaps can be achieved, and broaden the range of electronic device applications of Ti2CTx films.In spite of recent significant research into various two-dimensional (2D) materials after the emergence of graphene, the development of a new 2D material that provides both high mobility and an appropriate energy band gap (which are crucial for various device applications) remains elusive. In this report, we demonstrate that the carrier transport behaviour of 2D Ti2CTx, which belongs to the family of 2D transition metal carbides and nitrides

  1. Metal-like self-organization of periodic nanostructures on silicon and silicon carbide under femtosecond laser pulses

    SciTech Connect

    Gemini, Laura; Hashida, Masaki; Shimizu, Masahiro; Miyasaka, Yasuhiro; Inoue, Shunsuke; Tokita, Shigeki; Sakabe, Shuji; Limpouch, Jiri; Mocek, Tomas

    2013-11-21

    Periodic structures were generated on Si and SiC surfaces by irradiation with femtosecond laser pulses. Self-organized structures with spatial periodicity of approximately 600 nm appear on silicon and silicon carbide in the laser fluence range just above the ablation threshold and upon irradiation with a large number of pulses. As in the case of metals, the dependence of the spatial periodicity on laser fluence can be explained by the parametric decay of laser light into surface plasma waves. The results show that the proposed model might be universally applicable to any solid state material.

  2. The effect of formic acid concentration on the conductivity and corrosion resistance of chromium carbide coatings electroplated with trivalent chromium

    NASA Astrophysics Data System (ADS)

    Lu, Chen-En; Pu, Nen-Wen; Hou, Kung-Hsu; Tseng, Chun-Chieh; Ger, Ming-Der

    2013-10-01

    Different concentrations of formic acid were added into a trivalent chromium electroplating solution to produce chromium carbide (Crsbnd C) coatings. The influence of the formic acid concentration on chemical composition, microstructure, surface morphology, corrosion resistance, conductivity and carbon content of the resulting Crsbnd C coatings was studied. Formic acid was found to increase the carbon content in the coatings so as to form Crsbnd C films. These coatings had a nearly amorphous structure containing Cr, Cr2O3, and various Crsbnd C compounds with carbon content uniformly distributed throughout the coatings. The carbon content and the conductivity of the Crsbnd C layer were correlated with formic acid concentration. For a formic acid concentration of 2 M, the Crsbnd C layer had the highest carbon content (∼28%), the lowest contact resistance, and the best corrosion resistance along with a corrosion current density of ∼6.4 × 10-7 A/cm2.

  3. Large-scale delamination of multi-layers transition metal carbides and carbonitrides “MXenes”

    SciTech Connect

    Naguib, Michael; Unocic, Raymond R.; Armstrong, Beth L.; Nanda, Jagjit

    2015-04-17

    Herein we report on a general approach to delaminate multi-layered MXenes using an organic base to induce swelling that in turn weakens the bonds between the MX layers. Simple agitation or mild sonication of the swollen MXene in water resulted in the large-scale delamination of the MXene layers. The delamination method is demonstrated for vanadium carbide, and titanium carbonitrides MXenes.

  4. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals. Quarterly technical status report, October 1--December 31, 1992

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Howard, J.B.; Peters, W.A.

    1993-02-01

    Light hydrocarbon gases could be reacted with low cost alkaline earth metal oxide (CaO, MgO) in high-temperature plasma reactor to achieve very high ({le}100%) gas conversion to H{sub 2}, CO, and the corresponding metal carbides. These carbides could be stored, transported, and hydrolyzed to acetylene or methyl acetylene, which in turn could be upgraded to a wide range of chemicals and premium liquid hydrocarbon fuels. An electric arc discharge reactor was built for converting methane. Literature reviews were made.

  5. Process for microwave sintering boron carbide

    DOEpatents

    Holcombe, Cressie E.; Morrow, Marvin S.

    1993-01-01

    A method of microwave sintering boron carbide comprises leaching boron carbide powder with an aqueous solution of nitric acid to form a leached boron carbide powder. The leached boron carbide powder is coated with a glassy carbon precursor to form a coated boron carbide powder. The coated boron carbide powder is consolidated in an enclosure of boron nitride particles coated with a layer of glassy carbon within a container for microwave heating to form an enclosed coated boron carbide powder. The enclosed coated boron carbide powder is sintered within the container for microwave heating with microwave energy.

  6. Process for microwave sintering boron carbide

    DOEpatents

    Holcombe, C.E.; Morrow, M.S.

    1993-10-12

    A method of microwave sintering boron carbide comprises leaching boron carbide powder with an aqueous solution of nitric acid to form a leached boron carbide powder. The leached boron carbide powder is coated with a glassy carbon precursor to form a coated boron carbide powder. The coated boron carbide powder is consolidated in an enclosure of boron nitride particles coated with a layer of glassy carbon within a container for microwave heating to form an enclosed coated boron carbide powder. The enclosed coated boron carbide powder is sintered within the container for microwave heating with microwave energy.

  7. Determination of carbide-forming metals, chromium and barium, by graphite furnace atomic absorption spectrometry using a tungsten coil platform

    NASA Astrophysics Data System (ADS)

    Moreno Camero, Rosa; Alvarado, José

    2000-07-01

    The use of a tungsten coil as a platform has been evaluated for the determination of carbide-forming metals, Cr and Ba. The methodology developed has been used for Cr and Ba determinations in HPS CRM, Trace Metals in Drinking Water, and NIST SRM 1643b, Trace Elements in Water. Good agreement was found between the results obtained and the certified values for Cr in both reference materials and for Ba in the NIST SRM. Barium results were approximately 14% lower than the certified results for the HPS CRM. This inaccuracy was ascribed to the presence of considerable amounts of Ca in this particular material. Precision of the measurements, 3σ relative standard deviation as percentage, were 2.5 and 5.8 for Cr and Ba, respectively. Characteristic masses, in picograms, were 1.70 for Cr and 19.0 for Ba. These results compare favorably with the literature values for Cr but not for Ba.

  8. Influence of carbides and microstructure of CoCrMo alloys on their metallic dissolution resistance.

    PubMed

    Valero-Vidal, C; Casabán-Julián, L; Herraiz-Cardona, I; Igual-Muñoz, A

    2013-12-01

    CoCrMo alloys are passive and biocompatible materials widely used as joint replacements due to their good mechanical properties and corrosion resistance. Electrochemical behaviour of thermal treated CoCrMo alloys with different carbon content in their bulk alloy composition has been analysed. Both the amount of carbides in the CoCrMo alloys and the chemical composition of the simulated body fluid affect the electrochemical properties of these biomedical alloys, thus passive dissolution rate was influenced by the mentioned parameters. Lower percentage of carbon in the chemical composition of the bulk alloy and thermal treatments favour the homogenization of the surface (less amount of carbides), thus increasing the availability of Cr to form the oxide film and improving the corrosion resistance of the alloy. PMID:24094174

  9. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals. Quarterly technical status report, July 1, 1995--September 30, 1995

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Howard, J.B.

    1995-11-01

    Two final scoping runs were conducted to test the experimental protocol for methane conversion to alkaline earth metal carbides in the thermal plasma reactor and to refine the techniques for carbide analysis. Having demonstrated the adequacy of the experimental protocol, the systematic study of metal carbide synthesis from methane and MgO commenced. Initial runs with MgO/CH{sub 4} gave surprisingly low methane conversions (<2%) to magnesium carbides, despite high conversions (65-90%) to hydrogen. An X-ray diffraction analysis showed the presence of a significant amount of elemental magnesium, a finding supported by the observation of bright lights upon hydrolysis of the solid products in the open air. The high conversion to hydrogen and the presence of elemental Mg in the solid products suggest that the plasma effluent is not being quenched rapidly enough and any magnesium carbides formed may be decomposing into the elements. To test this hypothesis, attempts to increase quench rates were made including lowering the arc power level, decreasing the anode nozzle-to-probe distance and introducing more quench gas.

  10. Nanostructured metal carbides for aprotic Li-O2 batteries. New insights into interfacial reactions and cathode stability

    SciTech Connect

    Kundu, Dipan; Black, Robert; Adams, Brian; Harrison, Katharine; Zavadil, Kevin R.; Nazar, Linda F.

    2015-05-01

    The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O2 to give lithium peroxide (Li2O2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li2O2 oxidation on a passivated nanostructured metallic carbide (Mo2C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the LixMoO3-passivated conductive interface formed on the carbide, owing to their close redox potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing LixMoO3 into the electrolyte, explaining the low charging potential.

  11. Nitrogen doped carbon nanotubes with encapsulated ferric carbide as excellent electrocatalyst for oxygen reduction reaction in acid and alkaline media

    NASA Astrophysics Data System (ADS)

    Zhong, Guoyu; Wang, Hongjuan; Yu, Hao; Peng, Feng

    2015-07-01

    Nitrogen doped carbon nanotubes (NCNTs) with encapsulated Fe3C nanoparticles (Fe3C@NCNTs) are synthesized by a simple direct pyrolysis of melamine and ferric chloride. The characterization results reveal that Fe3C is mainly encapsulated in the interior of NCNTs and N species is mainly distributed on the outside surface of NCNTs. Iron and iron carbide catalyze the growth of NCNTs and are wrapped by carbon to form Fe3C@NCNTs. The as-prepared Fe3C@NCNTs catalyst exhibits superior oxygen reduction reaction (ORR) activity, excellent methanol tolerance and long-term stability in both acid and alkaline media. It is proven that the doped N is the main active site for ORR and the inner Fe3C with outside carbon form the synergetic active site to enhance ORR activity. The ORR mechanism of direct four electron transfer pathway is proved in acid and alkaline media.

  12. Gallic Acid, Ellagic Acid and Pyrogallol Reaction with Metallic Iron

    NASA Astrophysics Data System (ADS)

    Jaén, J. A.; González, L.; Vargas, A.; Olave, G.

    2003-06-01

    The reaction between gallic acid, ellagic acid and pyrogallol with metallic iron was studied using infrared and Mössbauer spectroscopy. Most hydrolysable tannins with interesting anticorrosive or inhibition properties are structurally related to these compounds, thus they may be used as models for the study of hydrolysable tannins and related polyphenols. The interaction was followed up to 3 months. Results indicated two different behaviors. At polyphenol concentrations higher than 1% iron converts to sparingly soluble and amorphous ferric (and ferrous) polyphenolate complexes. At lower concentrations (0.1%), the hydrolysis reactions are dominant, resulting in the formation of oxyhydroxides, which can be further reduced to compounds like magnetite by the polyphenols.

  13. Ion intercalation into two-dimensional transition-metal carbides: global screening for new high-capacity battery materials.

    PubMed

    Eames, Christopher; Islam, M Saiful

    2014-11-19

    Two-dimensional transition metal carbides (termed MXenes) are a new family of compounds generating considerable interest due to their unique properties and potential applications. Intercalation of ions into MXenes has recently been demonstrated with good electrochemical performance, making them viable electrode materials for rechargeable batteries. Here we have performed global screening of the capacity and voltage for a variety of intercalation ions (Li(+), Na(+), K(+), and Mg(2+)) into a large number of M2C-based compounds (M = Sc, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta) with F-, H-, O-, and OH-functionalized surfaces using density functional theory methods. In terms of gravimetric capacity a greater amount of Li(+) or Mg(2+) can be intercalated into an MXene than Na(+) or K(+), which is related to the size of the intercalating ion. Variation of the surface functional group and transition metal species can significantly affect the voltage and capacity of an MXene, with oxygen termination leading to the highest capacity. The most promising group of M2C materials in terms of anode voltage and gravimetric capacity (>400 mAh/g) are compounds containing light transition metals (e.g., Sc, Ti, V, and Cr) with nonfunctionalized or O-terminated surfaces. The results presented here provide valuable insights into exploring a rich variety of high-capacity MXenes for potential battery applications. PMID:25310601

  14. Uptake of metal ions on humic acids

    SciTech Connect

    Pehlivan, E.; Arslan, G.

    2006-09-15

    The kinetics, the sorption capacities, pH and temperature dependence of sorption of humic acids (HAs) of Turkish brown coals with respect to Zn(II), Cu(II), Ni(II), Co(II) and Pb(II) ions were investigated, and the roles of the carboxylic and phenolic groups in the adsorption of metals ion on HAs were searched in this work. These metal ions are able to form complex compounds with carboxylic and phenolic groups of HAs. Adsorption equilibrium was achieved in between 50 and 60 min for all studied cations. HAs extracted from different brown coals have been characterized by chemical and physical methods. The chemical properties of HAs showed differences depending on the source from which they were obtained. The sorption of metals on the surface of HAs depends strongly on the pH, and sorption decreases with decreasing pH. Maximum removal of metal ions was demonstrated at pH values of 4.1-5.0. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The {Delta}G{sup 0} became negative as the temperature increased, and so the equilibrium constant decreased slightly. The investigation proved that the HAs are suitable materials for the studied heavy metal ion removal from aqueous solution and could be considered as potential material for purification of effluent polluted with toxic metal ions.

  15. Adhesion of metal carbide/nitride interfaces: Al/TiC and Al/TiN

    NASA Astrophysics Data System (ADS)

    Liu, L. M.; Wang, S. Q.; Ye, H. Q.

    2003-12-01

    We employ density functional theory to investigate and compare Al/TiC and Al/TiN interfaces by electronic structures, relaxed atomic geometries and adhesions. The results show that the preferred bonding site is the interfacial Al atoms above the ceramic's metalloid atoms for both systems. The calculated adhesion energies are quantitatively in agreement with other calculated and experimental results of Al on the carbide and nitride. A detailed comparison of the adhesion energies and relaxed structures shows weaker bonding and less relaxation in the Al/nitride case, which is correlated with the lower surface energy of the ceramic. We have thoroughly characterized the electronic structure and determined that the polar covalent Al3sp-C(N)2s bonds constitute the primary interfacial bonding interaction. The larger overlapping bonding states at the Al/TiC interface reveal the reason why it exhibits relatively larger adhesion energy. Cleavage may take place preferentially at the interface, especially for the Al/TiN, which is in agreement with experimental results.

  16. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    DOE PAGESBeta

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOHmore » and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.« less

  17. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    SciTech Connect

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOH and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

  18. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2016-01-01

    In this work, a detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented for select MXenes-a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Herein we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, sbnd O, sbnd OH and sbnd F, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. From XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

  19. High temperature brush seal tuft testing of metallic bristles versus chrome carbide

    NASA Technical Reports Server (NTRS)

    Fellenstein, James A.; DellaCorte, Christopher; Moore, Kenneth D.; Boyes, Esther

    1996-01-01

    The tribology of brush seals is of considerable interest to turbine engine designers because bristle wear continues to limit long term seal performance and life. To provide better materials characterization and foster the development of improved seals, NASA Lewis has developed a brush seal tuft tester. In this test, a 'paintbrush' sample tuft is loaded under constant contact pressure against the outside diameter of a rotating journal. With this configuration a direct measurement of load and friction is made. Accurate wear rate measurements are possible due to the known contact pressure. Previously reported baseline research using this facility showed good data repeatability and wear morphology similar to published seal data. This paper extends and expands the database for candidate brush seal materials. A series of tuft tests were completed to evaluate the performance of five high temperature superalloy wires sliding against plasma sprayed nichrome-bonded chrome carbide. Wire materials were either nickel-chrome or cobalt-chrome based superalloys. Good corroboration of the tuft results with dynamic seal rig tests was observed; giving additional confidence in the tuft test as a screening and development tool.

  20. AES XPS study of chromium carbides and chromium iron carbides

    NASA Astrophysics Data System (ADS)

    Detroye, M.; Reniers, F.; Buess-Herman, C.; Vereecken, J.

    1999-04-01

    The nature of chromium rich carbides which precipitate at grain boundaries in steels is still not perfectly understood. We performed a multitechnique approach on model chromium carbide and chromium-iron carbide samples: Auger Electron Spectroscopy (AES), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), and High Energy Electron Diffraction (HEED) were used to characterise the samples. Significant chemical shifts were observed for the Cr, Fe and C XPS peaks in the M 7C 3 compound (M stands for metal), indicating unambiguously that the compound formed is a mixed iron-chromium carbide.

  1. Analytical and experimental evaluation of joining silicon nitride to metal and silicon carbide to metal for advanced heat engine applications. Final report

    SciTech Connect

    Kang, S.; Selverian, J.H.; O`Neil, D.; Kim, H.; Kim, K.

    1993-05-01

    This report summarizes the results of Phase 2 of Analytical and Experimental Evaluation of Joining Silicon Nitride to Metal and Silicon Carbide to Metal for Advanced Heat Engine Applications. A general methodology was developed to optimize the joint geometry and material systems for 650{degrees}C applications. Failure criteria were derived to predict the fracture of the braze and ceramic. Extensive finite element analyses (FEA) were performed to examine various joint geometries and to evaluate the affect of different interlayers on the residual stress state. Also, material systems composed of coating materials, interlayers, and braze alloys were developed for the program based on the chemical stability and strength of the joints during processing, and service. The FEA results were compared with experiments using two methods: (1) an idealized strength relationship of the ceramic, and (2) a probabilistic analysis of the ceramic strength (NASA CARES). The results showed that the measured strength of the joint reached 30--80% of the strength predicted by FEA. Also, potential high-temperature braze alloys were developed and evaluated for the high-temperature application of ceramic-metal joints. 38 tabs, 29 figs, 20 refs.

  2. Nucleic acids encoding metal uptake transporters and their uses

    DOEpatents

    Schroeder, Julian I.; Antosiewicz, Danuta M.; Schachtman, Daniel P.; Clemens, Stephan

    1999-01-01

    The invention provides LCT1 nucleic acids which encode metal ion uptake transporters. The invention also provides methods of modulating heavy metal and alkali metal uptake in plants. The methods involve producing transgenic plants comprising a recombinant expression cassette containing an LCT1 nucleic acid linked to a plant promoter.

  3. Neutron diffraction measurements and first-principles study of thermal motion of atoms in select Mn+1AXn and binary MX transition-metal carbide phases

    NASA Astrophysics Data System (ADS)

    Lane, Nina J.; Vogel, Sven C.; Hug, Gilles; Togo, Atsushi; Chaput, Laurent; Hultman, Lars; Barsoum, Michel W.

    2012-12-01

    Herein, we compare the thermal vibrations of atoms in select ternary carbides with the formula Mn+1AXn (“MAX phases,” M = Ti, Cr; A = Al, Si, Ge; X = C, N) as determined from first-principles phonon calculations to those obtained from high-temperature neutron powder diffraction studies. The transition metal carbides TiC, TaC, and WC are also studied to test our methodology on simpler carbides. Good qualitative and quantitative agreement is found between predicted and experimental values for the binary carbides. For all the MAX phases studied—Ti3SiC2, Ti3GeC2, Ti2AlN, Cr2GeC and Ti4AlN3—density functional theory calculations predict that the A element vibrates with the highest amplitude and does so anisotropically with a higher amplitude within the basal plane, which is in line with earlier results from high-temperature neutron diffraction studies. In some cases, there are quantitative differences in the absolute values between the theoretical and experimental atomic displacement parameters (ADPs), such as reversal of anisotropy or a systematic offset of temperature-dependent ADPs. The mode-dependent Grüneisen parameters are also computed to explore the anharmonicity in the system.

  4. Poor mid-term survival of the low-carbide metal-on-metal Zweymüller-plus total hip arthroplasty system: a concise follow-up, at a minimum of ten years, of a previous report*.

    PubMed

    Repantis, Thomas; Vitsas, Vasilis; Korovessis, Panagiotis

    2013-03-20

    Between 1994 and 1999, 217 metal-on-metal total hip arthroplasties with a low-carbide bearing surface were performed with use of the cementless Zweymüller SL-Plus stem and the Bicon-Plus threaded cup in 194 consecutive patients. After a minimum follow-up of ten years, 181 living patients (203 hips) were available for evaluation. The revision rate after an average of twelve years was 18% (thirty-six hips in thirty-six patients were revised). The main reason for revision was aseptic loosening of one or both components. The probability of survival of the stem at fifteen years was 77% (95% confidence interval [CI], 65% to 86%). The probability of survival of the cup was 80% (95% CI, 62% to 90%). These high failure rates at mid-term follow-up led us to abandon the use of low-carbide metal-on-metal total hip arthroplasty components. PMID:23515994

  5. Deterioration of yttria-stabilized zirconia by boron carbide alone or mixed with metallic or oxidized Fe, Cr, Zr mixtures

    NASA Astrophysics Data System (ADS)

    De Bremaecker, A.; Ayrault, L.; Clément, B.

    2014-08-01

    In the frame of severe accident conditions (PHEBUS FPT3 test), different experiments were carried out on the interactions of 20% yttria-stabilized zirconia (YSZ) and 20% ceria-stab zirconia with boron carbide or its oxidation products (B2O3): either tests under steam between 1230° and 1700 °C with B4C alone or B4C mixed with metals, either tests under Ar with boron oxide present in a mixture of iron and chromium oxides. In all cases an interaction was observed with formation of intergranular yttrium borate. At 1700 °C boron oxide is able to “pump out” the Y stabiliser from the YSZ grains but also some trace elements (Ca and Al) and to form a eutectic containing YBO3 and yttrium calcium oxy-borate (YCOB). At the same time a substantial swelling (“bloating”) of the zirconia happens, qualitatively similar to the foaming of irradiated fuel in contact with a Zr-melt. In all samples the lowering of the Y (or Ce)-content in the YSZ grains is so sharp that in the interaction layers zirconia is no longer stabilized. This is important when YSZ is envisaged as simulant of UO2 or as inert matrix for Am-transmutation.

  6. Direct Chemical Synthesis of MnO2 Nanowhiskers on Transition-Metal Carbide Surfaces for Supercapacitor Applications.

    PubMed

    Rakhi, Raghavan Baby; Ahmed, Bilal; Anjum, Dalaver; Alshareef, Husam N

    2016-07-27

    Transition-metal carbides (MXenes) are an emerging class of two-dimensional materials with promising electrochemical energy storage performance. Herein, for the first time, by direct chemical synthesis, nanocrystalline ε-MnO2 whiskers were formed on MXene nanosheet surfaces (ε-MnO2/Ti2CTx and ε-MnO2/Ti3C2Tx) to make nanocomposite electrodes for aqueous pseudocapacitors. The ε-MnO2 nanowhiskers increase the surface area of the composite electrode and enhance the specific capacitance by nearly 3 orders of magnitude compared to that of pure MXene-based symmetric supercapacitors. Combined with enhanced pseudocapacitance, the fabricated ε-MnO2/MXene supercapacitors exhibited excellent cycling stability with ∼88% of the initial specific capacitance retained after 10000 cycles which is much higher than pure ε-MnO2-based supercapacitors (∼74%). The proposed electrode structure capitalizes on the high specific capacitance of MnO2 and the ability of MXenes to improve conductivity and cycling stability. PMID:27377125

  7. Titania Composites with 2 D Transition Metal Carbides as Photocatalysts for Hydrogen Production under Visible-Light Irradiation

    DOE PAGESBeta

    Wang, Hui; Peng, Rui; Hood, Zachary D.; Naguib, Michael; Adhikari, Shiba P.; Wu, Zili

    2016-05-24

    In the MXenes family of two-dimensional transition-metal carbides there were successful demonstrations of co-catalysts with rutile TiO2 for visible-light-induced solar hydrogen production from water splitting. The physicochemical properties of Ti3C2Tx MXene coupled with TiO2 were investigated by a variety of characterization techniques. The effect of the Ti3C2Tx loading on the photocatalytic performance of the TiO2/Ti3C2Tx composites was elucidated. Moreover, with an optimized Ti3C2Tx content of 5 wt %, the TiO2/Ti3C2Tx composite shows a 400 % enhancement in the photocatalytic hydrogen evolution reaction compared with that of pure rutile TiO2. We also expanded our exploration to other MXenes (Nb2CTx and Ti2CTx)more » as co-catalysts coupled with TiO2, and these materials also exhibited enhanced hydrogen production. These results manifest the generality of MXenes as effective co-catalysts for solar hydrogen production.« less

  8. Titania Composites with 2 D Transition Metal Carbides as Photocatalysts for Hydrogen Production under Visible-Light Irradiation.

    PubMed

    Wang, Hui; Peng, Rui; Hood, Zachary D; Naguib, Michael; Adhikari, Shiba P; Wu, Zili

    2016-06-22

    MXenes, a family of two-dimensional transition-metal carbides, were successfully demonstrated as co-catalysts with rutile TiO2 for visible-light-induced solar hydrogen production from water splitting. The physicochemical properties of Ti3 C2 Tx MXene coupled with TiO2 were investigated by a variety of characterization techniques. The effect of the Ti3 C2 Tx loading on the photocatalytic performance of the TiO2 /Ti3 C2 Tx composites was elucidated. With an optimized Ti3 C2 Tx content of 5 wt %, the TiO2 /Ti3 C2 Tx composite shows a 400 % enhancement in the photocatalytic hydrogen evolution reaction compared with that of pure rutile TiO2 . We also expanded our exploration to other MXenes (Nb2 CTx and Ti2 CTx ) as co-catalysts coupled with TiO2 , and these materials also exhibited enhanced hydrogen production. These results manifest the generality of MXenes as effective co-catalysts for solar hydrogen production. PMID:27219205

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

    DOEpatents

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

    2003-09-23

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

  10. Metal DiCarbides as Intermediate Species in thermal Ion Formation Mechanisms

    SciTech Connect

    Matthew G. Watrous; James E. Delmore

    2009-09-01

    The lanthanide elements (lanthanum to lutetium) adsorbed onto resin beads have been studied as thermal ionization sources. Temperatures at which these ion sources gave maximum intensities were measured for each of these elements. The temperature trends track the trends in the dissociation energies of the corresponding metal dicarbide compounds. The metal dicarbide functions as a carrier to take the lanthanide element to higher temperatures than otherwise attainable. This results in the release of the atomic species at a higher temperature where the ionization probability is significantly increased. This breaking of molecular bonds releasing the atoms at these elevated temperatures is hypothesized as the reason for high ionization efficiencies.

  11. Laser doping and metallization of wide bandgap materials: silicon carbide, gallium nitride, and aluminum nitride

    NASA Astrophysics Data System (ADS)

    Salama, Islam Abdel Haleem

    A laser direct write and doping (LDWD) system is designed and utilized for direct metallization and selective area doping in different SiC polytypes, GaN and in dielectrics including AlN. Laser direct metallization in 4H- and 6H-SiC generates metal-like conductive phases that are produced as both rectifying and ohmic contacts without metal deposition. Nd:YAG (lambda = 532, 1064 nm) nanosecond pulsed laser irradiation in SiC induces carbon-rich conductive phases by thermal decomposition of SiC while UV excimer (lambda = 193 nm) laser irradiation produces a silicon-rich phase due to selective carbon photoablation. Linear transmission line method (TLM) pattern is directly fabricated in single crystals SiC by pulsed laser irradiation allowing characterization of the laser fabricated metal-like contacts. Activation of a self focusing effect at the frequency doubled Nd:YAG laser irradiation (lambda = 532 nm) allows to fabricate buried metal like contacts in SiC wafers while maintaining their device-ready surface condition. Gas immersion laser doping (GILD) and laser doping from a molten precursor are utilized to dope both GaN and SiC. Trimethylaluminum (TMAl) and nitrogen are the precursors used to produce p-type and n-type doped SiC; respectively. Nd:YAG and excimer laser nitrogen doping in SiC epilayer and single crystal substrates increases the dopant concentration by two orders of magnitude and produces both deep (500--600 nm) and shallow (50 nm) junctions, respectively. Laser assisted effusion/diffusion is introduced and utilized to dope Al in SiC wafers. Using this technique, a150 nm p-type doped junction is fabricated in semi-insulating 6H- and n-type doped 4H-SiC wafers. Laser-induced p-type doping of Mg in single crystal GaN is conducted using Bis-magnesium dihydrate [Mg(TMHD)2]. Mg concentration and penetration depth up to 10 20--1021 cm-3 and 5mum, respectively are achieved using various laser doping techniques. Laser direct writing and doping (LDWD) is a

  12. Superhard composite materials including compounds of carbon and nitrogen deposited on metal and metal nitride, carbide and carbonitride

    DOEpatents

    Wong, Ming-Show; Li, Dong; Chung, Yip-Wah; Sproul, William D.; Chu, Xi; Barnett, Scott A.

    1998-01-01

    A composite material having high hardness comprises a carbon nitrogen compound, such as CN.sub.x where x is greater than 0.1 and up to 1.33, deposited on a metal or metal compound selected to promote deposition of substantially crystalline CN.sub.x. The carbon nitrogen compound is deposited on a crystal plane of the metal or metal compound sufficiently lattice-matched with a crystal plane of the carbon nitrogen compound that the carbon nitrogen compound is substantially crystalline. A plurality of layers of the compounds can be formed in alternating sequence to provide a multi-layered, superlattice coating having a coating hardness in the range of 45-55 GPa, which corresponds to the hardness of a BN coating and approaches that of a diamond coating.

  13. Superhard composite materials including compounds of carbon and nitrogen deposited on metal and metal nitride carbide and carbonitride

    DOEpatents

    Wong, Ming-Show; Li, Dong; Chung, Yin-Wah; Sproul, William D.; Chu, Xi; Barnett, Scott A.

    1998-01-01

    A composite material having high hardness comprises a carbon nitrogen compound, such as CN.sub.x where x is greater than 0.1 and up to 1.33, deposited on a metal or metal compound selected to promote deposition of substantially crystalline CN.sub.x. The carbon nitrogen compound is deposited on a crystal plane of the metal or metal compound sufficiently lattice-matched with a crystal plane of the carbon nitrogen compound that the carbon nitrogen compound is substantially crystalline. A plurality of layers of the compounds can be formed in alternating sequence to provide a multi-layered, superlattice coating having a coating hardness in the range of 45-55 GPa, which corresponds to the hardness of a BN coating and approaches that of a diamond coating.

  14. Superhard composite materials including compounds of carbon and nitrogen deposited on metal and metal nitride carbide and carbonitride

    DOEpatents

    Wong, M.S.; Li, D.; Chung, Y.W.; Sproul, W.D.; Xi Chu; Barnett, S.A.

    1998-03-10

    A composite material having high hardness comprises a carbon nitrogen compound, such as CN{sub x} where x is greater than 0.1 and up to 1.33, deposited on a metal or metal compound selected to promote deposition of substantially crystalline CN{sub x}. The carbon nitrogen compound is deposited on a crystal plane of the metal or metal compound sufficiently lattice-matched with a crystal plane of the carbon nitrogen compound that the carbon nitrogen compound is substantially crystalline. A plurality of layers of the compounds can be formed in alternating sequence to provide a multi-layered, superlattice coating having a coating hardness in the range of 45--55 GPa, which corresponds to the hardness of a BN coating and approaches that of a diamond coating. 10 figs.

  15. Superhard composite materials including compounds of carbon and nitrogen deposited on metal and metal nitride, carbide and carbonitride

    DOEpatents

    Wong, M.S.; Li, D.; Chung, Y.W.; Sproul, W.D.; Chu, X.; Barnett, S.A.

    1998-07-07

    A composite material having high hardness comprises a carbon nitrogen compound, such as CN{sub x} where x is greater than 0.1 and up to 1.33, deposited on a metal or metal compound selected to promote deposition of substantially crystalline CN{sub x}. The carbon nitrogen compound is deposited on a crystal plane of the metal or metal compound sufficiently lattice-matched with a crystal plane of the carbon nitrogen compound that the carbon nitrogen compound is substantially crystalline. A plurality of layers of the compounds can be formed in alternating sequence to provide a multi-layered, superlattice coating having a coating hardness in the range of 45--55 GPa, which corresponds to the hardness of a BN coating and approaches that of a diamond coating. 10 figs.

  16. Pr 2ReC 2 and other ternary rare earth metal rhenium carbides with filled PbCl 2 (Co 2Si) structure

    NASA Astrophysics Data System (ADS)

    Jeitschko, W.; Block, G.; Kahnert, G. E.; Behrens, R. K.

    1990-11-01

    The carbides R2ReC 2 ( R = Y, CeNd, Sm, GdTm, Lu) were prepared by arc-melting of cold-pressed pellets of the elemental components. They crystallize with the orthorhombic space group Pnma and Z = 4 formula units per cell. The lattice constants for Pr 2ReC 2 are; a = 655.69(6) pm, b = 509.46(5) pm, c = 984.42(8) pm. The crystal structure was determined from quantitative evaluations of Guinier powder data for Y 2ReC 2 and Pr 2ReC 2, which refined to conventional residuals of R = 0.088 and R = 0.072, respectively. The structure of the isotypic carbide Er 2ReC 2 was determined from single-crystal diffractometer data: R = 0.032 for 842 structure factors and 26 variable parameters. The positions of the metal atoms correspond to those of the Co 2Si-branch of the "anti"-PbCl 2 structure. The carbon atoms are isolated from each other and occupy two different octahedral voids (4 R + 2Re, 5 R + 1Re). There are no bonding ReRe interactions in the one-dimensionally infinite [ReC -62] n polyanions. The ReC bond lengths of between 192 pm and 203 pm suggest bond orders of about two and the rhenium atoms seem to obey the 18-electron rule. The metal atom positions of the Pr 2ReC 2 type carbides correspond to those of a distorted cubic body-centered structure, as is also found for several other complex carbides. The average valence electron number of the metal atoms is usually greater in unfilled (host) structures than in the corresponding filled (interstitial) structures.

  17. Anisotropic Tribological Properties of Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1980-01-01

    The anisotropic friction, deformation and fracture behavior of single crystal silicon carbide surfaces were investigated in two categories. The categories were called adhesive and abrasive wear processes, respectively. In the adhesive wear process, the adhesion, friction and wear of silicon carbide were markedly dependent on crystallographic orientation. The force to reestablish the shearing fracture of adhesive bond at the interface between silicon carbide and metal was the lowest in the preferred orientation of silicon carbide slip system. The fracturing of silicon carbide occurred near the adhesive bond to metal and it was due to primary cleavages of both prismatic (10(-1)0) and basal (0001) planes.

  18. Processing, characterization and mechanical behavior of novel aluminum/silicon carbide metal-ceramic nanolaminates

    NASA Astrophysics Data System (ADS)

    Singh, Danny Rao Pratap

    Nanoscale laminated composites are a novel class of materials with excellent mechanical properties like strength, flexibility, and toughness. Properties in these materials can be tailored by varying layer thicknesses, microstructure, and controlling internal stresses. Most of research to-date has focused on metal-metal and ceramic-ceramic laminates. The field of metal-ceramic laminates has remained relatively unexplored. From a mechanical structure point of view, metal-ceramic systems present a good combination of strength and hardness. Hence, there is a need for understanding and evaluating these composites in nanolaminate form. In this work, the deformation behavior of Al-SiC nanolaminates as a model system has been studied. The work has been categorized into 3 major areas of research. The first involves processing and microstructural characterization of these novel materials. Nanoscale Al/SiC layered composites were fabricated using magnetron sputtering. Samples with varying volume fractions of Al and SiC were synthesized. The second area involves quantifying the residual stresses in these materials. These are quantified by x-ray synchrotron and beam-curvature techniques. The third area focuses on understanding the fundamental mechanisms for deformation damage, and fracture under indentation and micro-compression loading. Fracture/Damage analysis is carried out using focused ion beam (FIB) and scanning electron microscopy (SEM). The systematic study has revealed the enhanced mechanical properties of metal-ceramic nanolaminates and the fundamental mechanisms governing the strength and failure of these materials. It has been found that Al/SiC metal-ceramic systems can exhibit high strength together with high toughness and flexibility. High compressive residual stresses are generated during the sputter deposition of these nanolaminates which are associated with the large number of interfaces present in the nanolaminate architecture. The mechanical properties

  19. Water–gas shift catalysis over transition metals supported on molybdenum carbide

    SciTech Connect

    Kaiwalya, Sabnis D; Cui, Yanran; Akatay, M. Cem; Shekhar, Mayank; Lee, Wen-Sheng; Miller, Jeffrey T.; Delgass, W. Nicholas; Ribeiro, Fabio

    2015-11-01

    We report here that WGS rates per total surface area at 120 degrees C, 7% CO, 22% H2O, 8.5% CO2, 37% H-2 for Pt, Au, Pd and Ni supported over MO2C were 4-8 times higher than those of the commercial Cu/ZnO/Al2O3 catalyst. In agreement with previous literature, the WGS rate per total moles of Pt over Pt/MO2C at 120 degrees C has been shown to be higher than on any Pt/Metal oxide catalyst. We have made use of systematic changes in the apparent kinetic parameters with various admetals (decrease in apparent CO order and apparent activation energy and increase in apparent H2O order compared to unpromoted MO2C) to conclude that the function of the rate-promoting admetals is to enhance the relative surface concentration of the adsorbed CO, thereby leading to a promotion in the WGS rate per total surface area of the catalyst. Temperature programmed desorption of CO was used to show that the CO adsorption properties of MO2C were modified by the various admetals by creating new metallic sites. In situ X-ray absorption on Pt and Au and STEM-EELS experiments showed that the supported Au nanoparticles over MO2C decrease in average particle size from similar to 9 nm to 3 nm after a 600 degrees C carburization pretreatment. Pt was also shown to have assumed a stable structure at 600 degrees C in the form of a Pt-Mo alloy. We suggest that MO2C can be used to synthesize thermally robust supported metal catalysts.

  20. Heavy metals influence on ascorbic acid level

    NASA Astrophysics Data System (ADS)

    Kamaldinov, E. V.; Patrashkov, S. A.; Batenyeva, E. V.; Korotkevich, O. S.

    2003-05-01

    It is well known that heavy metals (HM) are extremely dangerous pollutants influencing to metabolism in animals' organisms. The vitamin C is one of the most important metabolites taking part in many biochemical processes. We studied the influence of main essential HM-Zn and Cu as well as the based supertoxical elements - Cd and Pd on ascorbic acid level in serum. The studies were carried out in Tulinskoe farm of Novosibirsk region. The objects of investigations were piglets (2 month after weaning) and 6-month pigs of Early Ripe Meat breed. The levels of HM in bristle were found by stripping voltammetric analysis using the TA-2 analyzer. Vitamin C content was determined by I.P. Kondrakhin (1985) method using 2,2-dipyridyl. The significant negative correlations between Pb, Cd content and vitamin C (-0.46 ± 0.18, -0.47 ± 0.19) in 6-month pigs were determined. The tendencies of negative correlation between all HM levels in hair and ascorbic acid level in plasma of piglets were revealed. Thus, the obtained correlations let us to suppose that all studied HM influence on 1-gulono-gamma-lactone oxidase and other vitamin C metabolism enzymes activity.

  1. Persistent Luminescence Hole-Type Materials by Design: Transition-Metal-Doped Carbon Allotrope and Carbides.

    PubMed

    Qu, Bingyan; Zhang, Bo; Wang, Lei; Zhou, Rulong; Zeng, Xiao Cheng; Li, Liang

    2016-03-01

    Electron traps play a crucial role in a wide variety of compounds of persistent luminescence (PL) materials. However, little attention has been placed on the hole-trap-type PL materials. In this study, a novel hole-dominated persistent luminescence (PL) mechanism is predicted. The mechanism is validated in the night pearl diamond (NPD) composed of lonsdaleite with ultralong persistent luminescence (PL) (more than 72 h). The computed band structures suggest that the Fe ion dopant in lonsdaleite is responsible for the luminescence of NPD due to the desired defect levels within the band gap for electronic transition. Other possible impurity defects in lonsdaleite, such as K, Ca, Mg, Zn, or Tl dopants, or C vacancy can also serve as the hole-trap centers to enhance the PL. Among other 3d transition-metal-ion dopants considered, Cr and Mn ions are predicted to give rise to PL property. The predicted PL mechanism via transition-metal doping of lonsdaleite offers an exciting opportunity for engineering new PL materials by design. PMID:26849004

  2. Development of Plasma-Sprayed Molybdenum Carbide-Based Anode Layers with Various Metal Oxides for SOFC

    NASA Astrophysics Data System (ADS)

    Faisal, N. H.; Ahmed, R.; Katikaneni, S. P.; Souentie, S.; Goosen, M. F. A.

    2015-12-01

    Air plasma-sprayed (APS) coatings provide an ability to deposit a range of novel fuel cell materials at competitive costs. This work develops three separate types of composite anodes (Mo-Mo2C/Al2O3, Mo-Mo2C/ZrO2, Mo-Mo2C/TiO2) using a combination of APS process parameters on Hastelloy®X for application in intermediate temperature proton-conducting solid oxide fuel cells. Commercially available carbide of molybdenum powder catalyst (Mo-Mo2C) and three metal oxides (Al2O3, ZrO2, TiO2) was used to prepare three separate composite feedstock powders to fabricate three different anodes. Each of the modified composition anode feedstock powders included a stoichiometric weight ratio of 0.8:0.2. The coatings were characterized by scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction, nanoindentation, and conductivity. We report herein that three optimized anode layers of thicknesses between 200 and 300 µm and porosity as high as 20% for Mo-Mo2C/Al2O3 (250-µm thick) and Mo-Mo2C/TiO2 (300 µm thick) and 17% for Mo-Mo2C/ZrO2 (220-µm thick), controllable by a selection of the APS process parameters with no addition of sacrificial pore-forming material. The nanohardness results indicate the upper layers of the coatings have higher values than the subsurface layers in coatings with some effect of the deposition on the substrate. Mo-Mo2C/ZrO2 shows high electrical conductivity.

  3. Thermodynamics of several lewis-acid-base stabilized transition metal alloys

    NASA Astrophysics Data System (ADS)

    Gibson, John K.; Brewer, Leo; Gingerich, Karl A.

    1984-11-01

    High-temperature (1425 to 2750 K) thermodynamic activities of one or both components of twenty-five binary alloys of a group IVB-VIB element (Ti, Zr, Hf, Nb, Ta, or W) with a platinum group element (Ru, Os, Ir, Pd, Pt, or Au) have been determined by equilibrating the alloy with the appropriate carbide and graphite, equilibrating with the nitride and nitrogen gas, or measuring the partial vapor pressure(s) thermogravimetrically or mass spectrometrically. The extraordinary stability of this class of transition metal alloy is attributed to a generalized Lewis-acid-base interaction involving valence d electrons, and the results of these investigations are interpreted within the context of this effect. Among the conclusions made are that a non-spherically-symmetrical crystal field significantly reduces the bonding effectiveness of certain valence d orbitals; the effect of the extent of derealization of these orbitals is also considered.

  4. Leaching of metals from steel samples in peracetic acid

    NASA Astrophysics Data System (ADS)

    Yabutani, Tomoki; Nakamura, Takamasa; Takayabagi, Toshio

    2015-03-01

    In this paper, leaching behavior of metallic species from steel samples in peracetic acid was investigated. We compared the leaching efficiency between peracetic acid and acetic acid to estimate the role of peroxo functional group for the leaching. As a result, peracetic acid enhanced the leaching ability of metallic species from the high speed steel and the alloy steel samples. MoO3, Mo, MO2C, W, WO3, VC and MnO2 were effectively leached by peracetic acid, while the stainless steel had a high resistance against corrosion by peracetic acid.

  5. Hydrogen Interaction with Titanium Carbide-Coated Metals for Fusion Technology Application

    NASA Astrophysics Data System (ADS)

    Caorlin, Marco

    Available from UMI in association with The British Library. The interaction of gaseous hydrogen with TiC coatings deposited on metals by Chemical Vapour Deposition was studied. The prime aim of this study was to determine whether such coatings could affect the rate of absorption and desorption by the metallic substrate. Developing and testing simple models for the experiments in terms of diffusivity D, Sieverts' constant K_{s} and surface reaction rates k_1, k_2, was another goal of the work. Both aims are closely linked to the use of tritium in present and future fusion devices. Two manometric techniques were used. At Ispra, the hydrogen pressure increase in a closed vessel was recorded in time, after loading the sample with hydrogen to equilibrium and evacuating the chamber. Loading pressures between 10^3 Pa and 10^5 Pa were used, with temperatures in the range 673 K-873 K. At Oxford, a similar equilibrium state was perturbed by a imposed periodic volume variation. The corresponding pressure response, in a closed chamber containing the specimen immersed in hydrogen, was recorded in time. Pressures between 4 Pa and 74 Pa were used and the temperature range was 883 K-1083 K. The substrates used were the AISI 316L steel and the molybdenum alloy TZM at Ispra, while only TZM at Oxford. With both methods, a marked increase of the times to reach equilibrium was detected with respect to uncoated samples, while the equilibrium absorption behaviour of the coated specimens was not significantly different from that of the bare ones. Very low diffusivity values were obtained for hydrogen in TiC. For the Ispra samples, the temperature dependence found is D/{rm(m ^2s}^{-1}) = 1.08 times 10^{-12} exp(-{6800 over T/K})while that determined at Oxford, for different TiC specimens, is D/{rm (m^2s}^ {-1}) = 9.60 times 10^{-12} exp (-{6010over T/K}). The surface rate constants determined at Ispra are represented by eqalign {k_1/({rm mol m^{ -2}s^{-1}Pa^{-1}) }&= 4.10 times 10^{-8} exp

  6. Correlated Strontium and Barium Isotopic Compositions of Acid-cleaned Single Mainstream Silicon Carbides from Murchison

    NASA Astrophysics Data System (ADS)

    Liu, Nan; Savina, Michael R.; Gallino, Roberto; Davis, Andrew M.; Bisterzo, Sara; Gyngard, Frank; Käppeler, Franz; Cristallo, Sergio; Dauphas, Nicolas; Pellin, Michael J.; Dillmann, Iris

    2015-04-01

    We present strontium, barium, carbon, and silicon isotopic compositions of 61 acid-cleaned presolar SiC grains from Murchison. Comparison with previous data shows that acid washing is highly effective in removing both strontium and barium contamination. For the first time, by using correlated 88Sr/86Sr and 138Ba/136Ba ratios in mainstream SiC grains, we are able to resolve the effect of 13C concentration from that of 13C-pocket mass on s-process nucleosynthesis, which points toward the existence of large 13C pockets with low 13C concentrations in asymptotic giant branch stars. The presence of such large 13C pockets with a variety of relatively low 13C concentrations seems to require multiple mixing processes in parent asymptotic giant branch stars of mainstream SiC grains.

  7. Uniform nano-ripples on the sidewall of silicon carbide micro-hole fabricated by femtosecond laser irradiation and acid etching

    SciTech Connect

    Khuat, Vanthanh; Chen, Tao; Gao, Bo; Si, Jinhai Ma, Yuncan; Hou, Xun

    2014-06-16

    Uniform nano-ripples were observed on the sidewall of micro-holes in silicon carbide fabricated by 800-nm femtosecond laser and chemical selective etching. The morphology of the ripple was analyzed using scanning electronic microscopy. The formation mechanism of the micro-holes was attributed to the chemical reaction of the laser affected zone with mixed solution of hydrofluoric acid and nitric acid. The formation of nano-ripples on the sidewall of the holes could be attributed to the standing wave generated in z direction due to the interference between the incident wave and the reflected wave.

  8. First-principles calculations of the twin boundary energies and adhesion energies of interfaces for cubic face-centered transition-metal nitrides and carbides

    NASA Astrophysics Data System (ADS)

    Li, Tengfei; Liu, Tianmo; Wei, Hongmei; Hussain, Shahid; Wang, Jinxing; Zeng, Wen; Peng, Xianghe; Wang, Zhongchang

    2015-11-01

    The twin boundary energies of TiN, ZrN, HfN, TiC, ZrC, HfC, VC, NbC and TaC and the adhesion energies of twin interfaces and interfaces of TiN/ZrN, VC/TiC and TiN/TiC were calculated using first-principles methods. A new route in the preparation of mechanically superhard films has been proposed by introducing twin into the multilayer of transition-metal nitrides and carbides.

  9. The friction and wear of metals and binary alloys in contact with an abrasive grit of single-crystal silicon carbide

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1979-01-01

    Sliding friction experiments were conducted with various metals and iron-base binary alloys (alloying elements Ti, Cr, Mn, Ni, Rh and W) in contact with single crystal silicon carbide riders. Results indicate that the friction force in the plowing of metal and the groove height (corresponding to the wear volume of the groove) decrease linearly as the shear strength of the bulk metal increases. The coefficient of friction and groove height generally decrease, and the contact pressure increases with an increase in solute content of binary alloys. There appears to be very good correlation of the solute to iron atomic ratio with the decreasing rate of change of coefficient of friction, the decreasing rate of change of groove height and the increasing rate of change of contact pressure with increasing solute content. These rates of change increase as the solute to iron atomic radius ratio increases or decreases from unity.

  10. Isotopic compositions of s-process elements in acid-cleaned mainstream presolar silicon carbide

    NASA Astrophysics Data System (ADS)

    Liu, Nan

    Pristine meteorites contain ancient stellar relicts that survived destructions in the early solar system. Isotopic studies of these presolar grains have proven to be a unique method to understand various known and unknown nucleosynthetic processes occurred in their parent stars. Previous studies of isotopic compositions of heavy elements in mainstream SiC grains from low-mass asymptotic giant branch (AGB) stars reported contamination from solar system materials with normal isotopic compositions on grain surfaces and prevented the authors from obtaining the pure nucleosynthetic isotopic signature from stars. In addition, in these previous studies uncertainties in the major neutron source 13C within the 13C-pocket were underestimated because only the 13C mass fraction was considered as a parameter with the 13C-pocket mass and the 13C profile fixed in model calculations. The oversimplified treatment of the 13C-pocket mainly resulted from the fact that it was unclear if there exists any tracer to distinguish different effects of the 13C concentration, the 13C-pocket mass, and the 13C profile within the 13C-pocket. To address these issues, we acid-cleaned all the presolar SiC grains used in this study after their separation from the bulk Murchison meteorite. In addition, we chose to measure strontium and barium isotopic compositions in these acid-cleaned SiC grains, because both elements sit at the first and second s-process peaks along the s-process path, and are sensitive to varying parameters for the s-process in model calculations. By comparing our new acid-cleaned grain data with single grain data from previous studies for barium isotopes, we conclude that the acid-cleaning procedure is quite effective in removing surface barium contamination. For the first time, we find that model predictions for 138Ba/ 136Ba are sensitive to all three variables of the 13C-pocket adopted in AGB model calculations. In order to match the low 138Ba/ 136Ba values in a minor group of

  11. Extracting metal ions with diphosphonic acid, or derivative thereof

    DOEpatents

    Horwitz, Earl P.; Gatrone, Ralph C.; Nash, Kenneth L.

    1994-01-01

    Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.

  12. Extracting metal ions with diphosphonic acid, or derivative thereof

    DOEpatents

    Horwitz, E.P.; Gatrone, R.C.; Nash, K.L.

    1994-07-26

    Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulfur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described. 1 fig.

  13. Lewis Acid Coupled Electron Transfer of Metal-Oxygen Intermediates.

    PubMed

    Fukuzumi, Shunichi; Ohkubo, Kei; Lee, Yong-Min; Nam, Wonwoo

    2015-12-01

    Redox-inactive metal ions and Brønsted acids that function as Lewis acids play pivotal roles in modulating the redox reactivity of metal-oxygen intermediates, such as metal-oxo and metal-peroxo complexes. The mechanisms of the oxidative CH bond cleavage of toluene derivatives, sulfoxidation of thioanisole derivatives, and epoxidation of styrene derivatives by mononuclear nonheme iron(IV)-oxo complexes in the presence of triflic acid (HOTf) and Sc(OTf)3 have been unified as rate-determining electron transfer coupled with binding of Lewis acids (HOTf and Sc(OTf)3 ) by iron(III)-oxo complexes. All logarithms of the observed second-order rate constants of Lewis acid-promoted oxidative CH bond cleavage, sulfoxidation, and epoxidation reactions of iron(IV)-oxo complexes exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes were taken into account. The binding of HOTf and Sc(OTf)3 to the metal-oxo moiety has been confirmed for Mn(IV) -oxo complexes. The enhancement of the electron-transfer reactivity of metal-oxo complexes by binding of Lewis acids increases with increasing the Lewis acidity of redox-inactive metal ions. Metal ions can also bind to mononuclear nonheme iron(III)-peroxo complexes, resulting in acceleration of the electron-transfer reduction but deceleration of the electron-transfer oxidation. Such a control on the reactivity of metal-oxygen intermediates by binding of Lewis acids provides valuable insight into the role of Ca(2+) in the oxidation of water to dioxygen by the oxygen-evolving complex in photosystem II. PMID:26404482

  14. Growth of boric acid crystallites on the surface of boron-doped silicon carbide samples

    SciTech Connect

    Vassen, R.; Stoever, D.

    1996-06-01

    White crystallites were visually observed on fractured or polished surfaces of SiC samples (grain sizes below {approx}500 nm) during exposure to air at room temperature for several days. Characterization of the crystallites by scanning electron microscopy, secondary ion mass spectroscopy, and X-ray diffraction identified B(OH){sub 3} crystals with a strong (002) texture. The rate of boric acid formation was determined by a gravimetric experiment. The rate of weight gain increased significantly after an incubation period of 1 week. Nucleation is initially the rate-limiting process. Subsequently small B(OH){sub 3} crystals form on the surface, whose growth rate is determined by grain boundary diffusion of boron to the SiC surface. An estimated grain boundary boron to the SiC surface. An estimated grain boundary diffusion coefficient of boron in SiC was many orders of magnitude higher than extrapolated literature values.

  15. Adherence of sputtered titanium carbides

    NASA Technical Reports Server (NTRS)

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

    1979-01-01

    Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited, in practice, by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium based alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

  16. Synthesis of Nanoporous Iminodiacetic Acid Sorbents for Binding Transition Metals

    PubMed Central

    Busche, Brad; Wiacek, Robert; Davidson, Joseph; Koonsiripaiboon, View; Yantasee, Wassana; Addleman, R. Shane; Fryxell, Glen E.

    2009-01-01

    Iminodiacetic acid (IDAA) forms strong complexes with a wide variety of metal ions. Using self-assembled monolayers in mesoporous supports (SAMMS) to present the IDAA ligand potentially allows for multiple metal-ligand interactions to enhance the metal binding affinity relative to that of randomly oriented polymer-based supports. This manuscript describes the synthesis of a novel nanostructured sorbent material built using self-assembly of a IDAA ligand inside a nanoporous silica, and demonstrates its use for capturing transition metal cations, and anionic metal complexes, such as PdCl4−2. PMID:22068901

  17. The friction and wear of metals and binary alloys in contact with an abrasive grit of single-crystal silicon carbide

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Buckley, D. H.

    1979-01-01

    Sliding friction experiments were conducted with various metals and iron-base binary alloys (alloying elements Ti, Cr, Mn, Ni, Rh, and W) in contact with single-crystal silicon carbide riders. Results indicate that the coefficient of friction and groove height (corresponding to the wear volume) decrease linearly as the shear strength of the bulk metal increases. The coefficient of friction and groove height generally decrease with an increase in solute content of binary alloys. A separate correlation exists between the solute to iron atomic radius ratio and the decreasing rates of change of coefficient of friction and groove height with increasing solute content. These rates of change are minimum at a solute to iron radius ratio of unity. They increase as the atomic ratio increases or decreases linearly from unity. The correlations indicate that atomic size is an important parameter in controlling friction and wear of alloys.

  18. Acid Strength and Bifunctional Catalytic Behavior of Alloys Comprised of Noble Metals and Oxophilic Metal Promoters

    SciTech Connect

    Hibbitts, David D.; Tan, Qiaohua; Neurock, Matthew

    2014-06-01

    The promotion of metal catalysts with partially oxidized oxophilic MOx species, such as ReOx-promoted Rh, has been demonstrated to produce Brønsted acid sites that can promote hydrogenolysis of oxygenate intermediates such as those found in biomass-derived species. A wide variety of alloy compositions and structures are examined in this work to investigate strongly acidic promoters by using DFT-calculated deprotonation energies (DPE) as a measure of acid strength. Sites with the highest acid strength had DPE less than 1100 kJ mol-1, similar to DPE values of heteropolyacids or acid-containing zeolites, and were found on alloys composed of an oxophilic metal (such as Re or W) with a noble metal (such as Rh or Pt). NH3 adsorbs more strongly to sites with increasing acid strength and the activation barriers for acid-catalyzed ring opening of a furan ring decrease with increasing acid strength, which was also shown to be stronger for OH acid sites bound to multiple oxophilic metal atoms in a three-fold configuration rather than OH sites adsorbed in an atop configuration on one oxophilic metal, indicating that small MOx clusters may yield sites with the highest acid strength.

  19. VOLTAMMETRIC METHODS FOR DETERMINATION OF METAL BINDING BY FULVIC ACID

    EPA Science Inventory

    The use of anodic stripping voltammetry (ASV) and differential pulse polarography (DPP) for the measurement of the concentrations of aquo ions in the presence of fulvic acid, and the subsequent use of these data for estimation of the metal--fulvic acid conditional stability const...

  20. Metal ion adsorption to complexes of humic acid and metal oxides: Deviations from the additivity rule

    SciTech Connect

    Vermeer, A.W.P.; McCulloch, J.K.; Van Riemsdijk, W.H.; Koopal, L.K.

    1999-11-01

    The adsorption of cadmium ions to a mixture of Aldrich humic acid and hematite is investigated. The actual adsorption to the humic acid-hematite complex is compared with the sum of the cadmium ion adsorptivities to each of the isolated components. It is shown that the sum of the cadmium ion adsorptivities is not equal to the adsorption to the complex. In general, the adsorption of a specific metal ion to the complex can be understood and qualitatively predicted using the adsorptivities to each of the pure components and taking into account the effect of the pH on the interaction between humic acid and iron oxide on the metal ion adsorption. Due to the interaction between the negatively charged humic acid and the positively charged iron oxide, the adsorption of metal ions on the mineral oxide in the complex will increase as compared to that on the isolated oxide, whereas the adsorption to the humic acid will decrease as compared to that on the isolated humic acid. As a result, the overall adsorption of a specific metal ion to the complex will be smaller than predicted by the additivity rule when this metal ion has a more pronounced affinity for the humic acid than for the mineral oxide, whereas it will be larger than predicted by the additivity rule when the metal ion has a higher affinity for the oxide than for the humic acid.

  1. Pr sub 2 ReC sub 2 and other ternary rare earth metal rhenium carbides with filled PbCl sub 2 (Co sub 2 Si) structure

    SciTech Connect

    Jeitschko, W.; Block, G.; Kahnert, G.E.; Behrens, R.K. )

    1990-11-01

    The carbides R{sub 2}ReC{sub 2} (R = Y, Ce-Nd, Sm, Gd-Tm, Lu) were prepared by arc-melting of cold-pressed pellets of the elemental components. They crystallize with the orthorhombic space group Pnma and Z = 4 formula units per cell. The lattice constants for Pr{sub 2}ReC{sub 2} are: a = 655.69(6) pm, b = 509.46(5) pm, c = 984.42(8) pm. The crystal structure was determined from quantitative evaluations of Guinier powder data for Y{sub 2}ReC{sub 2} and Pr{sub 2}ReC{sub 2}, which refined to conventional residuals of R = 0.088 and R = 0.072, respectively. The structure of the isotypic carbide Er{sub 2}ReC{sub 2} was determined from single-crystal diffractometer data: R = 0.032 for 842 structure factors and 26 variable parameters. The positions of the metal atoms correspond to those of the Co{sub 2}Si-branch of the anti-PbCl{sub 2} structure. The carbon atoms are isolated from each other and occupy two different octahedral voids (4R + 2Re, 5R + 1Re).

  2. Silicon carbide sewing thread

    NASA Technical Reports Server (NTRS)

    Sawko, Paul M. (Inventor)

    1995-01-01

    Composite flexible multilayer insulation systems (MLI) were evaluated for thermal performance and compared with currently used fibrous silica (baseline) insulation system. The systems described are multilayer insulations consisting of alternating layers of metal foil and scrim ceramic cloth or vacuum metallized polymeric films quilted together using ceramic thread. A silicon carbide thread for use in the quilting and the method of making it are also described. These systems provide lightweight thermal insulation for a variety of uses, particularly on the surface of aerospace vehicles subject to very high temperatures during flight.

  3. Microbial community potentially responsible for acid and metal release from an Ostrobothnian acid sulfate soil

    PubMed Central

    Wu, Xiaofen; Lim Wong, Zhen; Sten, Pekka; Engblom, Sten; Österholm, Peter; Dopson, Mark; Nakatsu, Cindy

    2013-01-01

    Soils containing an approximately equal mixture of metastable iron sulfides and pyrite occur in the boreal Ostrobothnian coastal region of Finland, termed ‘potential acid sulfate soil materials’. If the iron sulfides are exposed to air, oxidation reactions result in acid and metal release to the environment that can cause severe damage. Despite that acidophilic microorganisms catalyze acid and metal release from sulfide minerals, the microbiology of acid sulfate soil (ASS) materials has been neglected. The molecular phylogeny of a depth profile through the plough and oxidized ASS layers identified several known acidophilic microorganisms and environmental clones previously identified from acid- and metal-contaminated environments. In addition, several of the 16S rRNA gene sequences were more similar to sequences previously identified from cold environments. Leaching of the metastable iron sulfides and pyrite with an ASS microbial enrichment culture incubated at low pH accelerated metal release, suggesting microorganisms capable of catalyzing metal sulfide oxidation were present. The 16S rRNA gene analysis showed the presence of species similar to Acidocella sp. and other clones identified from acid mine environments. These data support that acid and metal release from ASSs was catalyzed by indigenous microorganisms adapted to low pH. PMID:23369102

  4. Dilute acid/metal salt hydrolysis of lignocellulosics

    DOEpatents

    Nguyen, Quang A.; Tucker, Melvin P.

    2002-01-01

    A modified dilute acid method of hydrolyzing the cellulose and hemicellulose in lignocellulosic material under conditions to obtain higher overall fermentable sugar yields than is obtainable using dilute acid alone, comprising: impregnating a lignocellulosic feedstock with a mixture of an amount of aqueous solution of a dilute acid catalyst and a metal salt catalyst sufficient to provide higher overall fermentable sugar yields than is obtainable when hydrolyzing with dilute acid alone; loading the impregnated lignocellulosic feedstock into a reactor and heating for a sufficient period of time to hydrolyze substantially all of the hemicellulose and greater than 45% of the cellulose to water soluble sugars; and recovering the water soluble sugars.

  5. Adsorption of heavy metal ions by immobilized phytic acid

    SciTech Connect

    Tsao, G.T.; Zheng, Yizhou; Lu, J.; Gong, Cheng S.

    1997-12-31

    Phytic acid (myoinositol hexaphosphate) or its calcium salt, phytate, is an important plant constituents. It accounts for up to 85% of total phosphorus in cereals and legumes. Phytic acid has 12 replaceable protons in the phytic molecule rendering it the ability to complex with multivalent cations and positively charged proteins. Poly 4-vinyl pyridine (PVP) and other strong-based resins have the ability to adsorb phytic acid. PVP has the highest adsorption capacity of 0.51 phytic acid/resins. The PVP resin was used as the support material for the immobilization of phytic acid. The immobilized phytic acid can adsorb heavy metal ions, such as cadmium, copper, lead, nickel, and zinc ions, from aqueous solutions. Adsorption isotherms of the selected ions by immobilized phytic acid were conducted in packed-bed column at room temperature. Results from the adsorption tests showed 6.6 mg of Cd{sup 2+}, 7 mg of Cu{sup 2+}, 7.2 mg of Ni{sup 2+}, 7.4 mg of Pb{sup 2+}, and 7.7 mg of Zn{sup 2+} can be adsorbed by each gram of PVP-phytic acid complex. The use of immobilized phytic acid has the potential for removing metal ions from industrial or mining waste water. 15 refs., 7 figs., 2 tabs.

  6. Molybdenum carbides, active and in situ regenerable catalysts in hydroprocessing of fast pyrolysis bio-oil

    DOE PAGESBeta

    Choi, Jae -Soon; Zacher, Alan; Wang, Huamin; Olarte, Mariefel V.; Armstrong, Beth L.; Meyer, III, Harry M.; Schwartz, Viviane; Soykal, I. Ilgaz

    2016-05-19

    This paper describes properties of molybdenum carbides as a potential catalyst for fast pyrolysis bio-oil hydroprocessing. Currently, high catalyst cost, short catalyst lifetime, and lack of effective regeneration methods are hampering the development of this otherwise attractive renewable hydrocarbon technology. A series of metal-doped bulk Mo carbides were synthesized, characterized, and evaluated in sequential low-temperature stabilization and high-temperature deoxygenation of a pine-derived bio-oil. During a typical 60 h run, Mo carbides were capable of upgrading raw bio-oil to a level suitable for direct insertion into the current hydrocarbon infrastructure with residual oxygen content and total acid number of upgraded oilsmore » below 2 wt % and 0.01 mg KOH g–1, respectively. The performance was shown to be sensitive to the type of metal dopant, Ni-doped Mo carbides outperforming Co-, Cu-, or Ca-doped counterparts; a higher Ni loading led to a superior catalytic performance. No bulk oxidation or other significant structural changes were observed. Besides the structural robustness, another attractive property of Mo carbides was in situ regenerability. The effectiveness of regeneration was demonstrated by successfully carrying out four consecutive 60 h runs with a reductive decoking between two adjacent runs. These results strongly suggest that Mo carbides are a good catalyst candidate which could lead to a significant cost reduction in hydroprocessing bio-oils. Furthermore, we highlight areas for future research which will be needed to further understand carbide structure–function relationships and help design practical bio-oil upgrading catalysts based on Mo carbides.« less

  7. Adsorption of humic acids and trace metals in natural waters

    NASA Technical Reports Server (NTRS)

    Leung, W. H.

    1982-01-01

    Studies concerning the interactions between suspended hydrous iron oxide and dissolved humic acids and trace metals are reported. As a major component of dissolved organic matters and its readiness for adsorption at the solid/water interface, humic acids may play a very important role in the organometallic geochemistry of suspended sediments and in determining the fate and distribution of trace metals, pesticides and anions in natural water systems. Most of the solid phases in natural waters contain oxides and hydroxides. The most simple promising theory to describe the interactions of hydrous iron oxide interface is the surface complex formation model. In this model, the adsorptions of humic acids on hydrous iron oxide may be interpreted as complex formation of the organic bases (humic acid oxyanions) with surface Fe ions. Measurements on adsorptions were made in both fresh water and seawater. Attempts have been made to fit our data to Langmuir adsorption isotherm. Adsorption equilibrium constants were determined.

  8. Generation of hydroxyl radicals from metal-loaded humic acids

    SciTech Connect

    Paciolla, M.D.; Jansen, S.A.; Davies, G.

    1999-06-01

    Humic acids (HAs) are naturally occurring biopolymers that are ubiquitous in the environment. They are most commonly found in the soil, drinking water, and a variety of plants. Pharmacological and therapeutic studies involving humic acids have been reported to some extent. However, when certain transition metals are bound to humic acids, e.g., iron and copper, they can be harmful to biological organisms. For this study, humic acids were extracted from German, Irish, and New Hampshire soils that were selectively chosen because of their reich abundance in humic material. Each sample was treated at room temperature with 0.1 M ferric and cupric solutions for 48 h. The amount of iron and copper adsorbed by humic acid was accurately quantitated using atomic absorption spectroscopy. The authors further demonstrate that these metal-loaded humic acids can produce deleterious oxidizing species such as the hydroxyl radical (HO*) through the metal-driven Fenton reaction. Electron paramagnetic resonance (EPR) employing spin trapping techniques with 5,5-dimethylpyrroline N-oxide (DMPO) is used to confirm the generation of hydroxyl radicals. The DMPO-OH adduct with hyperfine splitting constants A{sub N} = A{sub H} = 14.9 G is observed upon the addition of exogenous hydrogen peroxide. The concentration of hydroxyl radical was determined using 4-hydroxytempo (TEMPO-OH) as a spin standard. The presence of another oxidizing species, Fe{double_bond}O{sup 2+}, is also proposed in the absence of hydrogen peroxide.

  9. Effects of Electric Discharge Plasma Treatment on the Thermal Conductivity of Polymer-Metal Nitride/Carbide Composites

    NASA Astrophysics Data System (ADS)

    Parali, Levent; Kurbanov, Mirza A.; Bayramov, Azad A.; Tatardar, Farida N.; Sultanakhmedova, Ramazanova I.; Xanlar, Huseynova Gulnara

    2015-11-01

    High-density polymer composites with semiconductor or dielectric fillers such as aluminum nitride (AIN), aluminum oxide (Al2O3), titanium carbide (TiC), titanium nitride (TiN), boron nitride (BN), silicon nitride (Si3N4), and titanium carbonitride (TiCN) were prepared by the hot pressing method. Each powder phase of the composites was exposed to an electric discharge plasma process before composite formation. The effects of the electric discharge plasma process and the filler content (volume fraction) on the thermal conductivity, volt-ampere characteristics, thermally stimulated depolarization current, as well as electrical and mechanical strength were investigated. The results of the study indicate that, with increasing filler volume fraction, the thermal conductivity of the samples also increased. Furthermore, the thermal conductivity, and electrophysical and mechanical properties of the high-density polyethylene + 70% BN composite modified using the electric discharge plasma showed improvement when compared with that without electric discharge plasma treatment.

  10. Silicon carbide reinforced silicon carbide composite

    NASA Technical Reports Server (NTRS)

    Lau, Sai-Kwing (Inventor); Calandra, Salvatore J. (Inventor); Ohnsorg, Roger W. (Inventor)

    2001-01-01

    This invention relates to a process comprising the steps of: a) providing a fiber preform comprising a non-oxide ceramic fiber with at least one coating, the coating comprising a coating element selected from the group consisting of carbon, nitrogen, aluminum and titanium, and the fiber having a degradation temperature of between 1400.degree. C. and 1450.degree. C., b) impregnating the preform with a slurry comprising silicon carbide particles and between 0.1 wt % and 3 wt % added carbon c) providing a cover mix comprising: i) an alloy comprising a metallic infiltrant and the coating element, and ii) a resin, d) placing the cover mix on at least a portion of the surface of the porous silicon carbide body, e) heating the cover mix to a temperature between 1410.degree. C. and 1450.degree. C. to melt the alloy, and f) infiltrating the fiber preform with the melted alloy for a time period of between 15 minutes and 240 minutes, to produce a ceramic fiber reinforced ceramic composite.

  11. Metals in crayfish from neutralized acidic and non-acidic lakes

    SciTech Connect

    Bagatto, G.; Alikhan, M.A.

    1987-09-01

    Large amounts of acid forming SO/sub 2/, as well as Cu, Ni and other metals are being continuously released into the environment by mining and smelting activities at Sudbury, Ontario, Canada. Consequently, a number of lakes in this region has become both acid and metal stressed. The addition of basic calcium compounds to acidic ponds and lakes has long been recognized as beneficial, as it contributes to increased fish production and water quality. In addition to increases in pH and alkalinity, such additions may reduce water-dissolved metal concentrations, change water transparency and bring about alterations in species diversity. Neutralization experiments have shown that an increase in water alkalinity and DOC may reduce the acute toxicity of Cu to fish. However, the influence of water quality on metal availability and accumulation has received scant attention. Earlier work showed that tissue metal concentrations in crayfish were related to the distance from the emission site. The purpose of the present study is to compare concentrations of six metals in freshwater crayfish from a neutralized acidic lake and a closely situated non-acidic lake. Various tissue concentrations in crayfish are also examined to determine specific tissue sites for these accumulations.

  12. RECOVERY OF METALS FROM ACID MINE DRAINAGE: JOURNAL ARTICLE

    EPA Science Inventory

    NRMRL-CIN-1349A Scharp*, R.A., Kawahara*, F.K., Burckle, J.O., Allen J., and Govind, R. "Recovery of Metals from Acid Mine Drainage." In: Bioremediation of Inorganic Compounds, In Situ and On-Site Bioremediation Sixth International Symposium, San Diego, CA, 6/4-7/2001. Andrea Le...

  13. ACID EXTRACTION TREATMENT SYSTEM FOR TREATMENT OF METAL CONTAMINATED SOILS

    EPA Science Inventory

    The Acid Extraction Treatment System (AETS) reduces the concentrations and/or leachability of heavy metals in contaminated soils so the soil can be returned to the site from which it originated. he objective of the project was to determine the effectiveness and commercial viabili...

  14. Impact of effects of acid precipitation on toxicity of metals.

    PubMed Central

    Nordberg, G F; Goyer, R A; Clarkson, T W

    1985-01-01

    Acid precipitation may increase human exposure to several potentially toxic metals by increasing metal concentrations in major pathways to man, particularly food and water, and in some instances by enhancing the conversion of metal species to more toxic forms. Human exposures to methylmercury are almost entirely by way of consumption of fish and seafood. In some countries, intakes by this route may approach the levels that can give rise to adverse health effects for population groups with a high consumption of these food items. A possible increase in methylmercury concentrations in fish from lakes affected by acid precipitation may thus be of concern to selected population groups. Human exposures to lead reach levels that are near those associated with adverse health effects in certain sensitive segments of the general population in several countries. The possibility exists that increased exposures to lead may be caused by acid precipitation through a mobilization of lead from soils into crops. A route of exposure to lead that may possibly be influenced by acid precipitation is an increased deterioration of surface materials containing lead and a subsequent ingestion by small children. A similar situation with regard to uptake from food exists for cadmium (at least in some countries). Human metal exposures via drinking water may be increased by acid precipitation. Decreasing pH increases corrosiveness of water enhancing the mobilization of metal salts from soil; metallic compounds may be mobilized from minerals, which may eventually reach drinking water. Also, the dissolution of metals (Pb, Cd, Cu) from piping systems for drinking water by soft acidic waters of high corrosivity may increase metal concentrations in drinking water. Exposures have occasionally reached concentrations which are in the range where adverse health effects may be expected in otherwise healthy persons. Dissolution from piping systems can be prevented by neutralizing the water before

  15. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals. Quarterly technical status report, April 1--June 30, 1993

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Howard, J.B.; Peters, W.A.

    1993-08-01

    Previous work at MIT indicates that essentially stoichiometric, rather than catalytic, reactions with alkaline earth metal oxides offer technical and economic promise as an innovative approach to upgrading natural gas to premium products such as liquid hydrocarbon fuels and chemicals. In this approach, methane would be reacted with relatively low cost and recyclable alkaline earth metal oxides, such as CaO and MgO, at high temperatures (>1500{degrees}C) to achieve very high (i.e. approaching 100%) gas conversions to H{sub 2}, CO and the corresponding alkaline earth metal carbides. These carbides exist stably in solid form at dry ambient conditions and show promise for energy storage and long distance transport. The overall objective of the proposed research is to develop new scientific and engineering knowledge bases for further assessment of the approach by performing laboratory-scale experiments and thermodynamic and thermochemical kinetics calculations. Work on this project will be performed according to two tasks. Under Task 1 (Industrial Chemistry), a laboratory-scale electric arc discharge plasma reactor is being constructed and will be used to assess the technical feasibility of producing Mg{sub 2}C{sub 3} from MgO and methane, and to identify the operating conditions of interest for the commercial production of Mg{sub 2}C{sub 3} and/or CaC{sub 2} from MgO and/or CaO and methane. Under Task 2 (Mechanistic Foundations), preliminary thermodynamic calculations were performed for the Ca-C-H-O and Mg-C-H-O systems using the Chemkin program. A scoping run with CaO in an electrical screen heater reactor under reduced methane pressure was also conducted. No appreciable quantity of acetylene was detected upon hydrolysis of the solid residue. This can be attributed to the very small quantity of methane at the very low pressure coupled with inadequate contacting of whatever methane was present with the CaO powder.

  16. Measurements of Total Hemispherical Emissivity of Several Stably Oxidized Nickel-Titanium Carbide Cemented Hard Metals from 600 F to 1,600 F

    NASA Technical Reports Server (NTRS)

    Wade, William R.; Casey, F. W., Jr.

    1959-01-01

    The total hemispherical emissivity of several nickel-titanium carbide cemented hard metals have been measured over a temperature range from 600 F to l,600 F. A variety of cemented hard metals were obtained from the Kennametal Corporation. A brief discussion of the apparatus employed and the procedures used for this investigation is included. The results of the tests of specimens in the as-received and polished states indicate a nearly constant emissivity for each material tested over the temperature range considered and only slight differences in emissivity values for the different materials. Values obtained on the stably oxidized specimens range from 0.90 to 0.94 at 6000 F and o.88 to 0.92 at 1,600 F for the as-received specimens and from 0.82 to 0.89 at 600 F and 0.85 to 0.87 at 1,600 F for the polished specimens. The surface analysis of the oxidized materials as obtained by X-ray diffraction methods and metallographic techniques are presented as an aid to reproducing the surface on which these measurements were made.

  17. Metal-support interactions in zeolite-supported noble metals: influence of metal crystallites on the support acidity.

    PubMed

    Kubicka, David; Kumar, Narendra; Venäläinen, Tapani; Karhu, Hannu; Kubicková, Iva; Osterholm, Heidi; Murzin, Dmitry Yu

    2006-03-16

    The metal-support interactions on a series of catalysts of different acidities, including platinum-modified zeolites and H-MCM-41, are investigated by means of XPS, CO and pyridine adsorption, and a model reaction (ring opening of decalin). The electronic properties of Pt are influenced by the acidity of the support, and the alteration of Pt properties increases with increasing acidity of the support, as can be seen from the changes in the Pt binding energy and stretching frequency of adsorbed CO. At the same time, the presence of platinum affects the acidic properties of the supports by reducing the strength of the acid sites. This is observed directly as the changes in desorption of pyridine from the acid sites and indirectly as the suppression of cracking reactions during the ring opening of decalin on the Pt-modified catalysts. The observed results are discussed in terms of the interatomic potential model. PMID:16526734

  18. Water and acid soluble trace metals in atmospheric particles

    NASA Technical Reports Server (NTRS)

    Lindberg, S. E.; Harriss, R. C.

    1983-01-01

    Continental aerosols are collected above a deciduous forest in eastern Tennessee and subjected to selective extractions to determine the water-soluble and acid-leachable concentrations of Cd, Mn, Pb, and Zn. The combined contributions of these metals to the total aerosol mass is 0.5 percent, with approximately 70 percent of this attributable to Pb alone. A substantial fraction (approximately 50 percent or more) of the acid-leachable metals is soluble in distilled water. In general, this water-soluble fraction increases with decreasing particle size and with increasing frequency of atmospheric water vapor saturation during the sampling period. The pattern of relative solubilities (Zn being greater than Mn, which is approximately equal to Cd, which is greater than Pb) is found to be similar to the general order of the thermodynamic solubilities of the most probable salts of these elements in continental aerosols with mixed fossil fuel and soil sources.

  19. 40 CFR 721.10487 - Alkylbenzenes sulfonic acids, metal salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylbenzenes sulfonic acids, metal... Specific Chemical Substances § 721.10487 Alkylbenzenes sulfonic acids, metal salts (generic). (a) Chemical... as alkylbenzenes sulfonic acids, metal salts (PMNs P-04-599, P-04-600, P-04-605, and P-04-606)...

  20. Chill steel-pickling acids to ease metals recovery

    SciTech Connect

    1995-11-01

    New Jersey Galvanizing coats steel with zinc using a hot dip process. The spent pickling acid contains metal in concentrations well above the amounts allowed for wastewater discharge. If removed as a clean, crystalline precipitate, these waste metals can be sold for use as fertilizer additives. To recover the metals, New Jersey Galvanizing cools the spent acid with refrigerated glycol and filters out the precipitated metal. The original refrigeration unit needed to operate 24 hours, 7 days a week to meet production requirements. It also required a full-time employee to monitor the operation of the refrigeration and recovery equipment. When the refrigeration unit needed routine maintenance, the loss of refrigeration often caused the pickling operation to shut down. To reduce operating costs and boost production capacity, the old chiller was replaced with a larger, automatic unit from Refrigeration Resources. The new refrigeration unit can handle the required cooling load by operating only three, 8-hour shifts per week, rather than by operating continuously, so routine maintenance can be performed on the unit without affecting production capacity. The new chiller system paid for itself in only one month through increased production and reduced labor costs.

  1. Method of forming impermeable carbide coats on graphite

    DOEpatents

    Wohlberg, C.

    1973-12-11

    A method of forming an impermeable refractory metal carbide coating on graphite is described in which a metal containing oxidant and a carbide former are applied to the surface of the graphite, heated to a temperature of between 1200 and 1500 deg C in an inert gas, under a vacuum and continuing to heat to about 2300 deg C. (Official Gazette)

  2. Estimating the acidity of transition metal hydride and dihydrogen complexes by adding ligand acidity constants.

    PubMed

    Morris, Robert H

    2014-02-01

    A simple equation (pKa(THF) = ∑AL + Ccharge + Cnd + Cd6) can be used to obtain an estimate of the pKa of diamagnetic transition metal hydride and dihydrogen complexes in tetrahydrofuran, and, by use of conversion equations, in other solvents. It involves adding acidity constants AL for each of the ligands in the 5-, 6-, 7-, or 8-coordinate conjugate base complex of the hydride or dihydrogen complex along with a correction for the charge (Ccharge = -15, 0 or 30 for x = +1, 0 or -1 charge, respectively) and the periodic row of the transition metal (Cnd = 0 for 3d or 4d metal, 2 for 5d metal) as well as a correction for d(6) octahedral acids (Cd6 = 6 for d(6) metal ion in the acid, 0 for others) that are not dihydrogen complexes. Constants AL are provided for 13 commonly occurring ligand types; of these, nine neutral ligands are correlated with Lever's electrochemical ligand parameters EL. This method gives good estimates of the over 170 literature pKa values that range from less than zero to 50 with a standard deviation of 3 pKa units for complexes of the metals chromium to nickel, molybdenum, ruthenium to palladium, and tungsten to platinum in the periodic table. This approach allows a quick assessment of the acidity of hydride complexes found in nature (e.g., hydrogenases) and in industry (e.g., catalysis and hydrogen energy applications). The pKa values calculated for acids that have bulky or large bite angle chelating ligands deviate the most from this correlation. The method also provides an estimate of the base strength of the deprotonated form of the complex. PMID:24410025

  3. Deposition of mullite and mullite-like coatings on silicon carbide by dual-source metal plasma immersion. Topical report, October 1995--September 1996

    SciTech Connect

    Brown, I.G.; Monteiro, O.R.

    1997-04-01

    Mullite and mullite-like coatings on silicon carbide have been produced by a Metal Plasma Immersion Ion Implantation and Deposition (Mepiiid) technique based on two cathodic vacuum arc sources and concurrent pulse biasing of the substrate in an oxygen atmosphere. The deposition was carried out at oxygen partial pressures of between 0.66 and 3.33 Pa. The Al:Si ratio in the films varied from 1:1 to 8:1 and was controlled by varying the pulse duration of the separate plasma guns. High bias voltage was used early in the deposition process in order to produce atomic mixing at the film-substrate interface, while lower bias voltage was used later in the deposition; low ion energy allows control of the physical properties of the film as well as faster deposition rates. The as-deposited films were amorphous, and crystalline mullite was formed by subsequent annealing at 1,100 C for 2 hours in air. Strong adhesion between the mullite and the SiC was achieved, in some cases exceeding the 70 MPa instrumental limit of the pull-tester.

  4. XPS analysis by exclusion of a-carbon layer on silicon carbide nanowires by a gold catalyst-supported metal-organic chemical vapor deposition method.

    PubMed

    Nam, Sang-Hun; Kim, Myoung-Hwa; Hyun, Jae-Sung; Kim, Young Dok; Boo, Jin-Hyo

    2010-04-01

    Silicon carbide (SiC) nano-structures would be favorable for application in high temperature, high power, and high frequency nanoelectronic devices. In this study, we have deposited cubic-SiC nanowires on Au-deposited Si(001) substrates using 1,3-disilabutane as a single molecular precursor through a metal-organic chemical vapor deposition (MOCVD) method. The general deposition pressure and temperature were 3.0 x 10(-6) Torr and 1000 degrees C respectively, with the deposition carried out for 1 h. Au played an important role as a catalyst in growing the SiC nanowires. SiC nanowires were grown using a gold catalyst, with amorphous carbon surrounding the final SiC nanowire. Thus, the first step involved removal of the remaining SiO2, followed by slicing of the amorphous carbon into thin layers using a heating method. Finally, the thinly sliced amorphous carbon is perfectly removed using an Ar sputtering method. As a result, this method may provide more field emission properties for the SiC nanowires that are normally inhibited by the amorphous carbon layer. Therefore, exclusion of the amorphous carbon layer is expected to improve the overall emission properties of SiC nanowires. PMID:20355494

  5. Effect of Transition Metals on Polysialic Acid Structure and Functions.

    PubMed

    Murthy, Raghavendra Vasudeva; Bharate, Priya; Gade, Madhuri; Sangabathuni, Sivakoti; Kikkeri, Raghavendra

    2016-04-01

    Polysialic acid (PSA) is one of the most abundant glycopolymer present in embryonic brain, and it is known to be involved in key roles such as plasticity in the central nervous system, cell adhesion, migration and localization of neurotrophins. However, in adult brain, its expression is quite low. The exception to this is in Alzheimer's disease (AD) brain, where significantly increased levels of polysilylated neural cell adhesion molecule (PSA-NCAM) have been reported. Here, we confirm the role of PSA as a metal chelator, allowing it to decrease cytotoxicity caused by high levels of transition metals, commonly found in AD brain, and as a regulator of cell behavior. UV-visible (UV-vis) and circular dichroism (CD) spectroscopy, atomic force microscopy (AFM), and isothermal titration calorimetry (ITC) techniques were used to investigate the assembly of PSA-metals complexes. These PSA-metal complexes exhibited less toxicity compared to free metal ions, and in particular, the PSA-Cu(2+) complex synergistically promoted neurite outgrowth in PC12 cells. PMID:26990355

  6. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide.

    PubMed

    Abou-Melha, Khlood S

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria (Staphylococcus aureus), Gram -ve bacteria (Escherichia coli), and Fungi (Candida albicans). The tested compounds exhibited higher antibacterial activities. PMID:17728178

  7. Transition metal complexes of isonicotinic acid (2-hydroxybenzylidene)hydrazide

    NASA Astrophysics Data System (ADS)

    Abou-Melha, Khlood S.

    2008-06-01

    A new series of transition metal complexes of Schiff base isonicotinic acid (2-hydroxybenzylidene)hydrazide, HL, have been synthesized. The Schiff base reacted with Cu(II), Ni(II), Co(II), Mn(II), Fe(III) and UO 2(II) ions as monobasic tridentate ligand to yield mononuclear complexes of 1:2 (metal:ligand) except that of Cu(II) which form complex of 1:1 (metal:ligand). The ligand and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square planar geometry distorted towards tetrahedral. While, the UO 2(II) complex has its favour hepta-coordination. The ligand and its metal complexes were tested against one strain Gram +ve bacteria ( Staphylococcus aureus), Gram -ve bacteria (Escherichia coli) , and Fungi ( Candida albicans). The tested compounds exhibited higher antibacterial activities.

  8. Tungsten carbide: Crystals by the ton

    NASA Astrophysics Data System (ADS)

    Smith, E. N.

    1988-06-01

    A comparison is made of the conventional process of making tungsten carbide by carburizing tungsten powder and the Macro Process wherein the tungsten carbide is formed directly from the ore concentrate by an exothermic reaction of ingredients causing a simultaneous reduction and carburization. Tons of tungsten monocarbide crystals are formed in a very rapid reaction. The process is unique in that it is self regulating and produces a tungsten carbide compound with the correct stoichiometry. The high purity with respect to oxygen and nitrogen is achieved because the reactions occur beneath the molten metal. The morphology and hardness of these crystals has been studied by various investigators and reported in the listed references.

  9. ADVANCES IN BIOTREATMENT OF ACID MINE DRAINAGE AND BIORECOVERY OF METALS: 1. METAL PRECIPITATION FOR RECOVERY AND RECYCLE

    EPA Science Inventory

    Acid-mine drainage (AMD) is a severe pollution problem attributed to past mining activities. AMD is an acidic, metal-bearing wastewater generated by the oxidation of metal sulfides to sulfates by Thiobacillus bacteria in both active and abandoned mining operations. The wastewater...

  10. Influence of acid volatile sulfides and metal concentrations on metal partitioning in contaminated sediments

    USGS Publications Warehouse

    Lee, J.-S.; Lee, B.-G.; Luoma, S.N.; Choi, H.J.; Koh, C.-H.; Brown, C.L.

    2000-01-01

    The influence of acid volatile sulfide (AVS) on the partitioning of Cd, Ni, and Zn in porewater (PW) and sediment as reactive metals (SEM, simultaneously extracted metals) was investigated in laboratory microcosms. Two spiking procedures were compared, and the effects of vertical geochemical gradients and infaunal activity were evaluated. Sediments were spiked with a Cd-Ni-Zn mixture (0.06, 3, 7.5 ??mol/g, respectively) containing four levels of AVS (0.5, 7.5, 15, 35 ??mol/g). The results were compared to sediments spiked with four levels of Cd-Ni-Zn mixtures at one AVS concentration (7.5 ??mol/g). A vertical redox gradient was generated in each treatment by an 18-d incubation with an oxidized water column. [AVS] in the surface sediments decreased by 65-95% due to oxidation during incubation; initial [AVS] was maintained at 0.5-7.5 cm depth. PW metal concentrations were correlated with [SEM - AVS] among all data. But PW metal concentrations were variable, causing the distribution coefficient, Kd(pw) (the ratio of [SEM] to PW metal concentrations) to vary by 2-3 orders of magnitude at a given [SEM - AVS]. One reason for the variability was that vertical profiles in PW metal concentrations appeared to be influenced by diffusion as well as [SEM - AVS]. The presence of animals appeared to enhance the diffusion of at least Zn. The generalization that PW metal concentrations are controlled by [SEM - AVS] is subject to some important qualifications if vertical gradients are complicated, metal concentrations vary, or equilibration times differ.The influence of acid volatile sulfide (AVS) on the partitioning of Cd, Ni, and Zn in porewater (PW) and sediment as reactive metals (SEM, simultaneously extracted metals) was investigated in laboratory microcosms. Two spiking procedures were compared, and the effects of vertical geochemical gradients and infaunal activity were evaluated. Sediments were spiked with a Cd-Ni-Zn mixture (0.06, 3, 7.5 ??mol/g, respectively) containing

  11. A methodology to identify and quantify mobility-reducing defects in 4H-silicon carbide power metal-oxide-semiconductor field-effect transistors

    SciTech Connect

    Ettisserry, D. P. Goldsman, N.; Lelis, A.

    2014-03-14

    In this paper, we present a methodology for the identification and quantification of defects responsible for low channel mobility in 4H-Silicon Carbide (SiC) power metal-oxide-semiconductor field-effect transistors (MOSFETs). To achieve this, we use an algorithm based on 2D-device simulations of a power MOSFET, density functional simulations, and measurement data. Using physical modeling of carrier mobility and interface traps, we reproduce the experimental I-V characteristics of a 4H-SiC doubly implanted MOSFET through drift-diffusion simulation. We extract the position of Fermi level and the occupied trap density as a function of applied bias and temperature. Using these inputs, our algorithm estimates the number of possible trap types, their energy levels, and concentrations at 4H-SiC/SiO{sub 2} interface. Subsequently, we use density functional theory (DFT)-based ab initio simulations to identify the atomic make-up of defects causing these trap levels. We study silicon vacancy and carbon di-interstitial defects in the SiC side of the interface. Our algorithm indicates that the D{sub it} spectrum near the conduction band edge (3.25 eV) is composed of three trap types located at 2.8–2.85 eV, 3.05 eV, and 3.1–3.2 eV, and also calculates their densities. Based on DFT simulations, this work attributes the trap levels very close to the conduction band edge to the C di-interstitial defect.

  12. A methodology to identify and quantify mobility-reducing defects in 4H-silicon carbide power metal-oxide-semiconductor field-effect transistors

    NASA Astrophysics Data System (ADS)

    Ettisserry, D. P.; Goldsman, N.; Lelis, A.

    2014-03-01

    In this paper, we present a methodology for the identification and quantification of defects responsible for low channel mobility in 4H-Silicon Carbide (SiC) power metal-oxide-semiconductor field-effect transistors (MOSFETs). To achieve this, we use an algorithm based on 2D-device simulations of a power MOSFET, density functional simulations, and measurement data. Using physical modeling of carrier mobility and interface traps, we reproduce the experimental I-V characteristics of a 4H-SiC doubly implanted MOSFET through drift-diffusion simulation. We extract the position of Fermi level and the occupied trap density as a function of applied bias and temperature. Using these inputs, our algorithm estimates the number of possible trap types, their energy levels, and concentrations at 4H-SiC/SiO2 interface. Subsequently, we use density functional theory (DFT)-based ab initio simulations to identify the atomic make-up of defects causing these trap levels. We study silicon vacancy and carbon di-interstitial defects in the SiC side of the interface. Our algorithm indicates that the Dit spectrum near the conduction band edge (3.25 eV) is composed of three trap types located at 2.8-2.85 eV, 3.05 eV, and 3.1-3.2 eV, and also calculates their densities. Based on DFT simulations, this work attributes the trap levels very close to the conduction band edge to the C di-interstitial defect.

  13. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  14. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  15. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  16. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  17. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  18. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  19. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal salt... identified generically as disubstituted benzoic acid, alkali metal salt (PMN P-03-643) is subject...

  20. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  1. Effects of humic acid-metal complexes on hepatic carnitine palmitoyltransferase, carnitine acetyltransferase and catalase activities

    SciTech Connect

    Fungjou Lu; Youngshin Chen . Dept. of Biochemistry); Tienshang Huang . Dept. of Medicine)

    1994-03-01

    A significant increase in activities of hepatic carnitine palmitoyltransferase and carnitine acetyltransferase was observed in male Balb/c mice intraperitoneally injected for 40 d with 0.125 mg/0.1 ml/d humic acid-metal complexes. Among these complexes, the humic acid-As complex was relatively effective, whereas humic acid-25 metal complex was more effective, and humic acid-26 metal complex was most effective. However, humic acid or metal mixtures, or metal such as As alone, was not effective. Humic acid-metal complexes also significantly decreased hepatic catalase activity. A marked decrease of 60-kDa polypeptide in liver cytoplasm was also observed on SDS-polyacrylamide gel electrophoresis after the mice had been injected with the complexes. Morphological analysis of a histopathological biopsy of such treated mice revealed several changes in hepatocytes, including focal necrosis and cell infiltration, mild fatty changes, reactive nuclei, and hypertrophy. Humic acid-metal complexes affect activities of metabolic enzymes of fatty acids, and this results in accumulation of hydrogen peroxide and increase of the lipid peroxidation. The products of lipid peroxidation may be responsible for liver damage and possible carcinogenesis. Previous studies in this laboratory had shown that humic acid-metal complex altered the coagulation system and that humic acid, per se, caused vasculopathy. Therefore, humic acid-metal complexes may be main causal factors of not only so-called blackfoot disease, but also the liver cancer prevailing on the southwestern coast of Taiwan.

  2. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

    DOE PAGESBeta

    Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; Stachiola, Dario; Brito, Joaquin L.

    2015-05-06

    A new approach has been tested for the preparation of metal/Mo₂C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu₃(MoO₄)₂(OH)₂, a-NiMoO₄ and CoMoO₄•nH₂O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo₂C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu²⁺, Ni²⁺ and Co²⁺ cations inside each molybdate. The synthesized Cu/Mo₂C, Ni/Mo₂C and Co/Mo₂C catalysts were highlymore » active for the hydrogenation of CO₂. The metal/Mo₂C systems exhibited large variations in the selectivity towards methanol, methane and CnH₂n₊₂ (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C-O bonds. Cu/Mo₂C displayed a high selectivity for CO and methanol production. Ni/Mo₂C and Co/Mo₂C were the most active catalysts for the activation and full decomposition of CO₂, showing high selectivity for the production of methane (Ni case) and CnH₂n₊₂ (n > 2) hydrocarbons (Co case).« less

  3. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

    SciTech Connect

    Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; Stachiola, Dario; Brito, Joaquin L.

    2015-05-06

    A new approach has been tested for the preparation of metal/Mo₂C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu₃(MoO₄)₂(OH)₂, a-NiMoO₄ and CoMoO₄•nH₂O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo₂C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu²⁺, Ni²⁺ and Co²⁺ cations inside each molybdate. The synthesized Cu/Mo₂C, Ni/Mo₂C and Co/Mo₂C catalysts were highly active for the hydrogenation of CO₂. The metal/Mo₂C systems exhibited large variations in the selectivity towards methanol, methane and CnH₂n₊₂ (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C-O bonds. Cu/Mo₂C displayed a high selectivity for CO and methanol production. Ni/Mo₂C and Co/Mo₂C were the most active catalysts for the activation and full decomposition of CO₂, showing high selectivity for the production of methane (Ni case) and CnH₂n₊₂ (n > 2) hydrocarbons (Co case).

  4. Evaluation of the factors governing metal biosorption and metal toxicity in acidic soil isolates

    SciTech Connect

    Pradhan, A.A.

    1992-06-09

    This research project was designed to determine the feasibility of microbial biosorption processes for removing metal ions from aqueous systems. A culture of acidic soil actinomycetes, grown in an aerobic environment in a completely mixed, semibatch culture reactor, was used for the study. The experiments were based on removal of copper and lead from test solutions. The anionic systems tested were nitrate, sulfate, and chloride. To determine the factors influencing biosorption and to characterize metal uptake by cellular and extracellular components of the microbial system, a dialysis testing procedure was developed. The effectiveness of biosorption was influenced by pH, initial concentration of metals, type of anionic system, and organic content of the system. respirometric runs were carried out to identify potential inhibitory effects of metal accumulation on microbial activities. In general, metal accumulation resulted in a decrease in the microbial oxygen uptake rate. Also, a lag phase was observed before the onset of the respiratory activity particularly at concentrations of copper and lead greater than 100 ppM.

  5. Thermodynamics of the Si-C-O system for the production of silicon carbide and metallic silicon

    NASA Astrophysics Data System (ADS)

    Nagamori, M.; Malinsky, I.; Claveau, A.

    1986-09-01

    The predominance diagrams of the Si-C-O system for 1350 to 2200 °C have been constructed thermodynamically by taking into account the presence of liquid silicon monoxide. The high-temperature behavior of various feeds, such as the SiO2-C and SiO2-SiC systems, have been calculated as functions of mixing ratio and reaction temperature by using the method of equilibrium mass-balance. For an efficient SiC-making, a charge having a C/Si ratio of 2.91 should be heated between 2035 and 2045 °C, where SiC crystals can be grown mainly via gas-phase reactions of SiO(g). Metallic silicon cannot be produced unless a charge of the Si-C-O system is heated above 2037 °C. In Si-making, liquid SiO plays an important role in that the yield can be improved substantially by enhancing the condensation of SiO gas in the upper cooler part of the furnace. This work also lends thermodynamic proof and support to the double-reactor model, in which a greater fixation of ascending SiO gas on carbon as SiC is considered essential for obtaining a higher silicon yield in industrial furnaces. Some fundamental strategies useful to the improvements of commercial Si- and SiC-making operations have been described quantitatively.

  6. Ultrafine metal particles immobilized on styrene/acrylic acid copolymer particles

    SciTech Connect

    Tamai, Hisashi; Hamamoto, Shiro; Nishiyama, Fumitaka; Yasuda, Hajime

    1995-04-01

    Ultrafine metal particles immobilized on styrene/acrylic acid copolymer fine particles were produced by reducing the copolymer particles-metal ion complexes or refluxing an ethanol solution of metal ions in the presence of copolymer particles. The size of metal particles formed by reduction of the complex is smaller than that by reflux of the metal ion solution and depends on the amount of metal ions immobilized.

  7. Atomic and molecular adsorption on transition-metal carbide (111) surfaces from density-functional theory: a trend study of surface electronic factors

    NASA Astrophysics Data System (ADS)

    Vojvodic, A.; Ruberto, C.; Lundqvist, B. I.

    2010-09-01

    This study explores atomic and molecular adsorption on a number of early transition-metal carbides (TMCs) in NaCl structure by means of density-functional theory calculations. The investigated substrates are the TM-terminated TMC(111) surfaces, of interest because of the presence of different types of surface resonances (SRs) on them and because of their technological importance in growth processes. Also, TM compounds have shown potential in catalysis applications. Trend studies are conducted with respect to both period and group in the periodic table, choosing the substrates ScC, TiC, VC, ZrC, NbC, δ-MoC, TaC, and WC (in NaCl structure) and the adsorbates H, B, C, N, O, F, NH, NH2, and NH3. Trends in adsorption strength are explained in terms of surface electronic factors, by correlating the calculated adsorption-energy values with the calculated surface electronic structures. The results are rationalized by use of a concerted-coupling model (CCM), which has previously been applied successfully to the description of adsorption on TiC(111) and TiN(111) surfaces (Ruberto et al 2007 Solid State Commun. 141 48). First, the clean TMC(111) surfaces are characterized by calculating surface energies, surface relaxations, Bader charges, and surface-localized densities of states (DOSs). Detailed comparisons between surface and bulk DOSs reveal the existence of transition-metal localized SRs (TMSRs) in the pseudogap and of several C-localized SRs (CSRs) in the upper valence band on all considered TMC(111) surfaces. The spatial extent and the dangling bond nature of these SRs are supported by real-space analyses of the calculated Kohn-Sham wavefunctions. Then, atomic and molecular adsorption energies, geometries, and charge transfers are presented. An analysis of the adsorbate-induced changes in surface DOSs reveals a presence of both adsorbate-TMSR and adsorbate-CSRs interactions, of varying strengths depending on the surface and the adsorbate. These variations are

  8. Control of self-propagating high-temperature synthesis derived aluminum-titanium carbide metal matrix composites

    NASA Astrophysics Data System (ADS)

    Garrett, William

    Self-propagating High-temperature Synthesis (SHS) is a combustion process that can be used to form Metal Matrix Composite (MMC) reinforcing phases in situ. Generally, the kinetic processes in these reactions are poorly understood but are affected by reactant particle size, reactant green density, reactant stoichiometry, reaction preheat temperature, and reaction product cooling rate. These reaction parameters also affect the microstructure of the reaction products because of changes in the rate of heat evolution, reaction rate, surface area available for heterogeneous nucleation, reaction temperature, and the stable phases during and after the reaction. Post-reaction processes affecting the microstructure and properties of the SHS products include densification, melt alloying (SHS reaction products are used as a master alloy), and die casting techniques. Matrix alloy additions should be controlled to prevent unwanted reactions between the matrix and the reinforcement. In the present study, Ti + C + X → TiC + X (X = Al or TiC) is the SHS reaction system studied, with varying amounts of Al (10-50wt%) or TiC (0-20wt%) added to the reactants as a thermal diluent. Addition of these diluents decreases the reaction temperatures and decreases the TiC reinforcing particle size and interaction during particle growth. A method of direct thermal analysis of the self-heating behavior of diluted SHS reactions is developed and compared to existing methods used to measure the apparent activation energy of single step SHS reactions. The activation energies are used to determine a probable reaction path for Ti + C + Al → TiC + Al. SHS reaction products of various diluent concentrations are analyzed for TiC particle size and shape. SHS reaction products containing 55v% TiC - 45v% Al are dispersed as a master alloy in aluminum melts; reaction products containing higher concentrations of TiC particles are difficult to disperse. To show compatibility with the TiC reinforcing

  9. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  10. Immobilization of EAFD heavy metals using acidic materials.

    PubMed

    Mitrakas, Manassis G; Sikalidis, Constantinos A; Karamanli, Theoktisti P

    2007-03-01

    This study was undertaken to determine the chemical and leaching characteristics of the Electric Arc Furnace Dust (EAFD) generated by a Greek plant and to investigate various acidic materials efficiency on the EAFD stabilization. In order to investigate how [OH(-)] neutralization influences EAFD heavy metals leachability, Na HCO3(-), HNO3 and H3PO4 were used as acidic materials. The concentration of Pb in leachate was found between 40 and 3.7 x 10(3) mg Pb/kg of EAFD, exceeding in all EAFD samples the maximum acceptable limit (MAL) 25 mg/kg for landfill disposal. Neutralization of [OH(-)] with HCO3(-) decreased Pb concentration in leachate at 350 mg Pb/kg of EAFD, while excess over a stoichiometry in HCO3(-) addition increased leachability of Pb, Cd, Cr, Cu as well as F. Using HNO3 as an acidic material decreased leachability of almost all the parameters concerning the EC directive 33/19-01-2003 in a pH value up to 7.2, in exception of Zn. Zinc leachability showed a U shape curve as a function of pH value. The concentration of Zn was minimized in a concentration lower than 1 mg Zn/kg EAFD in a pH range 10.5 to 9 and exceeded the MAL 90 mg/kg at a pH value 7.2. However, the major disadvantage of HNO3 was proved to be its leachability, since NO3(-) concentration in leachate was equal to HNO3 dose. H3PO4 was found the most promising acidic material for the chemical immobilization of heavy metals, since it decreased their leachability in a concentration significantly lower than MAL at a pH value up to 7.1. Finally, the concentration of Cl(-) ranged between 18 and 33 x 10(3) mg Cl(-)/kg EAFD exceeding in all EAFD samples the MAL 17 x 10(3) mg/kg. This high concentration of Cl(-) is attributed to the scrap and it could be reduced only by modification of its composition. PMID:17365324

  11. Assessment of nanofiltration and reverse osmosis potentialities to recover metals, sulfuric acid, and recycled water from acid gold mining effluent.

    PubMed

    Ricci, Bárbara C; Ferreira, Carolina D; Marques, Larissa S; Martins, Sofia S; Amaral, Míriam C S

    2016-01-01

    This work assessed the potential of nanofiltration (NF) and reverse osmosis (RO) to treat acid streams contaminated with metals, such as effluent from the pressure oxidation process (POX) used in refractory gold ore processing. NF and RO were evaluated in terms of rejections of sulfuric acid and metals. Regarding NF, high sulfuric acid permeation (∼100%), was observed, while metals were retained with high efficiencies (∼90%), whereas RO led to high acid rejections (<88%) when conducted in pH values higher than 1. Thus, sequential use of NF and RO was proved to be a promising treatment for sulfuric acid solutions contaminated by metals, such as POX effluent. In this context, a purified acid stream could be recovered in NF permeate, which could be further concentrated in RO. Recovered acid stream could be reused in the gold ore processing or commercialized. A metal-enriched stream could be also recovered in NF retentate and transferred to a subsequent metal recovery stage. In addition, considering the high acid rejection obtained through the proposed system, RO permeate could be used as recycling water. PMID:27438241

  12. Salt flux synthesis of single and bimetallic carbide nanowires

    NASA Astrophysics Data System (ADS)

    Leonard, Brian M.; Waetzig, Gregory R.; Clouser, Dale A.; Schmuecker, Samantha M.; Harris, Daniel P.; Stacy, John M.; Duffee, Kyle D.; Wan, Cheng

    2016-07-01

    Metal carbide compounds have a broad range of interesting properties and are some of the hardest and highest melting point compounds known. However, their high melting points force very high reaction temperatures and thus limit the formation of high surface area nanomaterials. To avoid the extreme synthesis temperatures commonly associated with these materials, a new salt flux technique has been employed to reduce reaction temperatures and form these materials in the nanometer regime. Additionally, the use of multiwall carbon nanotubes as a reactant further reduces the diffusion distance and provides a template for the final carbide materials. The metal carbide compounds produced through this low temperature salt flux technique maintain the nanowire morphology of the carbon nanotubes but increase in size to ∼15–20 nm diameter due to the incorporation of metal in the carbon lattice. These nano-carbides not only have nanowire like shape but also have much higher surface areas than traditionally prepared metal carbides. Finally, bimetallic carbides with composition control can be produced with this method by simply using two metal precursors in the reaction. This method provides the ability to produce nano sized metal carbide materials with size, morphology, and composition control and will allow for these compounds to be synthesized and studied in a whole new size and temperature regime.

  13. Method for making hot-pressed fiber-reinforced carbide-graphite composite

    DOEpatents

    Riley, Robert E.; Wallace Sr., Terry C.

    1979-01-01

    A method for the chemical vapor deposition of a uniform coating of tantalum metal on fibers of a woven graphite cloth is described. Several layers of the coated cloth are hot pressed to produce a tantalum carbide-graphite composite having a uniformly dispersed, fine grained tantalum carbide in graphite with compositions in the range of 15 to 40 volume percent tantalum carbide.

  14. Low resistance barrier layer for isolating, adhering, and passivating copper metal in semiconductor fabrication

    DOEpatents

    Weihs, Timothy P.; Barbee, Jr., Troy W.

    2002-01-01

    Cubic or metastable cubic refractory metal carbides act as barrier layers to isolate, adhere, and passivate copper in semiconductor fabrication. One or more barrier layers of the metal carbide are deposited in conjunction with copper metallizations to form a multilayer characterized by a cubic crystal structure with a strong (100) texture. Suitable barrier layer materials include refractory transition metal carbides such as vanadium carbide (VC), niobium carbide (NbC), tantalum carbide (TaC), chromium carbide (Cr.sub.3 C.sub.2), tungsten carbide (WC), and molybdenum carbide (MoC).

  15. Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

    NASA Technical Reports Server (NTRS)

    Bridson, P. K.; Fakhrai, H.; Lohrmann, R.; Orgel, L. E.; Van Roode, M.

    1981-01-01

    The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

  16. Carbide coated fibers in graphite-aluminum composites

    NASA Technical Reports Server (NTRS)

    Imprescia, R. J.; Levinson, L. S.; Reiswig, R. D.; Wallace, T. C.; Williams, J. M.

    1975-01-01

    The study of protective-coupling layers of refractory metal carbides on the graphite fibers prior to their incorporation into composites is presented. Such layers should be directly wettable by liquid aluminum and should act as diffusion barriers to prevent the formation of aluminum carbide. Chemical vapor deposition was used to uniformly deposit thin, smooth, continuous coats of ZrC on the carbon fibers of tows derived from both rayon and polyacrylonitrile. A wet chemical coating of the fibers, followed by high-temperature treatment, was used, and showed promise as an alternative coating method. Experiments were performed to demonstrate the ability of aluminum alloys to wet carbide surfaces. Titanium carbide, zirconium carbide and carbide-coated graphite surfaces were successfully wetted. Results indicate that initial attempts to wet surfaces of ZrC-coated carbon fibers appear successful.

  17. Protic acid-fluorine interactions and reactions with acids of transition metal perfluoroalkyl and perfluoroolefin complexes

    SciTech Connect

    Barmore, R.M.; Richmond, T.G.

    1993-12-31

    The authors are interested in devising new methods of C-F and C-X bond activation which could be applied to destruction of environmentally significant molecules. Dihalocarbene complexes are thought to be intermediates in a variety of reactions of metal haloalkyl complexes which could be applied to this problem. This paper reports observations indicating initial interactions of protic acids and fluorocarbon complexes which can be applied toward the hydrolysis of C-F bonds. Reactions of long chain halocarbons and halolefins will also be discussed.

  18. Comparison of natural organic acids and synthetic chelates at enhancing phytoextraction of metals from a multi-metal contaminated soil.

    PubMed

    do Nascimento, Clístenes Williams A; Amarasiriwardena, Dula; Xing, Baoshan

    2006-03-01

    Chemically assisted phytoremediation has been developing to induce accumulation of metals by high biomass plants. Synthetic chelates have shown high effectiveness to reach such a goal, but they pose serious drawbacks in field application due to the excessive amount of metals solubilized. We compared the performance of synthetic chelates with naturally occurring low molecular weight organic acids (LMWOA) in enhancing phytoextraction of metals by Indian mustard (Brassica juncea) from multi-metal contaminated soils. Gallic and citric acids were able to induce removal of Cd, Zn, Cu, and Ni from soil without increasing the leaching risk. Net removal of these metals caused by LMWOA can be as much as synthetic chelates. A major reason for this is the lower phytotoxicity of LMWOA. Furthermore, supplying appropriate mineral nutrients increased biomass and metal removal. PMID:16125291

  19. Leaching with Penicillium simplicissimum: Influence of Metals and Buffers on Proton Extrusion and Citric Acid Production

    PubMed Central

    Franz, Andreas; Burgstaller, Wolfgang; Schinner, Franz

    1991-01-01

    In the presence of insoluble metal oxides (industrial filter dust, zinc oxide, synthetic mixture of metal oxides), Penicillium simplicissimum developed the ability to excrete considerable amounts of citric acid (>100 mM). Parallel with the increase of citric acid concentration in the culture broth, zinc was solubilized from zinc oxide. The adsorption of filter dust onto the mycelium (the pellets formed were less than 1 mm in diameter) was required for not only the citric acid excretion but also the leaching of zinc. When the filter dust was replaced with a synthetic mixture of metal oxides or with zinc oxide in combination with trace elements, levels of adsorption and citric acid production were observed to be similar to those in experiments where industrial filter dust was used. The two most important properties of the filter dust were its heavy-metal content and its buffering capacity. These properties were simulated by adding heavy metals in soluble form (as chlorides, sulfates, or nitrates) or soluble buffers to the medium. Both heavy metals and buffers were not able to induce a citric acid efflux. As with citric acid production by Aspergillus niger, the addition of manganese lowered citric acid excretion (by 40% with metal oxide-induced citric acid efflux and by 100% with urea-induced citric acid efflux). Copper antagonized the effect of manganese. The mechanism for the bulk of citric acid excretion by P. simplicissimum, however, seemed to be different from that described for citric acid accumulation by A. niger. Because of the inefficiency of metals in solubilized form and of soluble buffers to induce a strong citric acid efflux, adsorption of an insoluble metal compound (zinc oxide) turned out to be essential. Surface phenomena possibly involving the plasma membrane H+-ATPase are thought to participate in the induction of citric acid excretion by P. simplicissimum in the presence of industrial filter dust. PMID:16348442

  20. Interaction of metal ions with acid sites of biosorbents peat moss and Vaucheria and model substances alginic and humic acids

    SciTech Connect

    Crist, R.H.; Martin, J.R.; Crist, D.R.

    1999-07-01

    The interaction between added metal ions and acid sites of two biosorbents, peat moss and the alga Vaucheria, was studied. Results were interpreted in terms of two model substances, alginic acid, a copolymer of guluronic and mannuronic acids present in marine algae, and humic acid in peat moss. For peat moss and Vaucheria at pH 4--6, two protons were displaced per Cd sorbed, after correction for sorbed metals also displaced by the heavy metal. The frequent neglect of exchange of heavy metals for metals either sorbed on the native material or added for pH adjustment leads to erroneous conclusions about proton displacement stoichiometry. Proton displacement constants K{sub ex}{sup H} decreased logarithmically with pH and had similar slopes for alginic acid and biosorbents. This pH effect was interpreted as an electrostatic effect of increasing anionic charge making proton removal less favorable. The maximum number of exchangeable acid sites (capacity C{sub H}) decreased with pH for alginic acid but increased with pH for biosorbents. Consistent with titration behavior, this difference was explained in terms of more weak acid sites in the biosorbents.

  1. ENGINEERING ASSESSMENT OF HOT-ACID TREATMENT OF MUNICIPAL SLUDGE FOR HEAVY METALS REMOVAL

    EPA Science Inventory

    The hot-acid method for treating sludge was developed by the Walden Division of Abcor, Inc., to remove heavy metals from municipal wastewater sludge. Investigations by Walden have demonstrated the degrees to which heavy metals are solubilized. Sulfuric acid dosage at about 20 to ...

  2. Physicochemical aspects of inhibition of acid corrosion of metals by unsaturated organic compounds

    NASA Astrophysics Data System (ADS)

    Avdeev, Ya G.; Kuznetsov, Yurii I.

    2012-12-01

    The state-of-the-art in the development and improvement of methods for protecting metals from corrosion in mineral acid solutions using unsaturated organic compounds is considered. Characteristic features of the mechanism of their protective action on metal corrosion in acidic media are discussed. The bibliography includes 203 references.

  3. 40 CFR 721.10487 - Alkylbenzenes sulfonic acids, metal salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... salts (generic). 721.10487 Section 721.10487 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10487 Alkylbenzenes sulfonic acids, metal salts (generic). (a) Chemical... as alkylbenzenes sulfonic acids, metal salts (PMNs P-04-599, P-04-600, P-04-605, and P-04-606)...

  4. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  5. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  6. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  7. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  8. NOVEL POLY-GLUTAMIC ACID FUNCTIONALIZED MICROFILTRATION MEMBRANES FOR SORPTION OF HEAVY METALS AT HIGH CAPACITY

    EPA Science Inventory

    Various sorbent/ion exchange materials have been reported in the literature for metal ion entrapment. We have developed a highly innovative and new approach to obtain high metal pick-up utilizing poly-amino acids (poly-L-glutamic acid, 14,000 MW) covalently attached to membrane p...

  9. Leaching with Penicillium simplicissimum: Influence of metals and buffers on proton extrusion and citric acid production

    SciTech Connect

    Franz, A.; Burgstaller, W.; Schinner, F. )

    1991-03-01

    In the presence of insoluble metal oxides (industrial filter dust, zinc oxide, synthetic mixture of metal oxides), Penicillium simplicissimum developed the ability to excrete considerable amounts of citric acid (>100 mM). Parallel with the increase of citric acid concentration in the culture broth, zinc was solubilized from zinc oxide. The adsorption of filter dust onto the mycelium (the pellets formed were less than 1 mm in diameter) was required for not only the citric acid excretion but also the leaching of zinc. When the filter dust was replaced with a synthetic mixture of metal oxides or with zinc oxide in combination with trace elements, levels of adsorption and citric acid production were observed to be similar to those in experiments where industrial filter dust was used. The two most important properties of the filter dust were its heavy-metal content and its buffering capacity. These properties were simulated by adding heavy metals in soluble form (as chlorides, sulfates, or nitrates) or soluble buffers to the medium. Both heavy metals and buffers were not able to induce a citric acid efflux. As with citric acid production by Aspergillus niger, the addition of manganese lowered citric acid excretion (by 40% with metal oxide-induced citric acid efflux and by 100% with urea-induced citric acid efflux). Copper antagonized the effect of manganese. The mechanism for the bulk of citric acid excretion by P. simplicissimum, however, seemed to be different from that described for citric acid accumulation by A. niger. Because of the inefficiency of metals in solubilized form and of soluble buffers to induce a strong citric acid efflux, adsorption of an insoluble metal compound (zinc oxide) turned out to be essential.

  10. Sonochemical destruction of free and metal-binding ethylenediaminetetraacetic acid.

    PubMed

    Frim, J Aaron; Rathman, James F; Weavers, Linda K

    2003-07-01

    This study focused on the sonochemical degradation of ethylenediaminetetraacetic acid (EDTA) and chromium-EDTA complexes. Degradation of the copper(II)-EDTA complex was also investigated as a comparison metal complex. A 90% degradation of a 150-microM EDTA solution with continuous O2-bubbling was shown for the 20-kHz system in approximately 3 h (kpseudo-first order = 1.22 x 10(-2) min-1) and less than 1 h for the 354-kHz system (kpseudo-first order = 5.42 x 10(-2) min-1). These results are consistent with the higher concentrations of hydrogen peroxide found in the higher frequency system and an expected oxidation of EDTA in bulk solution. The presence of a chelated metal decreased the rate of degradation at both frequencies. Cr(III)-EDTA degraded the slowest, supporting the theory that the extremely slow ligand exchange rate of chromium is the determining factor in how fast degradation by hydroxyl radical can occur. The 354-kHz system showed a 17% decrease in the original 150-microM Cr(III)-EDTA complex after 3 h of sonication. All of the chromium from the degraded EDTA complex existed as a combination of oxidized Cr(VI) and possibly small amounts of a new Cr(III)-organic complex (Cr(III)-Y). The 20-kHz system showed a similar extent of degradation (16%) after 3 h of sonication, despite lower hydroxyl radical production. Fifty percent of the chromium from the degraded EDTA complex was found as free Cr3+ ion, with the remaining 50% existing as both Cr(III)-Y and Cr(VI). Varying degrees of bulk oxidation, near-bubble thermolysis, and perhaps different degradation pathways at the two frequencies are responsible for these differences. PMID:14509702

  11. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  12. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  13. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  14. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkali metal salt (generic). 721.10097 Section 721.10097 Protection of Environment ENVIRONMENTAL... metal salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as disubstituted benzenesulfonic acid, alkali metal salt (PMN...

  15. Evaluation of metal/acid-volatile sulfide relationships in the prediction of metal bioaccumulation by benthic macroinvertebrates

    SciTech Connect

    Ankley, G.T.

    1996-12-01

    Recent studies have demonstrated that the toxicity of divalent cationic metals (cadmium, copper, lead, nickel, and zinc) in sediments can be controlled through binding to acid-volatile sulfide (AVS). When the molar concentration of AVS exceeds that of the metals (i.e., the metal/AVS ratio is less than unity), they exist predominantly as insoluble metal sulfides, which presumably are not biologically available. Thus, at metal/AVS ratios less than 1, toxicity of sediment-associated metals to benthic macro-invertebrates has not been observed. However, bioaccumulation may provide a more direct assessment of contaminant bioavailability than the presence or absence of toxicity. The purpose of this report is to comprehensively review available literature on metal bioaccumulation versus sediment metal/AVS relationships to further examine the tenet that AVS controls metal bioavailability. In all, 12 studies were evaluated; these ranged from short-term (10-d) laboratory experiments with metal-spiked or field-collected sediments containing cadmium, copper, lead, nickel, and/or zinc to long-term (> 1-year) field studies with sediments spiked with cadmium or zinc. Test organisms included mollusks, oligochaetes, polychaetes, amphipods, and midges. The preponderance of studies indicated reduced accumulation of metals at sediment metal/AVS ratios of less than 1. However, there were exceptions to this general observation, two of which occurred in short-term laboratory experiments with cadmium- or nickel-spiked sediments. In these studies there appeared to be a linear accumulation of metals with increasing sediment metal concentrations irrespective of the metal/AVS ratio. Although there is experimental evidence suggesting that significant bioaccumulation of metals does not occur when there is sufficient AVS available to bind them, the existence of data to the contrary indicates the need for further research into factors controlling the bioaccumulation of metals from sediments.

  16. Vibrational studies of interstitial carbide atoms in nickel and rhenium carbonyl carbide clusters

    SciTech Connect

    Stanghellini, P.L.; Rossetti, R.; D'Alfonso, G.; Longoni, G.

    1987-08-26

    A vibrational spectroscopy study of the interstitial carbon atom in a series of Re and Ni carbide clusters enabled the M-C vibrational modes to be assigned and the effect of the metal atoms capping the Re/sub 6/(..mu../sub 6/-C) and Ni/sub 8/(..mu../sub 8/-C) cores to be investigated. The assignment of the M-C vibrational modes has been confirmed by /sup 13/C isotopic labeling of the interstitial carbide atom. A single force constant value accounts for the observed frequencies in the nickel carbide clusters, whether capped or uncapped, and in the uncapped rhenium carbide clusters. In contrast, the vibrational analysis for the capped rhenium clusters indicates that the force field around the carbon atom should be described by slightly different axial and equatorial force constants. A rationalization of the capping effect in terms of structural and electronic effects is proposed.

  17. Silicon carbide ceramic production

    NASA Technical Reports Server (NTRS)

    Suzuki, K.; Shinohara, N.

    1984-01-01

    A method to produce sintered silicon carbide ceramics in which powdery carbonaceous components with a dispersant are mixed with silicon carbide powder, shaped as required with or without drying, and fired in nonoxidation atmosphere is described. Carbon black is used as the carbonaceous component.

  18. Adsorption/desorption in a system consisting of humic acid, heavy metals, and clay minerals

    SciTech Connect

    Liu, A.; Gonzalez, R.D.

    1999-10-01

    Metal adsorption/desorption in a system consisting of humic acid, metal ions, and clay minerals is described. Montmorillonite and purified humic acid were selected as prototype materials for this study. At a constant ionic strength, the amount of humic acid adsorbed on montmorillonite decreases when pH is increased. A slight increase in humic acid adsorption on montmorillonite is observed when there are bivalent metals present in the system. The metal adsorption on montmorillonite does not correlate to the amount of humic acid adsorbed on montmorillonite. Montmorillonite with preadsorbed humic acid does not show a significant change in the capacity of adsorbed metal ions. An increase in the ionic strength at a pH of 6.5 results in an increase in the adsorption of lead on montmorillonite in the presence of humic acid, while at a lower pH, the increase in ionic strength results in a decrease in metal adsorption. The bridging of bivalent metal ions between montmorillonite and humic acid is proposed as the dominant adsorption mechanism.

  19. Direct bonding for dissimilar metals assisted by carboxylic acid vapor

    NASA Astrophysics Data System (ADS)

    Song, Jenn-Ming; Huang, Shang-Kun; Akaike, Masatake; Suga, Tadatomo

    2015-03-01

    This study developed a low-temperature low-vacuum direct bonding process for dissimilar metals via surface modification with formic acid vapor. Robust Cu/Ag and Cu/Zn bonding with a shear strength higher than 25 MPa can be achieved by thermal compression at 275 and 300 °C, respectively. CuZn5 and Cu5Zn8 formed at the interface of Cu/Zn joints, while no distinct interdiffusion layers appeared at the Cu/Ag interface. At elevated temperatures, the shear strength of Cu/Zn joints decreased significantly and turned to be weaker than Cu/Ag at 250 °C due to the softening of Zn. All the joints performed well subjected to thermal cycling up to 1000 times. However, compared with Cu/Ag joints with stable mechanical performance suffering aging at 250 °C, the shear strength of Cu/Zn degraded drastically up to 200 h, and after that it remained almost constant, which can be ascribed to the competitive growth between CuZn5 and Cu5Zn8, resulting in collapse and oxidation of CuZn5.

  20. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals. Quarterly technical status report, April 1, 1995--June 30, 1995

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Howard, J.B.

    1995-08-01

    Upgrading of the experimental apparatus was necessitated by problems encountered in the previous scoping runs with CH{sub 4}/MgO. To further improve plasma stability, a pressure controller was installed on the cooling chamber to maintain the chamber pressure constant at 1 atm and a mass flow controller was installed on the main plasma gas inlet line. With a fully functional data acquisition and control system, there is now the capability to record arc voltage, arc current, chamber pressure, feed gas mass flow, and cooling water and gas temperatures during the relatively short experimental runs. With this system, an improved sampling protocol can also be implemented whereby gas and solid sampling are initiated only when fully developed flowrates of methane and MgO are established in the plasma. Solid products from a scoping run under conditions of excess MgO above the stoichiometric requirement for 100% conversion of the methane exhibited intense reactivity in the open atmosphere, indicating high concentrations of magnesium carbide in the product. The hypothesis is that reaction begins with hydrolysis of the carbide by atmospheric moisture giving acetylene and/or methylacetylene which then, because of the intense local heating (possibly due to the fine particle sizes of the recently formed carbides), are ignited to produce flaming combustion.

  1. Synthesis of Nanostructured Carbides of Titanium and Vanadium from Metal Oxides and Ferroalloys Through High-energy Mechanical Milling and Heat Treatment

    SciTech Connect

    Basu, P.; Jian, P. F.; Seong, K. Y.; Seng, G. S.; Hussain, Z.; Aziz, A.; Masrom, A. K.

    2010-03-11

    Carbides of Ti and V have been synthesized directly from their oxides and ferroalloys through mechanical milling and heat treatment. The powder mixtures are milled in a planetary ball mill from 15-80 hours and subsequently heat treated at 1000-1300 deg. C for TiO{sub 2}-C mixtures, at 500-550 deg. C for V{sub 2}O{sub 5}-C mixtures and at 600-1000 deg. C for (Fe-V)-C mixtures. The milled and heat treated powders are characterized by SEM, EDAX, XRD, and BET techniques. Nanostructured TiC has been successfully synthesized under suitable processing conditions. However, carbides of vanadium is unidentified even though possibilities of V{sub 2}O{sub 5}-C reaction are indicated with an extent of induced amorphism in the powder mixture. Density, specific surface area and particle size of the milled and heat treated mixtures are correlated with heat treatment temperatures. Similar attempts are also made to synthesize vanadium carbides from industrial grade Fe-V.

  2. Influence of acid volatile sulfide and metal concentrations on metal bioavailability to marine invertebrates in contaminated sediments

    USGS Publications Warehouse

    Lee, B.-G.; Lee, J.-S.; Luoma, S.N.; Choi, H.J.; Koh, C.-H.

    2000-01-01

    An 18-day microcosm study was conducted to evaluate the influence of acid volatile sulfides (AVS) and metal additions on bioaccumulation from sediments of Cd, Ni, and Zn in two clams (Macoma balthica and Potamocorbula amurensis) and three marine polychaetes (Neanthes arenaceodentata, Heteromastus filiformis, and Spiophanes missionensis). Manipulation of AVS by oxidation of naturally anoxic sediments allowed use of metal concentrations typical of nature and evaluation of processes important to chronic metal exposure. A vertical sediment column similar to that often found in nature was used to facilitate realistic biological behavior. Results showed that AVS or porewater (PW) metals controlled bioaccumulation in only 2 of 15 metal-animal combinations. Bioaccumulation of all three metals by the bivalves was related significantly to metal concentrations extracted from sediments (SEM) but not to [SEM - AVS] or PW metals. SEM predominantly influenced bioaccumulation of Ni and Zn in N. arenaceodentata, but Cd bioaccumulation followed PW Cd concentrations. SEM controlled tissue concentrations of all three metals in H. filiformis and S. missionensis, with minor influences from metal-sulfide chemistry. Significant bioaccumulation occurred when SEM was only a small fraction of AVS in several treatments. Three factors appeared to contribute to the differences between these bioaccumulation results and the results from toxicity tests reported previously: differences in experimental design, dietary uptake, and biological attributes of the species, including mode and depth of feeding.An 18-day microcosm study was conducted to evaluate the influence of acid volatile sulfides (AVS) and metal additions on bioaccumulation from sediments of Cd, Ni, and Zn in two clams (Macoma balthica and Potamocorbula amurensis) and three marine polychaetes (Neanthes arenaceodentata, Heteromastus filiformis, and Spiophanes missionensis). Manipulation of AVS by oxidation of naturally anoxic sediments

  3. Characterization of amorphous silicon carbide and silicon carbonitride thin films synthesized by polymer-source chemical vapor deposition. Mechanical structural and metal-interface properties

    NASA Astrophysics Data System (ADS)

    Awad, Yousef

    Amorphous silicon carbide (a-SiC) and silicon carbonitride thin films have been deposited onto a variety of substrates by Polymer-Source Chemical Vapor Deposition (PS-CVD). The interfacial interaction between the a-SiC films and several substrates including silicon, SiO2, Si3N 4, Cr, Ti and refractory metal-coated silicon has been studied. The effect of thermal annealing on the structural and mechanical properties of the prepared films has been discussed in detail. The composition and bonding states are uniquely characterized with respect to the nitrogen atomic percentage introduced into the a-SiCN:H films. Capacitance-voltage (C-V) measurements were systematically used to evaluate the impurity level of the deposited a-SiC films. The chemical bonding of the films was systematically examined by means of Fourier transform infrared spectroscopy (FTIR). In addition, elastic recoil detection (ERD) and X-ray photoelectron spectroscopy (XPS) techniques were used to determine the elemental composition of the films and of their interface with substrates, while X-ray reflectivity measurements (XRR) were used to account for the film density. Spectral deconvolution was used to extract the individual components of the FTIR and XPS spectra. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were also employed to characterize the surface morphology of the films. In addition, their mechanical properties [(hardness (H) and Young's modulus (E)] were investigated by using the nanoindentation technique. The impurity levels of the a-SiC films were found to be clearly correlated with the nature of the underlying substrates. The Pt-Rh and TiN-coated Si substrates were shown to lead to the lowest impurity level (˜ 1x10 13 cm-3) in the PS-CVD grown a-SiC films, while Cr and Ti-coated Si substrates induced much higher impurity concentrations. Such high impurity levels were shown to be a consequence of a strong metallic diffusion of the metallic species (Cr or Ti). In

  4. Ligand-enhanced electrokinetic remediation of metal-contaminated marine sediments with high acid buffering capacity.

    PubMed

    Masi, Matteo; Iannelli, Renato; Losito, Gabriella

    2016-06-01

    The suitability of electrokinetic remediation for removing heavy metals from dredged marine sediments with high acid buffering capacity was investigated. Laboratory-scale electrokinetic remediation experiments were carried out by applying two different voltage gradients to the sediment (0.5 and 0.8 V/cm) while circulating water or two different chelating agents at the electrode compartments. Tap water, 0.1 M citric acid and 0.1 M ethylenediaminetetraacetic acid (EDTA) solutions were used respectively. The investigated metals were Zn, Pb, V, Ni and Cu. In the unenhanced experiment, the acid front could not propagate due to the high acid buffering capacity of the sediments; the production of OH(-) ions at the cathode resulted in a high-pH environment causing the precipitation of CaCO3 and metal hydroxides. The use of citric acid prevented the formation of precipitates, but solubilisation and mobilisation of metal species were not sufficiently achieved. Metal removal was relevant when EDTA was used as the conditioning agent, and the electric potential was raised up to 0.8 V/cm. EDTA led to the formation of negatively charged complexes with metals which migrated towards the anode compartment by electromigration. This result shows that metal removal from sediments with high acid buffering capacity may be achieved by enhancing the electrokinetic process by EDTA addition when the acidification of the medium is not economically and/or environmentally sustainable. PMID:26490900

  5. The crystallization of metal soaps and fatty acids in oil paint model systems.

    PubMed

    Hermans, Joen J; Keune, Katrien; van Loon, Annelies; Iedema, Piet D

    2016-04-28

    The formation and crystallization of metal soaps in oil paint layers is an important issue in the conservation of oil paintings. The chemical reactions and physical processes that are involved in releasing metal ions from pigments and fatty acids from the oil binder to form crystalline metal soap deposits have so far remained poorly understood. We have used a combination of differential scanning calorimetry (DSC) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) on model mixtures of palmitic acid, lead palmitate or zinc palmitate and linseed oil to study the transition from amorphous material to crystalline fatty acid or metal soap. This transition forms the final stage in the cascade of processes leading to metal soap-related oil paint degradation. Palmitic acid as well as the metal soaps showed nearly ideal solubility behavior. However, it was found that, near room temperature, both lead and zinc palmitate are practically insoluble in both liquid and partially polymerized linseed oil. Interestingly, the rate of metal soap and fatty acid crystallization decreased rapidly with the degree of linseed oil polymerization, possibly leading to systems where metal soaps are kinetically trapped in a semi-crystalline state. To explain the various morphologies of metal soap aggregates observed in oil paint layers, it is proposed that factors affecting the probability of crystal nucleation and the rate of crystal growth play a crucial role, like exposure to heat or cleaning solvents and the presence of microcracks. PMID:27039879

  6. Microwave sintering of boron carbide

    DOEpatents

    Blake, R.D.; Katz, J.D.; Petrovic, J.J.; Sheinberg, H.

    1988-06-10

    A method for forming boron carbide into a particular shape and densifying the green boron carbide shape. Boron carbide in powder form is pressed into a green shape and then sintered, using a microwave oven, to obtain a dense boron carbide body. Densities of greater than 95% of theoretical density have been obtained. 1 tab.

  7. Ternary rare earth metal boride carbides containing two-dimensional boron carbon network: The crystal and electronic structure of R2B4C (R=Tb, Dy, Ho, Er)

    NASA Astrophysics Data System (ADS)

    Babizhetskyy, Volodymyr; Zheng, Chong; Mattausch, Hansjürgen; Simon, Arndt

    2007-12-01

    The ternary rare earth boride carbides R2B4C (R=Tb, Dy, Ho, Er) have been synthesized by reacting the elements at temperatures between 1800 and 2000K. The crystal structure of Dy2B4C has been determined from single-crystal X-ray diffraction data. It crystallizes in a new structure type in the orthorhombic space group Immm (a=3.2772(6) Å, b=6.567(2) Å, c=7.542(1) Å, Z=2, R1=0.035 (wR2=0.10) for 224 reflections with Io>2σ(Io)). Boron atoms form infinite chains of fused B6 rings in [100] joined with carbon atoms into planar, two-dimensional networks which alternate with planar sheets of rare earth metal atoms. The electronic structure of Dy2B4C was also analyzed using the tight-binding extended Hückel method.

  8. Method for homogenizing alloys susceptible to the formation of carbide stringers and alloys prepared thereby

    DOEpatents

    Braski, David N.; Leitnaker, James M.

    1980-01-01

    A novel fabrication procedure prevents or eliminates the reprecipitation of segregated metal carbides such as stringers in Ti-modified Hastelloy N and stainless steels to provide a novel alloy having carbides uniformly dispersed throughout the matrix. The fabrication procedure is applicable to other alloys prone to the formation of carbide stringers. The process comprises first annealing the alloy at a temperature above the single phase temperature for sufficient time to completely dissolve carbides and then annealing the single phase alloy for an additional time to prevent the formation of carbide stringers upon subsequent aging or thermomechanical treatment.

  9. Mechanisms of Radionuclide-Hyroxycarboxylic Acid Interactions for Decontamination of Metallic Surfaces

    SciTech Connect

    A.J. Francis; C.J. Dodge; J.B. Gillow; G.P. Halada; C.R. Clayton

    2002-04-24

    Is this EMSP program we investigated the key fundamental issues involved in the use of simple and safe methods for the removal of radioactive contamination from equipment and facilities using hydroxycarboxylic acids. Specifically, we investigate (i) the association of uranium with various iron oxides commonly formed on corroding plain carbon steel surfaces, (ii) the association of uranium with corroding metal coupons under a variety of conditions, and (iii) the decontamination of the uranium contaminated metal coupons by citric acid or citric acid formulations containing oxalic acid and hydrogen peroxide.

  10. METHOD FOR PRODUCING CEMENTED CARBIDE ARTICLES

    DOEpatents

    Onstott, E.I.; Cremer, G.D.

    1959-07-14

    A method is described for making molded materials of intricate shape where the materials consist of mixtures of one or more hard metal carbides or oxides and matrix metals or binder metals thereof. In one embodiment of the invention 90% of finely comminuted tungsten carbide powder together with finely comminuted cobalt bonding agent is incorporated at 60 deg C into a slurry with methyl alcohol containing 1.5% paraffin, 3% camphor, 3.5% naphthalene, and 1.8% toluene. The compact is formed by the steps of placing the slurry in a mold at least one surface of which is porous to the fluid organic system, compacting the slurry, removing a portion of the mold from contact with the formed object and heating the formed object to remove the remaining organic matter and to sinter the compact.

  11. Antimicrobial Activity of Metal & Metal Oxide Nanoparticles Interfaced With Ligand Complexes Of 8-Hydroxyquinoline And α-Amino Acids

    NASA Astrophysics Data System (ADS)

    Bhanjana, Gaurav; Kumar, Neeraj; Thakur, Rajesh; Dilbaghi, Neeraj; Kumar, Sandeep

    2011-12-01

    Antimicrobial nanotechnology is a recent addition to the fight against disease causing organisms, replacing heavy metals and toxins. In the present work, mixed ligand complexes of metals like zinc, silver etc. and metal oxide have been synthesized using 8-hydroxyquinoline (HQ) as a primary ligand and N-and/O-donor amino acids such as L-serine, L-alanine, glycine, cysteine and histidine as secondary ligands. These complexes were characterized using different spectroscopic techniques. The complexes were tested for antifungal and antibacterial activity by using agar well diffusion bioassay.

  12. Zirconium carbide recrystallization

    SciTech Connect

    Lanin, A.G.; Erin, O.N.; Sul'Yanov, S.N.; Turchin, V.N.

    1986-02-01

    This paper studies the primary recrystallization process of the sintered polycrystalline zirconium carbide with a composition of ZrC /SUB 0.98/ . The properties of zirconium carbide samples deformed under compression are presented; the selected degree of deformation ensures a lower scatter of grain sizes at relative error of +/- 5% in the final deformation measurement. The established mechanisms of structural changes in zirconium carbide during plastic deformation and subsequent high temperature treatment indicate the possibility of using thermomechanical methods for the direct control of the structure of these mechanical methods for the direct control of the structure of these and obviously othe group IV and V carbides obtained by powder metallurgical methods.

  13. Survival of the fittest: overcoming oxidative stress at the extremes of Acid, heat and metal.

    PubMed

    Maezato, Yukari; Blum, Paul

    2012-01-01

    The habitat of metal respiring acidothermophilic lithoautotrophs is perhaps the most oxidizing environment yet identified. Geothermal heat, sulfuric acid and transition metals contribute both individually and synergistically under aerobic conditions to create this niche. Sulfuric acid and metals originating from sulfidic ores catalyze oxidative reactions attacking microbial cell surfaces including lipids, proteins and glycosyl groups. Sulfuric acid also promotes hydrocarbon dehydration contributing to the formation of black "burnt" carbon. Oxidative reactions leading to abstraction of electrons is further impacted by heat through an increase in the proportion of reactant molecules with sufficient energy to react. Collectively these factors and particularly those related to metals must be overcome by thermoacidophilic lithoautotrophs in order for them to survive and proliferate. The necessary mechanisms to achieve this goal are largely unknown however mechanistics insights have been gained through genomic studies. This review focuses on the specific role of metals in this extreme environment with an emphasis on resistance mechanisms in Archaea. PMID:25371104

  14. Survival of the Fittest: Overcoming Oxidative Stress at the Extremes of Acid, Heat and Metal

    PubMed Central

    Maezato, Yukari; Blum, Paul

    2012-01-01

    The habitat of metal respiring acidothermophilic lithoautotrophs is perhaps the most oxidizing environment yet identified. Geothermal heat, sulfuric acid and transition metals contribute both individually and synergistically under aerobic conditions to create this niche. Sulfuric acid and metals originating from sulfidic ores catalyze oxidative reactions attacking microbial cell surfaces including lipids, proteins and glycosyl groups. Sulfuric acid also promotes hydrocarbon dehydration contributing to the formation of black “burnt” carbon. Oxidative reactions leading to abstraction of electrons is further impacted by heat through an increase in the proportion of reactant molecules with sufficient energy to react. Collectively these factors and particularly those related to metals must be overcome by thermoacidophilic lithoautotrophs in order for them to survive and proliferate. The necessary mechanisms to achieve this goal are largely unknown however mechanistics insights have been gained through genomic studies. This review focuses on the specific role of metals in this extreme environment with an emphasis on resistance mechanisms in Archaea. PMID:25371104

  15. Interaction of metal ions and amino acids - Possible mechanisms for the adsorption of amino acids on homoionic smectite clays

    NASA Technical Reports Server (NTRS)

    Gupta, A.; Loew, G. H.; Lawless, J.

    1983-01-01

    A semiempirical molecular orbital method is used to characterize the binding of amino acids to hexahydrated Cu(2+) and Ni(2+), a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays. Five alpha-amino acids, beta-alanine, and gamma-aminobutyric acid were used to investigate the metal ion and amino acid specificity in binding. It was assumed that the alpha, beta, and gamma-amino acids would bind as bidentate anionic ligands, forming either 1:1 or 1:2 six-coordinated five, six, and seven-membered-ring chelate complexes, respectively. Energies of complex formation, optimized geometries, and electron and spin distribution were determined; and steric constraints of binding of the amino acids to the ion-exchanged cations in the interlamellar spacing of a clay were examined. Results indicate that hexahydrated Cu(2+) forms more stable complexes than hexahydrated Ni(2+) with all the amino acids studied. However, among these amino acids, complex formation does not favor the adsorption of the biological subset. Calculated energetics of complex formation and steric constraints are shown to predict that 1:1 rather than 1:2 metal-amino acid complexes are generally favored in the clay.

  16. Computational scheme for the prediction of metal ion binding by a soil fulvic acid

    USGS Publications Warehouse

    Marinsky, J.A.; Reddy, M.M.; Ephraim, J.H.; Mathuthu, A.S.

    1995-01-01

    The dissociation and metal ion binding properties of a soil fulvic acid have been characterized. Information thus gained was used to compensate for salt and site heterogeneity effects in metal ion complexation by the fulvic acid. An earlier computational scheme has been modified by incorporating an additional step which improves the accuracy of metal ion speciation estimates. An algorithm is employed for the prediction of metal ion binding by organic acid constituents of natural waters (once the organic acid is characterized in terms of functional group identity and abundance). The approach discussed here, currently used with a spreadsheet program on a personal computer, is conceptually envisaged to be compatible with computer programs available for ion binding by inorganic ligands in natural waters.

  17. Selective exchange of divalent transition metal ions in cryptomelane-type manganic acid with tunnel structure

    SciTech Connect

    Tsuji, M. ); Komarneni, S. )

    1993-03-01

    The ion-exchange selectivity of divalent transition metal ions on cryptomelane-type manganic acid (CMA) with tunnel structure has been studied using the distribution coefficients ([ital K][sub [ital d

  18. Steel--Project Fact Sheet: Recycling Acid and Metal Salts from Pickling Liquors

    SciTech Connect

    Poole, L.; Recca, L.

    1999-01-14

    Regenerating hydrochloric acids from metal finishing pickling baths reduces costs, wastes, and produces a valuable by-product--ferrous sulfate. Order your copy of this OIT project fact sheet and learn more about how your company can benefit.

  19. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals. Quarterly technical progress report, January 1--March 31, 1995

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Pride, J.D.; Howard, J.B.; Tester, J.W.; Peters, W.A.

    1995-05-01

    The methane plasma stabilization problem was resolved with the reconfiguration of the DC power supply to give a higher open circuit voltage to enable operation of the arc at higher voltage levels and with the installation of a solenoid around the plasma reactor to magnetically rotate the are. Cathode tip erosion problems were encountered with the 1/4-inch graphite and tungsten tips which necessitated a redesign of the plasma reactor. The new plasma reactor consists of an enlarged 3/4-inch O.D. graphite tip to reduce current density and a 1-inch I.D. graphite anode. Products from MgO/CH{sub 4} scoping runs in the redesigned reactor under conditions of excess MgO gave strong indications that a breakthrough has finally been achieved i.e. that synthesis of magnesium carbides from MgO and methane in the arc discharge reactor has been demonstrated. Significant quantities of hydrocarbons, primarily C{sub 3}H{sub 4} and C{sub 2}H{sub 2}, were detected in the headspace above hydrolyzed solid samples by GC analysis. In one run, solids glowed upon exposure to the atmosphere, strongly suggesting carbide reaction with moisture in the air, exothermically forming acetylenes which ignited instantaneously in the presence of oxygen and elevated temperatures arising from localized heat-up of the specimens.

  20. Acid Solutions for Etching Corrosion-Resistant Metals

    NASA Technical Reports Server (NTRS)

    Simmons, J. R.

    1982-01-01

    New study characterized solutions for etching austenitic stainless steels, nickel-base alloys, and titanium alloys (annealed). Solutions recommended for use remove at least 0.4 mil of metal from surface in less than an hour. Solutions do not cause intergranular attack on metals for which they are effective, when used under specified conditions.

  1. Transition-Metal-Free Stereospecific Cross-Coupling with Alkenylboronic Acids as Nucleophiles.

    PubMed

    Li, Chengxi; Zhang, Yuanyuan; Sun, Qi; Gu, Tongnian; Peng, Henian; Tang, Wenjun

    2016-08-31

    We herein report a transition-metal-free cross-coupling between secondary alkyl halides/mesylates and aryl/alkenylboronic acid, providing expedited access to a series of nonchiral/chiral coupling products in moderate to good yields. Stereospecific SN2-type coupling is developed for the first time with alkenylboronic acids as pure nucleophiles, offering an attractive alternative to the stereospecific transition-metal-catalyzed C(sp(2))-C(sp(3)) cross-coupling. PMID:27515390

  2. Distribution of trace impurities of metals during their adsorption from solutions of phosphoric acid

    SciTech Connect

    Toranov, A.N.; Evseeva, N.K.; Kremenskaya, I.N.

    1986-09-01

    The phase distribution of trace impurities of metals between solutions of phosphoric acid and a polymer adsorbent based on a copolymer of styrene with divinylbenzene, impregnated with di-2-ethylhexyldithiophosphoric acid, was investigated. The influence of the composition of the aqueous and solid phases on the distribution coefficients of trace impurities of metals is discussed. It was shown that the coefficients of interfacial distribution in the case of adsorption by an impregnated adsorbent is higher than in the case of liquid extraction.

  3. Electrokinetic remediation. II. Amphoteric metals and enhancement with a weak acid

    SciTech Connect

    Wilson, D.J.; Rodriguez-Maroto, J.M.; Gomez-Lahoz, C.

    1995-09-01

    A one-dimensional model is developed for the electrokinetic treatment of aquifers contaminated with an ionic salt. Electrokinetic removal of amphoteric metals such as zinc and lead is simulated. The use of a weak acid (acetic acid) to neutralize a portion of the OH{sup {minus}} generated electrolytically in the cathode compartment is explored in connection with the electrokinetic removal of nonamphoteric metals such as copper and cadmium.

  4. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    SciTech Connect

    Hagaman, Edward {Ed} W; Chen, Banghao; Jiao, Jian; Parsons, Williams

    2012-01-01

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  5. n-hydrocarbons conversions over metal-modified solid acid catalysts

    NASA Astrophysics Data System (ADS)

    Zarubica, A.; Ranđelović, M.; Momčilović, M.; Radulović, N.; Putanov, P.

    2013-12-01

    The quality of a straight-run fuel oil can be improved if saturated n-hydrocarbons of low octane number are converted to their branched counterparts. Poor reactivity of traditional catalysts in isomerization reactions imposed the need for the development of new catalysts among which noble metal promoted acid catalysts, liquid and/or solid acid catalysts take a prominent place. Sulfated zirconia and metal promoted sulfated zirconia exhibit high activity for the isomerization of light alkanes at low temperatures. The present paper highlights the original results which indicate that the modification of sulfated zirconia by incorporation of metals (platinum and rhenium) significantly affects catalytic performances in n-hydrocarbon conversion reactions. Favourable activity/selectivity of the promoted sulfated zirconia depends on the crystal phase composition, critical crystallites sizes, platinum dispersion, total acidity and type of acidity. Attention is also paid to the recently developed solid acid catalysts used in other conversion reactions of hydrocarbons.

  6. Influence of organic acids on the transport of heavy metals in soil.

    PubMed

    Schwab, A P; Zhu, D S; Banks, M K

    2008-06-01

    Vegetation historically has been an important part of reclamation of sites contaminated with metals, whether the objective was to stabilize the metals or remove them through phytoremediation. Understanding the impact of organic acids typically found in the rhizosphere would contribute to our knowledge of the impact of plants in contaminated environments. Heavy metal transport in soils in the presence of simple organic acids was assessed in two laboratory studies. In the first study, thin layer chromatography (TLC) was used to investigate Zn, Cd, and Pb movement in a sandy loam soil as affected by soluble organic acids in the rhizosphere. Many of these organic acids enhanced heavy metal movement. For organic acid concentrations of 10mM, citric acid had the highest R(f) values (frontal distance moved by metal divided by frontal distance moved by the solution) for Zn, followed by malic, tartaric, fumaric, and glutaric acids. Citric acid also has the highest R(f) value for Cd movement followed by fumaric acid. Citric acid and tartaric acid enhanced Pb transport to the greatest degree. For most organic acids studied, R(f) values followed the trend Zn>Cd>Pb. Citric acid (10mM) increased R(f) values of Zn and Cd by approximately three times relative to water. In the second study, small soil columns were used to test the impact of simple organic acids on Zn, Cd, and Pb leaching in soils. Citric acid greatly enhanced Zn and Cd movement in soils but had little influence on Pb movement. The Zn and Cd in the effluents from columns treated with 10mM citric acid attained influent metal concentrations by the end of the experiment, but effluent metal concentrations were much less than influent concentrations for citrate <10mM. Exchangeable Zn in the soil columns was about 40% of total Zn, and approximately 80% total Cd was in exchangeable form. Nearly all of the Pb retained by the soil columns was exchangeable. PMID:18482743

  7. Main Group Lewis Acid-Mediated Transformations of Transition-Metal Hydride Complexes.

    PubMed

    Maity, Ayan; Teets, Thomas S

    2016-08-10

    This Review highlights stoichiometric reactions and elementary steps of catalytic reactions involving cooperative participation of transition-metal hydrides and main group Lewis acids. Included are reactions where the transition-metal hydride acts as a reactant as well as transformations that form the metal hydride as a product. This Review is divided by reaction type, illustrating the diverse roles that Lewis acids can play in mediating transformations involving transition-metal hydrides as either reactants or products. We begin with a discussion of reactions where metal hydrides form direct adducts with Lewis acids, elaborating the structure and dynamics of the products of these reactions. The bulk of this Review focuses on reactions where the transition metal and Lewis acid act in cooperation, and includes sections on carbonyl reduction, H2 activation, and hydride elimination reactions, all of which can be promoted by Lewis acids. Also included is a section on Lewis acid-base secondary coordination sphere interactions, which can influence the reactivity of hydrides. Work from the past 50 years is included, but the majority of this Review focuses on research from the past decade, with the intent of showcasing the rapid emergence of this field and the potential for further development into the future. PMID:27164024

  8. Determination of the Molar Volume of Hydrogen from the Metal-Acid Reaction: An Experimental Alternative.

    ERIC Educational Resources Information Center

    de Berg, Kevin; Chapman, Ken

    1996-01-01

    Describes an alternative technique for determining the molar volume of hydrogen from the metal-acid reaction in which the metal sample is encased in a specially prepared cage and a pipette filler is used to fill an inverted burette with water. Eliminates some difficulties encountered with the conventional technique. (JRH)

  9. Method of dissolving metal oxides with di- or polyphosphonic acid and a redundant

    DOEpatents

    Horwitz, Earl P.; Chiarizia, Renato

    1996-01-01

    A method of dissolving metal oxides using a mixture of a di- or polyphosphonic acid and a reductant wherein each is present in a sufficient amount to provide a synergistic effect with respect to the dissolution of metal oxides and optionally containing corrosion inhibitors and pH adjusting agents.

  10. 40 CFR 721.10098 - Disubstituted benzoic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal salt (generic). 721.10098 Section 721.10098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10098 Disubstituted benzoic acid, alkali metal...

  11. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... metal salts. 721.4663 Section 721.4663 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a)...

  12. Ternary rare earth metal boride carbides containing two-dimensional boron-carbon network: The crystal and electronic structure of R{sub 2}B{sub 4}C (R=Tb, Dy, Ho, Er)

    SciTech Connect

    Babizhetskyy, Volodymyr Zheng Chong; Mattausch, Hansjuergen; Simon, Arndt

    2007-12-15

    The ternary rare earth boride carbides R{sub 2}B{sub 4}C (R=Tb, Dy, Ho, Er) have been synthesized by reacting the elements at temperatures between 1800 and 2000K. The crystal structure of Dy{sub 2}B{sub 4}C has been determined from single-crystal X-ray diffraction data. It crystallizes in a new structure type in the orthorhombic space group Immm (a=3.2772(6) A, b=6.567(2) A, c=7.542(1) A, Z=2, R1=0.035 (wR{sub 2}=0.10) for 224 reflections with I{sub o}>2{sigma}(I{sub o})). Boron atoms form infinite chains of fused B{sub 6} rings in [100] joined with carbon atoms into planar, two-dimensional networks which alternate with planar sheets of rare earth metal atoms. The electronic structure of Dy{sub 2}B{sub 4}C was also analyzed using the tight-binding extended Hueckel method. - Graphical abstract: Dy{sub 2}B{sub 4}C crystallizes a new structure type where planar 6{sup 3}-Dy metal atom layers alternate with planar non-metal layers consisting of ribbons of fused B{sub 6} hexagons bridged by carbon atoms. Isostructural analogues with Tb, Ho and Er have also been characterized.

  13. Phase equilibria and distribution constants of metal ions in diantipyryl alkane-organic acid-hydrochloric acid-water systems

    NASA Astrophysics Data System (ADS)

    Degtev, M. I.; Popova, O. N.; Yuminova, A. A.

    2014-08-01

    The ability of antipyrine and its derivatives (diantipyryl alkanes) to form separating systems in the presence of salicylic (sulfosalicylic) acid and hydrochloric acid and water is studied. The optimum volume of the organic phase, the composition of complexes, and the mechanism for the distribution of metal ions are determined, depending on the concentrations of the main components and the salting-out agent. The complex distribution and extraction constants are calculated.

  14. Magneto-Resistance in thin film boron carbides

    NASA Astrophysics Data System (ADS)

    Echeverria, Elena; Luo, Guangfu; Liu, J.; Mei, Wai-Ning; Pasquale, F. L.; Colon Santanta, J.; Dowben, P. A.; Zhang, Le; Kelber, J. A.

    2013-03-01

    Chromium doped semiconducting boron carbide devices were fabricated based on a carborane icosahedra (B10C2H12) precursor via plasma enhanced chemical vapor deposition, and the transition metal atoms found to dope pairwise on adjacent icosahedra site locations. Models spin-polarized electronic structure calculations of the doped semiconducting boron carbides indicate that some transition metal (such as Cr) doped semiconducting boron carbides may act as excellent spin filters when used as the dielectric barrier in a magnetic tunnel junction structure. In the case of chromium doping, there may be considerable enhancements in the magneto-resistance of the heterostructure. To this end, current to voltage curves and magneto-transport measurements were performed in various semiconducting boron carbide both in and out plane. The I-V curves as a function of external magnetic field exhibit strong magnetoresistive effects which are enhanced at liquid Nitrogen temperatures. The mechanism for these effects will be discussed in the context of theoretical calculations.

  15. Process for making silicon carbide reinforced silicon carbide composite

    NASA Technical Reports Server (NTRS)

    Lau, Sai-Kwing (Inventor); Calandra, Salavatore J. (Inventor); Ohnsorg, Roger W. (Inventor)

    1998-01-01

    A process comprising the steps of: a) providing a fiber preform comprising a non-oxide ceramic fiber with at least one coating, the coating comprising a coating element selected from the group consisting of carbon, nitrogen, aluminum and titanium, and the fiber having a degradation temperature of between 1400.degree. C. and 1450.degree. C., b) impregnating the preform with a slurry comprising silicon carbide particles and between 0.1 wt % and 3 wt % added carbon c) providing a cover mix comprising: i) an alloy comprising a metallic infiltrant and the coating element, and ii) a resin, d) placing the cover mix on at least a portion of the surface of the porous silicon carbide body, e) heating the cover mix to a temperature between 1410.degree. C. and 1450.degree. C. to melt the alloy, and f) infiltrating the fiber preform with the melted alloy for a time period of between 15 minutes and 240 minutes, to produce a ceramic fiber reinforced ceramic composite.

  16. Influence of alkaline earth metals on molecular structure of 3-nitrobenzoic acid in comparison with alkali metals effect

    NASA Astrophysics Data System (ADS)

    Samsonowicz, M.; Regulska, E.; Lewandowski, W.

    2011-11-01

    The influence of beryllium, magnesium, calcium, strontium and barium cations on the electronic system of 3-nitrobenzoic acid was studied in comparison with studied earlier alkali metal ions [1]. The vibrational FT-IR (in KBr and ATR techniques) and 1H and 13C NMR spectra were recorded for 3-nitrobenzoic acid and its salts. Characteristic shifts in IR and NMR spectra along 3-nitrobenzoates of divalent metal series Mg → Ba were compared with series of univalent metal Li → Cs salts. Good correlations between the wavenumbers of the vibrational bands in the IR spectra for 3-nitrobenzoates and ionic potential, electronegativity, inverse of atomic mass, atomic radius and ionization energy of metals were found for alkaline earth metals as well as for alkali metals. The density functional (DFT) hybrid method B3LYP with two basis sets: 6-311++G** and LANL2DZ were used to calculate optimized geometrical structures of studied compounds. The theoretical wavenumbers and intensities of IR spectra as well as chemical shifts in NMR spectra were obtained. Geometric aromaticity indices, atomic charges, dipole moments and energies were also calculated. The calculated parameters were compared to experimental characteristic of studied compounds.

  17. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic polycarboxylic acid...

  18. Continuous renal replacement therapy amino acid, trace metal and folate clearance in critically ill children

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We hypothesized that continuous veno-venous hemodialysis (CVVHD) results in amino acid, trace metals, and folate losses, thereby adversely impacting nutrient balance. Critically ill children receiving CVVHD were studied prospectively for 5 days. Blood concentrations, amino acids, copper, zinc, man...

  19. Surface and catalytic properties of acid metal carbons prepared by the sol gel method

    NASA Astrophysics Data System (ADS)

    Aguado-Serrano, J.; Rojas-Cervantes, M. L.; Martín-Aranda, R. M.; López-Peinado, A. J.; Gómez-Serrano, V.

    2006-06-01

    The sol-gel method has been applied for the synthesis of a series of acid metal-carbon xerogels (with M = V, Cr, Mo and Ni) by polymerisation of resorcinol with formaldehyde in the presence of metallic precursors. A blank sample was also prepared without any metal addition. The xerogels were heated in nitrogen at 1000 °C to obtain the pyrolysed products. The samples were characterised by different techniques such as thermal-mass spectrometry analysis, gas physisorption, and mercury porosimetry. In addition, the acid character of the pyrolysed products was tested by the Claisen-Schmidt condensation between benzaldehyde and acetophenone for the formation of chalcones.

  20. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals. Quarterly technical status report, October 1, 1994--December 31, 1994

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Pride, J.D.; Howard, J.B.; Tester, J.W.; Peters, W.A.

    1995-02-01

    Scoping runs with up to 0.125 cfm methane in 1 cfm (ambient temperature) of argon and 12g/min of MgO were performed in October using a graphite anode and tungsten cathode in the new plasma reactor. A GC analysis of the gas sample from the cooling chamber and of the head space gas above the hydrolyzed solid sample revealed the presence of C{sub 3}H{sub 4} and C{sub 2}H{sub 2}, which suggests the formation of magnesium carbide. However, a similar run performed with MgO feeding into a pure argon plasma gave similar results, indicating possible reaction of the graphite electrode with the MgO to form carbides and/or direct formation of C{sub 3}H{sub 4} and C{sub 2}H{sub 2} in the arc. A GC analysis of the gas sample taken from the cooling chamber from a run in an argon plasma without MgO feeding did no yield any C{sub 3}H{sub 4} and C{sub 2}H{sub 2}, suggesting that the MgO powder is hydrated and is a probable hydrogen source. Thus far, the main obstacle to performing a 100% methane/MgO scoping run is the instability of the methane plasma. Two approaches are being taken to address this issue: increasing the open circuit voltage of the power supply to permit operation of an arc at higher voltage levels and magnetically rotating the arc with a solenoid around the plasma reactor. The latter approach is currently being pursued.

  1. A new method for the removal of toxic metal ions from acid-sensitive biomaterial

    SciTech Connect

    Seki, Hideshi; Suzuki, Akira

    1997-06-01

    A new method (competitive adsorption method) for the removal of toxic heavy metals from acid-sensitive biomaterials was proposed and it was applied to the removal of cadmium from the midgut gland (MG) of scallop, Patinopecten yessoensis. Insolubilized humic acid, which has been developed in the laboratory, was used as a competitive adsorbent. A metal-complexation model was used to determine the adsorption characteristics of cadmium onto MG. Furthermore, the model was applied to the competitive adsorption system. The results showed that the competitive adsorption method enabled the simultaneous removal of toxic cadmium from both liquid and MG phase under mild acidic condition (pH 5).

  2. Magnetoresistance in Boron Carbide junctions

    NASA Astrophysics Data System (ADS)

    Day, Ellen; Sokolov, A.; Baruth, A.; Robertson, B. W.; Adenwalla, S.

    2007-03-01

    The properties of thin insulator layers are crucial to the performance of magnetic tunnel junctions. Commercial requirements are a device with a high tunnel magnetoresistance (TMR) with low cost and high stability. At present the vast majority of barriers are made from amorphous Al2O3 and crystalline MgO. The TMR value depends not only on the spin-dependent electronic structure of the electrodes, but on the metal-insulator interface. Oxide-type barriers may suffer from local vacancies and other type of defects, resulting in oxygen diffusion, making the TMR value unstable with time. We present TMR results obtained on a non-oxide barrier, boron carbide (B10C2) for applications in magnetic tunnel junctions. This low Z inorganic material can be grown by plasma enhanced chemical vapor deposition (PECVD) without pinholes in the ultra thin film regime. PECVD grown boron carbide is an excellent dielectric with resistivities in the range of 10^7 ohm-cm, with a band gap that can be adjusted from 0.7 eV to 1.9 eV by altering the boron to carbon ratio and to band gap values well above 2.7 eV by adding phosphorus. This creates a unique opportunity for experimental study of a broad spectrum of phenomena, related to the dielectric properties of the barrier.

  3. Advances in biotreatment of acid mine drainage and biorecovery of metals: 1. Metal precipitation for recovery and recycle.

    PubMed

    Tabak, Henry H; Scharp, Richard; Burckle, John; Kawahara, Fred K; Govind, Rakesh

    2003-12-01

    Acid mine drainage (AMD), an acidic metal-bearing wastewater, poses a severe pollution problem attributed to post mining activities. The metals usually encountered in AMD and considered of concern for risk assessment are arsenic, cadmium, iron, lead, manganese, zinc, copper and sulfate. The pollution generated by abandoned mining activities in the area of Butte, Montana has resulted in the designation of the Silver Bow Creek-Butte Area as the largest Superfund (National Priorities List) site in the U.S. This paper reports the results of bench-scale studies conducted to develop a resource recovery based remediation process for the clean up of the Berkeley Pit. The process utilizes selective, sequential precipitation (SSP) of metals as hydroxides and sulfides, such as copper, zinc, aluminum, iron and manganese, from the Berkeley Pit AMD for their removal from the water in a form suitable for additional processing into marketable precipitates and pigments. The metal biorecovery and recycle process is based on complete separation of the biological sulfate reduction step and the metal precipitation step. Hydrogen sulfide produced in the SRB bioreactor systems is used in the precipitation step to form insoluble metal sulfides. The average metal recoveries using the SSP process were as follows: aluminum (as hydroxide) 99.8%, cadmium (as sulfide) 99.7%, cobalt (as sulfide) 99.1% copper (as sulfide) 99.8%, ferrous iron (sulfide) 97.1%, manganese (as sulfide) 87.4%, nickel (as sulfide) 47.8%, and zinc (as sulfide) 100%. The average precipitate purity for metals, copper sulfide, ferric hydroxide, zinc sulfide, aluminum hydroxide and manganese sulfide were: 92.4, 81.5, 97.8, 95.6, 92.1 and 75.0%, respectively. The final produced water contained only calcium and magnesium and both sulfate and sulfide concentrations were below usable water limits. Water quality of this agriculturally usable water met the EPA's gold standard criterion. PMID:14669873

  4. Effects of environmental hypercapnia and metal (Cd and Cu) exposure on acid-base and metal homeostasis of marine bivalves.

    PubMed

    Ivanina, Anna V; Hawkins, Chelsea; Beniash, Elia; Sokolova, Inna M

    2015-01-01

    Elevated CO2 levels reduce seawater pH and may affect bioavailability of trace metals in estuaries. We studied the interactive effects of common metal pollutants (50 μg l(-1) Cd or Cu) and PCO2 (~395, 800 and 2000 μatm) on metal levels, intracellular pH, expression of metal binding proteins and stress biomarkers in estuarine bivalves Crassostrea virginica (oysters) and Mercenaria mercenaria (hard clams). Cd (but not Cu or hypercapnia) exposure affected the acid-base balance of hemocytes resulting in elevated intracellular pH. Cd and Cu exposure led to the increase in the tissue metal burdens, and metal accumulation was reduced by elevated PCO2 in the mantle but not hemocytes. No change was found in the intracellular free Cd(2+), Cu(2+) or Fe(2+) during Cu or Cd exposure indicating that these metals are bound to intracellular ligands. Free Zn(2+) content in oyster hemocytes was suppressed by Cd and Cu exposure and below the detection limits in clam hemocytes, which went hand-in-hand with the elevated mRNA expression of metallothioneins and ferritin in Cd- and Cu-exposed bivalves, enhanced by hypercapnia. The metal-binding and antioxidant mechanisms of oysters and clams were sufficient to effectively maintain intracellular redox status, even though metal exposure combined with moderate hypercapnia (~800 μatm PCO2) led to the elevated production of reactive oxygen species in hemocytes. Overall, while hypercapnia modulates metal accumulation, binding capacity and oxidative stress in estuarine bivalves, the physiological effects of elevated CO2 are mild compared to the effects of other common stressors. PMID:26008775

  5. Predicting the toxicity of metal-contaminated field sediments using interstitial concentration of metals and acid-volatile sulfide normalizations

    SciTech Connect

    Hansen, D.J.; Berry, W.J.; Mahony, J.D.

    1996-12-01

    The authors investigated the utility of interstitial water concentrations of metals and simultaneously extracted metal/acid-volatile sulfide (SEM/AVS) ratios to explain the biological availability of sediment-associated divalent metals to benthic organisms exposed in the laboratory to sediments from five saltwater and four freshwater locations in the US, Canada, and China. The amphipod Ampelisca abdita or the polychaete Neanthes arenaceodentata were exposed to 70 sediments from the five saltwater locations, and the amphipod Hyalella azteca or the oligochaete Lumbriculus variegatus were exposed to 55 sediments from four freshwater locations in 10-d lethality tests. Almost complete absence of toxicity in spiked sediments and field sediments where metals were the only known source of contamination and where interstitial water toxic units (IWTUs) were < 0.5 indicates that toxicity associated with sediments having SEM/AVS ratios < 1.0 from two saltwater locations in industrial harbors was not metals-related as these sediments contained <0.5 IWTU. Metals-associated toxicity was absent in 100% of sediments from the remaining three saltwater field locations, where metals were the only known source of contamination and SEM/AVS ratios were {le} 1.0. Two-thirds of 45 sediments from seven saltwater and freshwater field locations having both IWTUs > 0.5 (55%) were used alone. The difference between the molar concentrations of SEM and AVS (SEM-AVS) can provide important insight into the extent of additional available binding capacity, the magnitude by which AVS binding has been exceeded, and, when organism response is considered, the potential magnitude of importance of other metal binding phases. SEM-AVS should be used instead of SEM/AVS ratios as a measure of metals availability. In published experiments with both metal-spiked and field sediments, SEM-AVS and IWTUs accurately identified absence of sediment toxicity and with less accuracy identified the presence of toxicity.

  6. Improved toughness of silicon carbide

    NASA Technical Reports Server (NTRS)

    Palm, J. A.

    1976-01-01

    Impact energy absorbing layers (EALs) comprised of partially densified silicon carbide were formed in situ on fully sinterable silicon carbide substrates. After final sintering, duplex silicon carbide structures resulted which were comprised of a fully sintered, high density silicon carbide substrate or core, overlayed with an EAL of partially sintered silicon carbide integrally bonded to its core member. Thermal cycling tests proved such structures to be moderately resistant to oxidation and highly resistant to thermal shock stresses. The strength of the developed structures in some cases exceeded but essentially it remained the same as the fully sintered silicon carbide without the EAL. Ballistic impact tests indicated that substantial improvements in the toughness of sintered silicon carbide were achieved by the use of the partially densified silicon carbide EALs.

  7. Dissolved Divalent Metal and pH Effects on Amino Acid Polymerization: A Thermodynamic Evaluation

    NASA Astrophysics Data System (ADS)

    Kitadai, Norio

    2016-06-01

    Polymerization of amino acids is a fundamentally important step for the chemical evolution of life. Nevertheless, its response to changing environmental conditions has not yet been well understood because of the lack of reliable quantitative information. For thermodynamics, detailed prediction over diverse combinations of temperature and pH has been made only for a few amino acid-peptide systems. This study used recently reported thermodynamic dataset for the polymerization of the simplest amino acid "glycine (Gly)" to its short peptides (di-glycine and tri-glycine) to examine chemical and structural characteristics of amino acids and peptides that control the temperature and pH dependence of polymerization. Results showed that the dependency is strongly controlled by the intramolecular distance between the amino and carboxyl groups in an amino acid structure, although the side-chain group role is minor. The polymerization behavior of Gly reported earlier in the literature is therefore expected to be a typical feature for those of α-amino acids. Equilibrium calculations were conducted to examine effects of dissolved metals as a function of pH on the monomer-polymer equilibria of Gly. Results showed that metals shift the equilibria toward the monomer side, particularly at neutral and alkaline pH. Metals that form weak interaction with Gly (e.g., Mg2+) have no noticeable influence on the polymerization, although strong interaction engenders significant decrease of the equilibrium concentrations of Gly peptides. Considering chemical and structural characteristics of Gly and Gly peptides that control their interactions with metals, it can be expected that similar responses to the addition of metals are applicable in the polymerization of neutral α-amino acids. Neutral and alkaline aqueous environments with dissolved metals having high affinity with neutral α-amino acids (e.g., Cu2+) are therefore not beneficial places for peptide bond formation on the primitive

  8. Silicon carbide thyristor

    NASA Technical Reports Server (NTRS)

    Edmond, John A. (Inventor); Palmour, John W. (Inventor)

    1996-01-01

    The SiC thyristor has a substrate, an anode, a drift region, a gate, and a cathode. The substrate, the anode, the drift region, the gate, and the cathode are each preferably formed of silicon carbide. The substrate is formed of silicon carbide having one conductivity type and the anode or the cathode, depending on the embodiment, is formed adjacent the substrate and has the same conductivity type as the substrate. A drift region of silicon carbide is formed adjacent the anode or cathode and has an opposite conductivity type as the anode or cathode. A gate is formed adjacent the drift region or the cathode, also depending on the embodiment, and has an opposite conductivity type as the drift region or the cathode. An anode or cathode, again depending on the embodiment, is formed adjacent the gate or drift region and has an opposite conductivity type than the gate.

  9. An Experiment on Isomerism in Metal-Amino Acid Complexes.

    ERIC Educational Resources Information Center

    Harrison, R. Graeme; Nolan, Kevin B.

    1982-01-01

    Background information, laboratory procedures, and discussion of results are provided for syntheses of cobalt (III) complexes, I-III, illustrating three possible bonding modes of glycine to a metal ion (the complex cations II and III being linkage/geometric isomers). Includes spectrophotometric and potentiometric methods to distinguish among the…

  10. Waste acid/metal solution reduction and recovery by vacuum distillation

    SciTech Connect

    Jones, E.O.; Wilcox, W.A.; Johnson, N.T.; Bowdish, F.W.

    1995-07-01

    Processes involving distillation under reduced pressure were developed at the Pacific Northwest Laboratory several years ago to recover spent acid solutions generated during the manufacture of nuclear fuel for the N-Reactor at the Hanford site. Following construction and testing of a pilot-plant, the technology was licensed to Viatec Recovery Systems, Inc. for commercialization. The technology developed included specialized distillation and rectification of volatile acids, removal of water and/or volatile acid from sulfuric acid, and precipitation of salts. A key feature of the Waste Acid Detoxification and Reclamation (WADR) technology is the development and use of advanced thermoplastic and fluoropolymer materials of construction in all critical process equipment. The technology was then expanded to include crystallization to recover metal salts for possible reuse. Economic and environmental advantages of the procedures include recovery of acids for reuse, simplification or elimination of the disposal of waste solutions, and possible recovery of metals. Industries expected to benefit from such applications include galvanizing, electroplating, sand leaching and any where metals are cleaned in acid solutions. Currently a modular system has been assembled for recovery of several different spent acid solutions.

  11. Models of metal binding structures in fulvic acid from the Suwannee River, Georgia

    SciTech Connect

    Leenheer, J.A.; Brown, G.K.; Cabaniss, S.E.; MacCarthy, P.

    1998-08-15

    Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca{sup 2+}, Cd{sup 2+}, Cu{sup 2+}, Ni{sup 2+}, and Zn{sup 2+} ions at pH 6 before and after extensive fractionation that was designed to reveal the nature of metal binding functional groups. The binding constant for Ca{sup 2+} ion had the greatest increase of all the ions in a metal binding fraction that was selected for intensive characterization for the purpose of building quantitative average model structures. The metal binding fraction was characterized by quantitative {sup 13}C NMR, {sup 1}H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that carboxyl groups were clustered in short-chain aliphatic dibasic acid structures. The Ca{sup 2+} binding data suggested that ether-substituted oxysuccinic acid structures are good models for the metal binding sites at pH 6. Structural models were derived based upon oxidation and photolytic rearrangements of cutin, lignin, and tannin precursors. These structural models rich in substituted dibasic acid structures revealed polydentate binding sites with the potential for both inner-sphere and outer-sphere type binding. The majority of the fulvic acid molecule was involved with metal binding rather than a small substructural unit.

  12. Genome Sequence Analysis of the Naphthenic Acid Degrading and Metal Resistant Bacterium Cupriavidus gilardii CR3.

    PubMed

    Wang, Xiaoyu; Chen, Meili; Xiao, Jingfa; Hao, Lirui; Crowley, David E; Zhang, Zhewen; Yu, Jun; Huang, Ning; Huo, Mingxin; Wu, Jiayan

    2015-01-01

    Cupriavidus sp. are generally heavy metal tolerant bacteria with the ability to degrade a variety of aromatic hydrocarbon compounds, although the degradation pathways and substrate versatilities remain largely unknown. Here we studied the bacterium Cupriavidus gilardii strain CR3, which was isolated from a natural asphalt deposit, and which was shown to utilize naphthenic acids as a sole carbon source. Genome sequencing of C. gilardii CR3 was carried out to elucidate possible mechanisms for the naphthenic acid biodegradation. The genome of C. gilardii CR3 was composed of two circular chromosomes chr1 and chr2 of respectively 3,539,530 bp and 2,039,213 bp in size. The genome for strain CR3 encoded 4,502 putative protein-coding genes, 59 tRNA genes, and many other non-coding genes. Many genes were associated with xenobiotic biodegradation and metal resistance functions. Pathway prediction for degradation of cyclohexanecarboxylic acid, a representative naphthenic acid, suggested that naphthenic acid undergoes initial ring-cleavage, after which the ring fission products can be degraded via several plausible degradation pathways including a mechanism similar to that used for fatty acid oxidation. The final metabolic products of these pathways are unstable or volatile compounds that were not toxic to CR3. Strain CR3 was also shown to have tolerance to at least 10 heavy metals, which was mainly achieved by self-detoxification through ion efflux, metal-complexation and metal-reduction, and a powerful DNA self-repair mechanism. Our genomic analysis suggests that CR3 is well adapted to survive the harsh environment in natural asphalts containing naphthenic acids and high concentrations of heavy metals. PMID:26301592

  13. Genome Sequence Analysis of the Naphthenic Acid Degrading and Metal Resistant Bacterium Cupriavidus gilardii CR3

    PubMed Central

    Xiao, Jingfa; Hao, Lirui; Crowley, David E.; Zhang, Zhewen; Yu, Jun; Huang, Ning; Huo, Mingxin; Wu, Jiayan

    2015-01-01

    Cupriavidus sp. are generally heavy metal tolerant bacteria with the ability to degrade a variety of aromatic hydrocarbon compounds, although the degradation pathways and substrate versatilities remain largely unknown. Here we studied the bacterium Cupriavidus gilardii strain CR3, which was isolated from a natural asphalt deposit, and which was shown to utilize naphthenic acids as a sole carbon source. Genome sequencing of C. gilardii CR3 was carried out to elucidate possible mechanisms for the naphthenic acid biodegradation. The genome of C. gilardii CR3 was composed of two circular chromosomes chr1 and chr2 of respectively 3,539,530 bp and 2,039,213 bp in size. The genome for strain CR3 encoded 4,502 putative protein-coding genes, 59 tRNA genes, and many other non-coding genes. Many genes were associated with xenobiotic biodegradation and metal resistance functions. Pathway prediction for degradation of cyclohexanecarboxylic acid, a representative naphthenic acid, suggested that naphthenic acid undergoes initial ring-cleavage, after which the ring fission products can be degraded via several plausible degradation pathways including a mechanism similar to that used for fatty acid oxidation. The final metabolic products of these pathways are unstable or volatile compounds that were not toxic to CR3. Strain CR3 was also shown to have tolerance to at least 10 heavy metals, which was mainly achieved by self-detoxification through ion efflux, metal-complexation and metal-reduction, and a powerful DNA self-repair mechanism. Our genomic analysis suggests that CR3 is well adapted to survive the harsh environment in natural asphalts containing naphthenic acids and high concentrations of heavy metals. PMID:26301592

  14. Simulation of the influence of EDTA on the sorption of heavy metals by humic acids

    NASA Astrophysics Data System (ADS)

    Kropacheva, T. N.; Didik, M. V.; Kornev, V. I.

    2015-04-01

    The results of mathematical simulation of sorption equilibria with the participation of divalent cations of heavy metals (HMs), chelant (EDTA), and insoluble forms of humic acids (HAs) are discussed. It is shown that the formation of chelates of metals with EDTA in solutions results in the decreasing sorption of the metals by humic acids. We also analyzed the effect of the acidity of the medium and the HM: EDTA: HA ratio (in a wide range) on the desorption of metals. The desorbing effect of EDTA on the metals is the highest at pH 3-5 and increases with an increase in the concentration of EDTA and a decrease in the concentration of HAs. With respect to the remobilization of metals under the impact of EDTA, the metal cations can be arranged into the following sequence: Cu(II) > Ni(II) > Pb(II) ≫ Cd(II) > Co(II) > Zn(II). The obtained data have been used to analyze the remobilization / extraction of HMs from soils with a high content of humic substances.

  15. Complexations of polyoligothiophenes films with transition metals, and their use for electrocatalysis of ascorbic acid

    NASA Astrophysics Data System (ADS)

    Maouche, N.; Chelli, S.; Nessark, B.; Aeiyach, S.

    2009-11-01

    Chemically modified electrodes prepared by electropolymerization of oligothiophenes such as: 2,2'-bithiophene (BT), 2,2'-bithiophene-5-carboxylic acid (BTCA) and terthiophene aldehyde (TTCHO) on platinum (Pt) electrodes, in acetonitrile solution containing 0.1 M tetrabutylammonium perchlorate (TBAP) and 0.01 M of monomer, are characterized by cyclic volammetry (CV), and X-ray photoelectron spectroscopy (XPS) measurements. By immersing the prepared modified electrodes in transition metals (Cu2+, Co2+ and Ag+) solutions, the metal ions were complexed with films. The electrochemical response shows clearly, the presence of oxidation and reduction peaks corresponding to metallic couple redox. XPS technique reveal that the films complexed with metal ions and determine the mode of the connection with film's atoms. The obtained polyoligothiophenes-metal modified electrodes exhibited good electrocatalytic properties towards ascorbic acid (AA) oxidation after their complexation with metallic ions. The electrocatalytic response was evaluated by cyclic voltammetry with regard to the film nature, the metallic ion nature, immersion time, ascorbic acid concentration, and other variables. The results reveal that the catalytic activity of Ag+ complexed with BTCA thin-film is the best toward AA oxidation and it can be detected a very low concentration (∼1 μM), of AA in a solution which can be utilized as an efficient electrochemical sensor.

  16. A GREEN CHEMISTRY APPROACH TO PREPARATION OF CORE (FE OR CU)-SHELL (NOBLE METALS) NANOCOMPOSITES USING AQUEOUS ASCORBIC ACID

    EPA Science Inventory

    A greener method to fabricate novel core (Fe or Cu)-shell (noble metals) nanocomposites of transition metals such as Fe and Cu and noble metals such as Au, Pt, Pd, and Ag using aqueous ascorbic acid is described. Transition metal salts such as Cu and Fe were reduced using ascor...

  17. Factors affecting chromium carbide precipitate dissolution during alloy oxidation

    SciTech Connect

    Durham, R.N.; Gleeson, B.; Young, D.J.

    1998-08-01

    Ferrous alloys containing significant volume fractions of chromium carbides were formulated so as to contain an overall chromium level of 15% (by weight) but a nominal metal matrix chromium concentration of only 11%. Their oxidation at 850 C in pure oxygen led to either protective Cr{sub 2}O{sub 3} scale formation accompanied by subsurface carbide dissolution or rapid growth of iron-rich oxide scales associated with rapid alloy surface recession, which engulfed the carbides before they could dissolve. Carbide size was important in austenitic alloys: an as-cast Fe-15Cr-0.5C alloy contained relatively coarse carbides and failed to form a Cr{sub 2}O{sub 3} scale, whereas the same alloy when hot-forged to produce very fine carbides oxidized protectively. In ferritic alloys, however, even coarse carbides dissolved sufficiently rapidly to provide the chromium flux necessary to form and maintain the growth of a Cr{sub 2}O{sub 3} scale, a result attributed to the high diffusivity of the ferrite phase. Small additions of silicon to the as-cast Fe-15Cr-0.5C alloy rendered it ferritic and led to protective cr{sub 2}O{sub 3} growth. However, when the silicon-containing alloy was made austenitic (by the addition of nickel), it still formed a protective Cr{sub 2}O{sub 3} scale, showing that the principal function of silicon was in modifying the scale-alloy interface.

  18. Marsh plant response to metals: Exudation of aliphatic low molecular weight organic acids (ALMWOAs)

    NASA Astrophysics Data System (ADS)

    Rocha, A. Cristina S.; Almeida, C. Marisa R.; Basto, M. Clara P.; Vasconcelos, M. Teresa S. D.

    2016-03-01

    Metal exposure is known to induce the production and secretion of substances, such as aliphatic low molecular weight organic acids (ALMWOAs), into the rhizosphere by plant roots. Knowledge on this matter is extensive for soil plants but still considerably scarce regarding marsh plants roots adapted to high salinity media. Phragmites australis and Halimione portulacoides, two marsh plants commonly distributed in European estuarine salt marshes, were used to assess the response of roots of both species, in terms of ALMWOAs exudation, to Cu, Ni and Cd exposure (isolated and in mixture since in natural environment, they are exposed to mixture of metals). As previous studies were carried out in unrealistic and synthetic media, here a more natural medium was selected. Therefore, in vitro experiments were carried out, with specimens of both marsh plants, and in freshwater contaminated with two different Cu, Ni and Cd concentrations (individual metal and in mixture). Both marsh plants were capable of liberating ALMWOAs into the surrounding medium. Oxalic, citric and maleic acids were found in P. australis root exudate solutions and oxalic and maleic acids in H. portulacoides root exudate solutions. ALMWOA liberation by both plants was plant species and metal-dependent. For instance, Cu affected the exudation of oxalic acid by H. portulacoides and of oxalic and citric acids by P. australis roots. In contrast, Ni and Cd did not stimulate any specific response. Regarding the combination of all metals, H. portulacoides showed a similar response to that observed for Cu individually. However, in the P. australis case, at high metal concentration mixture, a synergetic effect led to the increase of oxalic acid levels in root exudate solution and to a decrease of citric acid liberation. A correlation between ALMWOAs exudation and metal accumulation could not be established. P. australis and H. portulacoides are considered suitable metal phytoremediators of estuarine impacted areas

  19. Analytical electron microscopy study of the high temperature carbide formed in a V-5 Ti-C alloy

    SciTech Connect

    Bruemmer, S.M.; Fluhr, C.P.; Beggs, D.V.; Wert, C.A.; Fraser, H.L.

    1980-05-01

    A finely dispersed high temperature carbide that precipitates at 1000/sup 0/C in a V-5 pct Ti-C alloy has been studied using analytical electron microscopy. The crystal structure has been determined using electron diffraction as B1 (NaCl-type) with a lattice parameter of 4.29A. The carbide develops a habit plane parallel to (001) of the matrix. The orientation relationship between the carbide and the matrix is (010) carbide parallel to (010) matrix, (001) carbide parallel to (101) matrix. The elemental concentrations of the metal constituents of the carbide have been deduced using energy dispersive x-ray spectroscopy and electron energy loss spectroscopy, through examination of core electron excitations. The composition of the carbide is found to be V/sub 11/Ti/sub 39/C/sub 50/, assuming a stoichiometric carbide.

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

    NASA Technical Reports Server (NTRS)

    Tanaka, Hidehiko

    1987-01-01

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

  1. Correlation between organic acid exudation and metal uptake by ectomycorrhizal fungi grown on pond ash in vitro.

    PubMed

    Ray, Prasun; Adholeya, Alok

    2009-04-01

    Experiments were conducted to investigate the effect of coal ash on organic acid exudation and subsequent metal uptake by ectomycorrhizal fungi. Four isolates of ectomycorrhizal fungi namely, Pisolithus tinctorius (EM-1293 and EM-1299), Scleroderma verucosum (EM-1283) and Scleroderma cepa (EM-1233) were grown on pond ash moistened with Modified Melin-Norkans medium in vitro. Exudation of formic acid, malic acid and succinic acid by these fungi were detected by HPLC. Mycelial accumulation of Al, As, Cd, Cr, Ni and Pb by these fungi was assayed by atomic absorption spectrophotometer. Relationship between organic acid exudation and metal uptake was determined using classical multivariate linear regression model. Correlation between organic acid exudation and metal uptake could be substantiated when several metals are considered collectively. The finding supports the widespread role of low molecular weight organic acid as a function of tolerance, when exposed to metals in vitro. PMID:18800194

  2. Remediation and selective recovery of metals from acidic mine waters using novel modular bioreactors.

    PubMed

    Hedrich, Sabrina; Johnson, D Barrie

    2014-10-21

    Mine waters are widely regarded as environmental pollutants, but are also potential sources of valuable metals. Water draining the Maurliden mine (Sweden) is highly acidic (pH 2.3) and rich in zinc (∼ 460 mg L(-1)) and iron (∼ 400 mg L(-1)), and contains smaller concentrations (0.3-49 mg L(-1)) of other transition metals and arsenic. We have developed novel techniques that promote the concurrent amelioration of acidic waste waters and selective recovery of metals, and have used these systems to treat synthetic Maurliden mine water in the laboratory. The two major metals present were removed via controlled biomineralization: zinc as ZnS in a sulfidogenic bioreactor, and iron as schwertmannite by microbial iron oxidation and precipitation of ferric iron. A small proportion (∼ 11%) of the schwertmannite produced was used to remove arsenic as the initial step in the process, and other chalcophilic metals (copper, cadmium and cobalt) were removed (as sulfides) in the stage 1 metal sulfide precipitation reactor. Results from this work have demonstrated that modular biomineralization units can be effective at processing complex mine waters and generating metal products that may be recycled. The economic and environmental benefits of using an integrated biological approach for treating metal-rich mine waters is discussed. PMID:25251612

  3. Synthesis of homo and hetero metal-phosphonate frameworks from bi-functional aminomethylphosphonic acid

    SciTech Connect

    Samanamu, Christian R.; Zamora, Elena Nicole; Montchamp, Jean-Luc; Richards, Anne F.

    2008-06-15

    The reaction between aminomethylphosphonic acid (ampa) and the metal salts of Zn, Cd, Hg, Pb, Ag, and Cu afforded seven metal-phosphonate polymers with unique structural features and includes the synthesis of a bimetallic metal-organic framework (Cu/Ag). The characterization of these metal phosphonates is reported by means of infrared spectroscopy, {sup 1}H-NMR, {sup 31}P-NMR, X-ray crystallography, energy dispersive X-ray (EDX), and thermogravimetric analysis (TGA). Individual structural features are compared based on the preferred coordination mode of ampa and the geometrical requirements for each metallic center that manipulates the structural motif. - Graphical abstract: The synthesis and characterization of polymeric metal phosphonates featuring zinc, cadmium, mercury, lead, and silver phosphonate are described from the reactions of the bi-funtional aminomethylphosphonic acid with the metal precursor in aqueous conditions. These previously undescribed polymers display unusual structural features and include the synthesis of a bimetallic metal-organic framework (Cu/Ag)

  4. [Preparation and spectra of the complexes of the first series transition metals with diphenic acid].

    PubMed

    Wu, Ai-zhi; Wang, Jian-jun; Ren, Yan-wei; Chen, Jing; Li, Jun; Zhang, Feng-xing

    2004-04-01

    The ligand diphenic acid has been synthesized and the corresponding complexes of transition metal Co, Ni and Mn with diphenic acid have been prepared and characterized by the elementary analysis, IR spectra and ultraviolet-visible spectra. The results of IR show that the vas and vs of -CO2- in the complexes are lower than those of ligand diphenic acid, which can be explained by the coordinating between metal and ligand. In addition, compared with the complex IR spectra, the IR spectra of ligand became complicated due to the ligand polymerization through hydrogen bond. The UV-Vis spectra show that the ligand has three absorption peaks at 288, 273 and 270 nm, respectively, and these are slightly shifted in the complexes. Because the metal d-d absorption is weak, only in Co(C14H8O4) x 2H2O there is a d-d absorption at 537 nm. PMID:15766146

  5. How fulvic acid affects heavy metal uptake on the muscovite (001) surface

    NASA Astrophysics Data System (ADS)

    Lee, S.; Fenter, P.; Park, C.; Sturchio, N. C.; Nagy, K.

    2009-12-01

    Understanding the molecular-scale reactions at mineral-solution interfaces is crucial for developing predictive models to assess the transport and bioavailability of dissolved heavy metals in the surface environment. We investigated the vertical distribution of divalent heavy metals (Cu, Zn, Sr, Hg, and Pb) adsorbed at the muscovite (001)-solution interface in the absence and presence of fulvic acid (FA) using interface-specific specular X-ray reflectivity combined with element-specific resonant anomalous X-ray reflectivity with a sub-angstrom resolution. The experimental solutions were prepared using 1-10 mmol/kg metal nitrates with or without 100 mg/kg Elliott Soil Fulvic Acid II or Suwannee River Fulvic Acid from the International Humic Substances Society at pH 2-5.5. Reflectivity data were measured at the Advanced Photon Source, Argonne National Laboratory. In the absence of FA, the results show a complex picture in which there are three distinct adsorbed species that coexist at the interface: classical inner- and outer-sphere complexes plus a third OS fraction that is more broadly distributed at heights farther from the surface than the other species. Systematic trends in cation adsorption show that these three species are correlated and that their partitioning can be explained by thermodynamic equilibrium among these three species which is controlled mainly by cation hydration energy. The presence of dissolved FA modifies heavy metal uptake by two different mechanisms: it can form complexes with metal cations in solution and adsorb on muscovite as metal-organic complexes when the metal has a relatively high affinity for organic matter. In this case, the adsorbed metal cation shows a characteristic broad distribution within the entire film, resulting in formation of a more electron-dense and thicker organic film on muscovite compared to that without metals. Metals with lower organophilicity show that the enhanced metal uptake occurs mainly within the outer

  6. Modelling metal accumulation using humic acid as a surrogate for plant roots.

    PubMed

    Le, T T Yen; Swartjes, Frank; Römkens, Paul; Groenenberg, Jan E; Wang, Peng; Lofts, Stephen; Hendriks, A Jan

    2015-04-01

    Metal accumulation in roots was modelled with WHAM VII using humic acid (HA) as a surrogate for root surface. Metal accumulation was simulated as a function of computed metal binding to HA, with a correction term (E(HA)) to account for the differences in binding site density between HA and root surface. The approach was able to model metal accumulation in roots to within one order of magnitude for 95% of the data points. Total concentrations of Mn in roots of Vigna unguiculata, total concentrations of Ni, Zn, Cu and Cd in roots of Pisum sativum, as well as internalized concentrations of Cd, Ni, Pb and Zn in roots of Lolium perenne, were significantly correlated to the computed metal binding to HA. The method was less successful at modelling metal accumulation at low concentrations and in soil experiments. Measured concentrations of Cu internalized in L. perenne roots were not related to Cu binding to HA modelled and deviated from the predictions by over one order of magnitude. The results indicate that metal uptake by roots may under certain conditions be influenced by conditional physiological processes that cannot simulated by geochemical equilibrium. Processes occurring in chronic exposure of plants grown in soil to metals at low concentrations complicate the relationship between computed metal binding to HA and measured metal accumulation in roots. PMID:25482978

  7. Composition Comprising Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Mehregany, Mehran (Inventor); Zorman, Christian A. (Inventor); Fu, Xiao-An (Inventor); Dunning, Jeremy L. (Inventor)

    2012-01-01

    A method of depositing a ceramic film, particularly a silicon carbide film, on a substrate is disclosed in which the residual stress, residual stress gradient, and resistivity are controlled. Also disclosed are substrates having a deposited film with these controlled properties and devices, particularly MEMS and NEMS devices, having substrates with films having these properties.

  8. Interaction of some metals between marine-origin humic acids and aqueous solutions

    SciTech Connect

    Huljev, D.J.

    1986-08-01

    The interaction of metal ions (carrier-free form) in aquatic medium with humic acids is a complicated process depending on the properties of humic acids (elementary, chemical, and trace element composition), metals studied (valence, charge, chemical form, concentration), and medium used (pH, ionic strength). The use of radionuclides was found to be very suitable for a rapid and precise determination of the distribution coefficient K/sub d/ (ratio of the concentration of a certain trace metal association with a gram of humic acid over the concentration of the same trace metal per milliliter of solution) of the investigated system. Isolated humic acids from offshore sediments from the North Adriatic (Lim channel, near Rovinj, Yugoslavia) were characterized according to their elementary composition, the amount of products of hydrolysis, and the trace elements bound. All experiments were carried out between pH 3 and 5. It was found that conditions usually present at the site where humic acid interacts with metal ions (anaerobic conditions, H/sub 2/S) in brackish (21% S) and standard seawater (38% S) are determined in the pH range 3 to 5. The results of the pick-up (uptake) and replacement (release) experiments are presented as a distribution coefficient (K/sub d/), as a function of contact time. Processes of pick-up and replacement of a number of metals under various physicochemical conditions were investigated and special attention was paid to the influence of salinity. With the increase in NaCl concentration and pH in the system, the fixation of ruthenium, zinc, cobalt, and mercury by humic acids decreased.

  9. Improved toughness of silicon carbide

    NASA Technical Reports Server (NTRS)

    Palm, J. A.

    1975-01-01

    Several techniques were employed to apply or otherwise form porous layers of various materials on the surface of hot-pressed silicon carbide ceramic. From mechanical properties measurements and studies, it was concluded that although porous layers could be applied to the silicon carbide ceramic, sufficient damage was done to the silicon carbide surface by the processing required so as to drastically reduce its mechanical strength. It was further concluded that there was little promise of success in forming an effective energy absorbing layer on the surface of already densified silicon carbide ceramic that would have the mechanical strength of the untreated or unsurfaced material. Using a process for the pressureless sintering of silicon carbide powders it was discovered that porous layers of silicon carbide could be formed on a dense, strong silicon carbide substrate in a single consolidation process.

  10. Methanol conversion over metal salts of 12-tungstophosphoric acid

    SciTech Connect

    Hayashi, H.; Moffat, J.B.

    1983-05-01

    The sodium, boron, calcium, magnesium, zinc, aluminum, and zirconium salts of 12-tungstophosphoric acid have been prepared and characterized using x-ray diffraction, mercury porosimetry, the chemisorption of ammonia, and Hammett indicators. Methanol conversion at 350/sup 0/C and a variety of residence times produced hydrocarbons ranging from C/sub 1/ to C/sub 5/ in amounts which varied with the cation. The more strongly acidic salts produced the higher yields of hydrocarbons. The maximum yield of the major product C/sub 4/ was found with the aluminum salt. The activities were related to the partial change on the oxygen atoms in the various catalysts. 3 figures, 1 table.

  11. Crystallography and metallography of carbides in high alloy steels

    SciTech Connect

    Hetzner, Dennis W. Van Geertruyden, William

    2008-07-15

    The carbides in high carbon, high chromium bearing steels, high chromium carburizing steels, newly developed easily carburizable low carbon, low chromium high speed steels and M62 high speed steel fabricated by powder metal processing were studied. The particular steels evaluated include 440C, BG42. M50-Nil, CHS1, CHS50, Pyrowear 675 , CSS-42L{sup TM} and M62. The morphology and structure of the carbides were evaluated by means of metallography, X-ray diffraction and electron beam backscattered diffraction. The combination of these three techniques has provided new insight into how different carbide morphologies form during processing and the carbide structures that can be expected to be present in components fabricated from these steels by various types of heat treating.

  12. Silicon carbide for high-temperature heat exchangers

    NASA Astrophysics Data System (ADS)

    Penty, R. A.; Bjerklie, J. W.

    1982-02-01

    It is noted that ceramic heat exchangers are now being used industrially in low-pressure applications, such as recuperators and air preheaters, and that serious consideration is being given to using ceramic materials for high-pressure heat exchangers. The principal advantage of using ceramic heat exchangers in the candidate applications is the potential for higher temperature service or increased life over that obtainable with metallic exchangers. Silicon carbide-based materials are now in service in many areas. The use of low-pressure ceramic recuperators constructed of silicon carbide has demonstrated fuel savings exceeding 40% in high-temperature industrial furnaces. At a material temperature of 1375 C, the demonstrated lifetime of some silicon carbide tubes is 12 to 15 months. The availability of silicon carbide materials is discussed, together with properties required for designing reliable heat exchangers. Attention is also given to the usual failure mode encountered in the field.

  13. Poly(isophthalic acid)(ethylene oxide) as a Macromolecular Modulator for Metal-Organic Polyhedra.

    PubMed

    Chen, Teng-Hao; Wang, Le; Trueblood, Jonathan V; Grassian, Vicki H; Cohen, Seth M

    2016-08-01

    A new strategy was developed by using a polymer ligand, poly(isophthalic acid)(ethylene oxide), to modulate the growth of metal-organic polyhedra (MOP) crystals. This macromolecular modulator can effectively control the crystal habit of several different Cu24L24 (L = isophthalic acid derivatives) MOPs. The polymer also directed the formation of MOP structures under reaction conditions that only produce metal-organic frameworks in the absence of modulator. Moreover, the polymer also enabled the deposition of MOP crystals on glass surfaces. This macromolecular modulator strategy provides an innovative approach to control the morphology and assembly of MOP particles. PMID:27400759

  14. Effect of amino acids on the toxicity of heavy metals to phytoplankton

    SciTech Connect

    Kosakowska, A.; Falkowski, L.; Lewandowska, J. )

    1988-05-01

    Heavy metals distribution in the sea water can be indispensable or delitorious for the organisms living in that environment depending on their concentration and speciation. The bioavailability as well as toxicity of the elements are strongly influenced by the organic matter dissolved in water. The effect of a number of organic compounds, including amino acids, on the toxicity of heavy metals was tested, but there were no reports elucidating compounds representing various types of structure. This paper deals with the effect of amino acids representing various structure groups on the toxicity of copper, cadmium and mercury against to Chlorella vulgaris and Anabeana variabilis.

  15. Conversion of light hydrocarbon gases to metal carbides for production of liquid fuels and chemicals. Quarterly technical status report, January 1--March 31, 1994

    SciTech Connect

    Diaz, A.F.; Modestino, A.J.; Howard, J.B.; Tester, J.W.; Peters, W.A.

    1994-07-01

    The thermal plasma reactor system has undergone shakedown testing. The system flow capacity (cold reactor) was determined to be 3.35 cfm of argon at ambient temperature. A stable argon plasma is found to be obtainable up to 20 kW power input at a gas flowrate of 1 cfm. Further increases in power input level will be explored in the future as needed. Temperature profile measurements in the cooling chamber were performed at distances of 10.5 to 4.5 inches from the anode nozzle exit at power input levels of 5 to 20 kW and an argon gas flowrate of 1 cfm. The sample collection system was completed and will be tested simultaneously with a powder feeder that was acquired from Miller Thermal, Inc., of Appleton, WI, on a loan basis for trials on our system. Effectiveness of powder feeding will be investigated under argon cold flow (without firing) and hot flow (with firing) conditions. X-ray Photoelectron Spectroscopy was examined as a semi-quantitative technique for assessing the surface composition of carbides. Equilibrium diagrams for the Ca-C-H-O and Mg-C-H-O systems with the formation of C(s) suppressed at 1 atm pressure and over a temperature range of 1500 - 3500 K suggest that formation of CaC{sub 2} can occur without C(s) but that the formation of significant quantities of either MgC{sub 2} or Mg{sub 2}C{sub 3} does not occur in the absence of C(s).

  16. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation

    SciTech Connect

    Landon, L.F.

    1991-01-01

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO[sub 3] and NaNO[sub 2] with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  17. Elucidation of noble metal/formic acid chemistry during DWPF feed preparation. Revision 1

    SciTech Connect

    Landon, L.F.

    1991-12-31

    Eleven reports are included: evaluation of noble metal compounds as catalysts for aerobic decomposition of formic acid; reaction of NaNO{sub 3} and NaNO{sub 2} with formic acid under argon; effects of Ru, Rh, Pd chlorides on formic acid decomposition in presence of IDMS (pH=11.0) sludge; effects of additives on catalysts on decomposition of formic acid to hydrogen; Rh-catalyzed decomposition of formic acid; the question of whether this decomposition can be heterogeneous catalysis; inhibition of this reaction by additives; nitrilotriacetic acid inhibitor; uses of gelatin and other water soluble polymers to control flocculation rate; comparison of catalytic activities of Rh, Ru, Pd in Purex and HM sludges; experiments on homogeneous vs heterogeneous nature of Rh catalyst. Figs, refs, tabs.

  18. Method of making metal oxide ceramic powders by using a combustible amino acid compound

    DOEpatents

    Pederson, L.R.; Chick, L.A.; Exarhos, G.J.

    1992-05-19

    This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

  19. Method of making metal oxide ceramic powders by using a combustible amino acid compound

    DOEpatents

    Pederson, Larry R.; Chick, Lawrence A.; Exarhos, Gregory J.

    1992-01-01

    This invention is directed to the formation of homogeneous, aqueous precursor mixtures of at least one substantially soluble metal salt and a substantially soluble, combustible co-reactant compound, typically an amino acid. This produces, upon evaporation, a substantially homogeneous intermediate material having a total solids level which would support combustion. The homogeneous intermediate material essentially comprises highly dispersed or solvated metal constituents and the co-reactant compound. The intermediate material is quite flammable. A metal oxide powder results on ignition of the intermediate product which combusts same to produce the product powder.

  20. Lightweight, durable lead-acid batteries

    DOEpatents

    Lara-Curzio, Edgar; An, Ke; Kiggans, Jr., James O; Dudney, Nancy J; Contescu, Cristian I; Baker, Frederick S; Armstrong, Beth L

    2013-05-21

    A lightweight, durable lead-acid battery is disclosed. Alternative electrode materials and configurations are used to reduce weight, to increase material utilization and to extend service life. The electrode can include a current collector having a buffer layer in contact with the current collector and an electrochemically active material in contact with the buffer layer. In one form, the buffer layer includes a carbide, and the current collector includes carbon fibers having the buffer layer. The buffer layer can include a carbide and/or a noble metal selected from of gold, silver, tantalum, platinum, palladium and rhodium. When the electrode is to be used in a lead-acid battery, the electrochemically active material is selected from metallic lead (for a negative electrode) or lead peroxide (for a positive electrode).

  1. Lightweight, durable lead-acid batteries

    DOEpatents

    Lara-Curzio, Edgar; An, Ke; Kiggans, Jr., James O.; Dudney, Nancy J.; Contescu, Cristian I.; Baker, Frederick S.; Armstrong, Beth L.

    2011-09-13

    A lightweight, durable lead-acid battery is disclosed. Alternative electrode materials and configurations are used to reduce weight, to increase material utilization and to extend service life. The electrode can include a current collector having a buffer layer in contact with the current collector and an electrochemically active material in contact with the buffer layer. In one form, the buffer layer includes a carbide, and the current collector includes carbon fibers having the buffer layer. The buffer layer can include a carbide and/or a noble metal selected from of gold, silver, tantalum, platinum, palladium and rhodium. When the electrode is to be used in a lead-acid battery, the electrochemically active material is selected from metallic lead (for a negative electrode) or lead peroxide (for a positive electrode).

  2. Transition-Metal-Free Decarboxylative Photoredox Coupling of Carboxylic Acids and Alcohols with Aromatic Nitriles.

    PubMed

    Lipp, Benjamin; Nauth, Alexander M; Opatz, Till

    2016-08-01

    A transition-metal-free protocol for the redox-neutral light-induced decarboxylative coupling of carboxylic acids with (hetero)aromatic nitriles at ambient temperature is presented. A broad scope of acids and nitriles is accepted, and alcohols can be coupled in a similar fashion through their oxalate half esters. Various inexpensive sources of UV light and even sunlight can be used to achieve this C-C bond formation proceeding through a free radical mechanism. PMID:27399619

  3. Strong dependence of fluorescence quenching on the transition metal in layered transition metal dichalcogenide nanoflakes for nucleic acid detection.

    PubMed

    Loo, Adeline Huiling; Bonanni, Alessandra; Pumera, Martin

    2016-08-01

    In recent years, the application of transition metal dichalcogenides for the development of biosensors has been receiving widespread attention from researchers, as demonstrated by the surge in studies present in the field. While different transition metal dichalcogenide materials have been employed for the fabrication of fluorescent biosensors with superior performance, no research has been conducted to draw comparisons across materials containing different transition metals. Herein, the performance of MoS2 and WS2 nanoflakes for the fluorescence detection of nucleic acids is assessed. It is discovered that, at the optimal amount, MoS2 and WS2 nanoflakes exhibit a similar degree of fluorescence quenching, at 75% and 71% respectively. However, MoS2 nanoflakes have better performance in the areas of detection range and selectivity than WS2 nanoflakes. The detection range achieved with MoS2 nanoflakes is 9.60-366 nM while 13.3-143 nM with WS2 nanoflakes. In the context of selectivity, MoS2 nanoflakes display a signal difference of 97.8% between complementary and non-complementary DNA targets, whereas WS2 nanoflakes only exhibit 44.3%. Such research is highly beneficial as it delivers vital insights on how the performance of a fluorescent biosensor can be affected by the transition metal present. Furthermore, these insights can assist in the selection of suitable transition metal dichalcogenide materials for utilization in biosensor development. PMID:27241269

  4. Interaction of lactic acid bacteria with metal ions: opportunities for improving food safety and quality.

    PubMed

    Mrvčić, Jasna; Stanzer, Damir; Solić, Ema; Stehlik-Tomas, Vesna

    2012-09-01

    Certain species of lactic acid bacteria (LAB), as well as other microorganisms, can bind metal ions to their cells surface or transport and store them inside the cell. Due to this fact, over the past few years interactions of metal ions with LAB have been intensively investigated in order to develop the usage of these bacteria in new biotechnology processes in addition to their health and probiotic aspects. Preliminary studies in model aqueous solutions yielded LAB with high absorption potential for toxic and essential metal ions, which can be used for improving food safety and quality. This paper provides an overview of results obtained by LAB application in toxic metal ions removing from drinking water, food and human body, as well as production of functional foods and nutraceutics. The biosorption abilities of LAB towards metal ions are emphasized. The binding mechanisms, as well as the parameters influencing the passive and active uptake are analyzed. PMID:22806724

  5. Weak acid extractable metals in Bramble Bay, Queensland, Australia: temporal behaviour, enrichment and source apportionment.

    PubMed

    Brady, James P; Ayoko, Godwin A; Martens, Wayde N; Goonetilleke, Ashantha

    2015-02-15

    Sediment samples were taken from six sampling sites in Bramble Bay, Queensland, Australia between February and November in 2012. They were analysed for a range of heavy metals including Al, Fe, Mn, Ti, Ce, Th, U, V, Cr, Co, Ni, Cu, Zn, As, Cd, Sb, Te, Hg, Tl and Pb. Fraction analysis, Enrichment Factors and Principal Component Analysis-Absolute Principal Component Scores (PCA-APCS) were carried out in order to assess metal pollution, potential bioavailability and source apportionment. Cr and Ni exceeded the Australian Interim Sediment Quality Guidelines at some sampling sites, while Hg was found to be the most enriched metal. Fraction analysis identified increased weak acid soluble Hg and Cd during the sampling period. Source apportionment via PCA-APCS found four sources of metals pollution, namely, marine sediments, shipping, antifouling coatings and a mixed source. These sources need to be considered in any metal pollution control measure within Bramble Bay. PMID:25537749

  6. Removal of heavy metals and lanthanides from industrial phosphoric acid process liquors

    SciTech Connect

    Koopman, C.; Witkamp, G.J.; Van Rosmalen, G.M.

    1999-11-01

    To diminish the discharge of heavy metals and lanthanides by the phosphoric acid industry, these impurities have to be removed from the mother liquor before their incorporation in the gypsum crystals. This can best be achieved by means of solvent extraction or ion exchange during the recrystallization of hemihydrate to dihydrate gypsum. Various commercial carriers and two ion-exchange resins were screened for their efficiency and selectivity. Light and heavy lanthanide ions are extracted from the recrystallization acid by didodecylnaphthalenesulfonic acid (Nacure 1052) and di(2-ethylhexyl)phosphoric acid (D2EHPA), and the heavy-metal ions by bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301) and by bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302). Mercury is also extracted by the anion carriers tri(C{sub 8}-C{sub 10})amine (Alamine 336) and tri(C{sub 8}-C{sub 10}) monomethyl ammonium chloride (Aliquat 336). Both Dowex C-500 and Amberlite IR-120 extract lanthanide and heavy-metal ions. Unfortunately, D2EHPA, Nacure 1052, and the two ion-exchange resins also show affinity for ions present in much higher concentrations, like calcium or iron ions.

  7. Structural arrangements of the ternary metal boride carbide compounds MB 2C 4 ( M=Mg, Ca, La and Ce) from first-principles theory

    NASA Astrophysics Data System (ADS)

    Fang, Chang-Ming; Bauer, Joseph; Saillard, Jean-Yves; Halet, Jean-François

    2007-09-01

    The structural arrangements of the ternary metal borocarbides MB 2C 4 ( M=Mg, Ca; La and Ce) are investigated using density-functional theory (DFT) calculations within the generalized gradient approximation (GGA). Results indicate that these compounds adopt a layered structure consisting of graphite-like B 2C 4 layers alternating with metal sheets. Within the hexagonal layers, the coloring with the -C-C-C-B-C-B- sequence is energetically more stable than that with the -C-C-C-C-B-B- one. The electronic structures of these compounds, mainly determined by the B 2C 4 sheets, can be rationalized with the simple valence electron distribution M2+[B 2C 4] 2-xe -, with the metals essentially acting as two-electron donors with respect to the boron-carbon network, the other x electrons remaining in the relatively narrow d and/or f bands of the metals. Accordingly, MB 2C 4 are narrow band-gap semiconductors (Δ E≈0.2-0.4 eV) with M=Mg and Ca. On the other hand, with M=La and Ce, the compounds are conducting with a relatively high density of states at the Fermi level predominantly metal in character with substantial B/C π* antibonding state admixture.

  8. Negative bias-and-temperature stress-assisted activation of oxygen-vacancy hole traps in 4H-silicon carbide metal-oxide-semiconductor field-effect transistors

    SciTech Connect

    Ettisserry, D. P. E-mail: neil@umd.edu; Goldsman, N. E-mail: neil@umd.edu; Akturk, A.; Lelis, A. J.

    2015-07-28

    We use hybrid-functional density functional theory-based Charge Transition Levels (CTLs) to study the electrical activity of near-interfacial oxygen vacancies located in the oxide side of 4H-Silicon Carbide (4H-SiC) power Metal-Oxide-Semiconductor Field-Effect Transistors (MOSFETs). Based on the “amorphousness” of their local atomic environment, oxygen vacancies are shown to introduce their CTLs either within (permanently electrically active) or outside of (electrically inactive) the 4H-SiC bandgap. The “permanently electrically active” centers are likely to cause threshold voltage (V{sub th}) instability at room temperature. On the other hand, we show that the “electrically inactive” defects could be transformed into various “electrically active” configurations under simultaneous application of negative bias and high temperature stresses. Based on this observation, we present a model for plausible oxygen vacancy defects that could be responsible for the recently observed excessive worsening of V{sub th} instability in 4H-SiC power MOSFETs under high temperature-and-gate bias stress. This model could also explain the recent electrically detected magnetic resonance observations in 4H-SiC MOSFETs.

  9. Negative bias-and-temperature stress-assisted activation of oxygen-vacancy hole traps in 4H-silicon carbide metal-oxide-semiconductor field-effect transistors

    NASA Astrophysics Data System (ADS)

    Ettisserry, D. P.; Goldsman, N.; Akturk, A.; Lelis, A. J.

    2015-07-01

    We use hybrid-functional density functional theory-based Charge Transition Levels (CTLs) to study the electrical activity of near-interfacial oxygen vacancies located in the oxide side of 4H-Silicon Carbide (4H-SiC) power Metal-Oxide-Semiconductor Field-Effect Transistors (MOSFETs). Based on the "amorphousness" of their local atomic environment, oxygen vacancies are shown to introduce their CTLs either within (permanently electrically active) or outside of (electrically inactive) the 4H-SiC bandgap. The "permanently electrically active" centers are likely to cause threshold voltage (Vth) instability at room temperature. On the other hand, we show that the "electrically inactive" defects could be transformed into various "electrically active" configurations under simultaneous application of negative bias and high temperature stresses. Based on this observation, we present a model for plausible oxygen vacancy defects that could be responsible for the recently observed excessive worsening of Vth instability in 4H-SiC power MOSFETs under high temperature-and-gate bias stress. This model could also explain the recent electrically detected magnetic resonance observations in 4H-SiC MOSFETs.

  10. Ultrasmall Carbide Nanospheres - Formation and Electronic Properties

    NASA Astrophysics Data System (ADS)

    Reinke, Petra; Monazami, Ehsan; McClimon, John

    2015-03-01

    Metallic nanoparticles are highly coveted but are subject to rapid Ostwald ripening even at moderate temperatures limiting study of their properties. Ultrasmall transition metal carbide ``nanospheres'' are synthesized by a solid-state reaction between fullerene as carbon scaffold, and a W surface. This produces nanospheres with a narrow size distribution below 2.5 nm diameter. The nanosphere shape is defined by the scaffold and densely packed arrays can be achieved. The metal-fullerene reaction is temperature driven and progresses through an intermediate semiconducting phase until the fully metallic nanospheres are created at about 350 C. The reaction sequence is observed with STM, and STS maps yield the local density of states. The reaction presumably progresses by stepwise introduction of W-atoms in the carbon scaffold. The results of high resolution STM/STS in combination with DFT calculations are used to unravel the reaction mechanism. We will discuss the transfer of this specific reaction mechanism to other transition metal carbides. The nanospheres are an excellent testbed for the physics and chemistry of highly curved surfaces.

  11. Carbide transformations in constructional steels

    SciTech Connect

    Vinokur, B.B.

    1986-01-01

    In connection with the type of carbides formed in general purpose constructional steels or on the mechanisms of carbide transformations and the influence of carbide formation on the properties, this work presents an investigation that was made of medium-carbon chrome-nickel and chrome-manganese steels with 1, 2, and 3% Cr, 1% Ni, and 1% Mn additionally alloyed with 0.25-2% Mo or W (every 0.25%). All of the steels were hardened from temperatures providing the fullest solution of carbides in austenite and were tempered at 400-650/sup 0/C every 25-50/sup 0/C. The composition of the carbides and their type were established by chemical, x-ray diffraction, and microdiffraction methods and the mechanism of the carbide transformations was determined on the basis of the changes in distortions of the second and third order of the matrix electrical resistance, and coercive force of the steel. All of the carbideforming elements present in steel participate in saturation of the carbides, as a result of which the formation of a special carbide is eased and the degree of alloying of the matrix increases. In the carbide transformation with a certain share of carbide phase an increase or retarding of the reduction in strength with an increase in tempering temperature with constant plasticity and impact strength is possible.

  12. Tunable carbon nanotube-tungsten carbide nanoparticles heterostructures by vapor deposition

    SciTech Connect

    Xia, Min; Guo, Hongyan; Ge, Changchun; Yan, Qingzhi Lang, Shaoting

    2014-05-14

    A simple, versatile route for the synthesis of carbon nanotube (CNT)-tungsten carbide nanoparticles heterostructures was set up via vapor deposition process. For the first time, amorphous CNTs (α-CNTs) were used to immobilized tungsten carbide nanoparticles. By adjusting the synthesis and annealing temperature, α-CNTs/amorphous tungsten carbide, α-CNTs/W{sub 2}C, and CNTs/W{sub 2}C/WC heterostructures were prepared. This approach provides an efficient method to attach other metal carbides and other nanoparticles to carbon nanotubes with tunable properties.

  13. A study of the effect of grain size on the ballistic performance of silicon carbide

    SciTech Connect

    Cline, C.F.

    1995-03-01

    The depth of penetration method was used to ballistically evaluate the performance of silicon carbide as a function of grain size. The hot-pressed silicon carbide was backed by 4340 steel Rc = 35 and impacted by tungsten heavy metal projectiles of L/D = 4 at velocities of 1.6 and 1/75 km/s. The hot-pressed silicon carbide was also compared with reaction-sintered silicon carbide of identical thickness in the current study. Results are compared with data previously reported by others.

  14. Hidden Brønsted acid catalysis: pathways of accidental or deliberate generation of triflic acid from metal triflates.

    PubMed

    Dang, Tuan Thanh; Boeck, Florian; Hintermann, Lukas

    2011-11-18

    The generation of a hidden Brønsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF(3)SO(3)H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl(2)/AgOTf/phosphane combination in toluene has been elucidated. The deliberate and controlled generation of HOTf from AgOTf and cocatalytic amounts of tert-butyl chloride in the cold or from AgOTf in DCE at elevated temperatures results in a hidden Brønsted acid catalyst useful for mechanistic control experiments or for synthetic applications. PMID:22010906

  15. Catalyst of a metal heteropoly acid salt that is insoluble in a polar solvent on a non-metallic porous support and method of making

    DOEpatents

    Wang, Yong [Richland, WA; Peden, Charles H. F. [West Richland, WA; Choi, Saemin [Richland, WA

    2002-10-29

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  16. Catalyst Of A Metal Heteropoly Acid Salt That Is Insoluble In A Polar Solvent On A Non-Metallic Porous Support And Method Of Making

    DOEpatents

    Wang. Yong; Peden. Charles H. F.; Choi. Saemin

    2004-11-09

    The present invention includes a catalyst having (a) a non-metallic support having a plurality of pores; (b) a metal heteropoly acid salt that is insoluble in a polar solvent on the non-metallic support; wherein at least a portion of the metal heteropoly acid salt is dispersed within said plurality of pores. The present invention also includes a method of depositing a metal heteropoly acid salt that is insoluble in a polar solvent onto a non-metallic support having a plurality of pores. The method has the steps of: (a) obtaining a first solution containing a first precursor of a metal salt cation; (b) obtaining a second solution containing a second precursor of a heteropoly acid anion in a solvent having a limited dissolution potential for said first precursor; (c) impregnating the non-metallic support with the first precursor forming a first precursor deposit within the plurality of pores, forming a first precursor impregnated support; (d) heating said first precursor impregnated support forming a bonded first precursor impregnated support; (e) impregnating the second precursor that reacts with the precursor deposit and forms the metal heteropoly acid salt.

  17. Synthesis of ferromagnetic nanoparticles, formic acid oxidation catalyst nanocomposites, and late-transition metal-boride intermetallics by unique synthetic methods and single-source precursors

    NASA Astrophysics Data System (ADS)

    Wellons, Matthew S.

    The design, synthesis, and characterization of magnetic alloy nanoparticles, supported formic acid oxidation catalysts, and superhard intermetallic composites are presented. Ferromagnetic equatomic alloy nanoparticles of FePt, FePd, and CoPt were synthesized utilizing single-source heteronuclear organometallic precursors supported on an inert water-soluble matrix. Direct conversion of the precursor-support composite to supported ferromagnetic nanoparticles occurs under elevated temperatures and reducing conditions with metal-ion reduction and minimal nanoparticle coalescence. Nanoparticles were easily extracted from the support by addition of water and characterized in structure and magnetic properties. Palladium and platinum based nanoparticles were synthesized with microwave-based and chemical metal-ion reduction strategies, respectively, and tested for catalytic performance in a direct formic acid fuel cell (DFAFC). A study of palladium carbide nanocomposites with various carbonaceous supports was conducted and demonstrated strong activity comparable to commercially available palladium black, but poor catalytic longevity. Platinum-lead alloy nanocomposites synthesized with chemical reduction and supported on Vulcan carbon demonstrated strong activity, excellent catalytic longevity, and were subsequently incorporated into a prototype DFAFC. A new method for the synthesis of superhard ceramics on polymer substrates called Confined Plasma Chemical Deposition (CPCD) was developed. The CPCD method utilizes a tuned Free Electron Laser to selectively decompose the single-source precursor, Re(CO)4(B3H8), in a plasma-like state resulting in the superhard intermetallic ReB2 deposited on polymer substrates. Extension of this method to the synthesis of other hard of superhard ceramics; WB4, RuB2, and B4C was demonstrated. These three areas of research show new synthetic methods and novel materials of technological importance, resulting in a substantial advance in their

  18. Method of making carbide/fluoride/silver composites

    NASA Technical Reports Server (NTRS)

    Sliney, Harold E. (Inventor); Dellacorte, Christopher (Inventor)

    1991-01-01

    A composition containing 30 to 70 percent chromium carbide, 5 to 20 percent soft noble metal, 5 to 20 percent metal fluorides, and 20 to 60 percent metal binder is used in a powdered metallurgy process for the production of self-lubricating components, such as bearings. The use of the material allows the self-lubricating bearing to maintain its low friction properties over an extended range of operating temperatures.

  19. Emerging Technology Summary. ACID EXTRACTION TREATMENT SYSTEM FOR TREATMENT OF METAL CONTAMINATED SOILS

    EPA Science Inventory

    The Acid Extraction Treatment System (AETS) is intended to reduce the concentrations and/or teachability of heavy metals in contaminated soils so the soil can be returned to the site from which it originated. The objective of the project was to determine the effectiveness and com...

  20. MECHANISMS OF HEAVY METAL REMOVAL FROM ACID MINE DRAINAGE USING CHITIN

    EPA Science Inventory

    Acid Mine Drainage (AMD) emanating from inactive or active mine sites contains elevated levels of toxic heavy metals, which can have an adverse impact to the surrounding environment. The major pathway involved in generation of AMD is weathering of pyritic mineral ores, where in s...

  1. Preliminary Results: Release Of Metals From Acid-Mine Drainage Contaminated Streambed Sediments Under Anaerobic Conditions

    EPA Science Inventory

    Many miles of streams in the western U.S. are contaminated with acid-mine drainage (AMD) from abandoned metal mines. Treatment of these streams may include removal of the existing sediments, with subsequent burial (e.g., in a repository). Burial of previously aerobic sediments ma...

  2. Mononuclear metal complexes of organic carboxylic acid derivatives: Synthesis, spectroscopic characterization, thermal investigation and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Abd El-Wahab, Zeinab H.

    2007-05-01

    Two Schiff base ligands bearing organic acid moiety, vis., N-(2-thienylmethylidene)-2-amino-4-chlorobenzoic acid (HL 1) and N-(2-hydroxybenzylidene)-2-amino-4-chlorobenzoic acid (H 2L 2) have been synthesized by the interaction of 2-thiophenecarboxaldehyde and 2-hydroxybenzaldehyde with 2-amino-4-chlorobenzoic acid. Co(II), Ni(II), Cu(II) and Zn(II) complexes of these ligands have been prepared. They are characterized on the basis of analytical data, molar conductance, IR, 1H NMR, UV-vis, mass spectra, magnetic measurements, thermal analysis and X-ray powder diffraction technique. The molar conductance data reveal that these complexes are non-electrolytes. The ligands are coordinated to the metal ions in a terdentate manner with ONO/ONS donor sites of the carbonyl oxygen, azomethine nitrogen and phenolic oxygen or thiophenic sulphur. An octahedral structure is proposed for the prepared metal complexes and some ligand field parameters ( Dq, B and β) in addition to CFSE were calculated. The thermal stability of the metal complexes is evaluated. The Schiff base ligands and their metal complexes have been tested against four species of bacteria as well as four species of fungi and the results have been compared with some known antibiotics.

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

    NASA Astrophysics Data System (ADS)

    Gaballa, Osama Gaballa Bahig

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

  4. Revisiting formic acid decomposition on metallic powder catalysts: Exploding the HCOOH decomposition volcano curve

    NASA Astrophysics Data System (ADS)

    Tang, Yadan; Roberts, Charles A.; Perkins, Ryan T.; Wachs, Israel E.

    2016-08-01

    This study revisits the classic volcano curve for HCOOH decomposition by metal catalysts by taking a modern catalysis approach. The metal catalysts (Au, Ag, Cu, Pt, Pd, Ni, Rh, Co and Fe) were prepared by H2 reduction of the corresponding metal oxides. The number of surface active sites (Ns) was determined by formic acid chemisorption. In situ IR indicated that both monodentate and bidentate/bridged surface HCOO* were present on the metals. Heats of adsorption (ΔHads) for surface HCOO* values on metals were taken from recently reported DFT calculations. Kinetics for surface HCOO* decomposition (krds) were determined with TPD spectroscopy. Steady-state specific activity (TOF = activity/Ns) for HCOOH decomposition over the metals was calculated from steady-state activity (μmol/g-s) and Ns (μmol/g). Steady-state TOFs for HCOOH decomposition weakly correlated with surface HCOO* decomposition kinetics (krds) and ΔHads of surface HCOO* intermediates. The plot of TOF vs. ΔHads for HCOOH decomposition on metal catalysts does not reproduce the classic volcano curve, but shows that TOF depends on both ΔHads and decomposition kinetics (krds) of surface HCOO* intermediates. This is the first time that the classic catalysis study of HCOOH decomposition on metallic powder catalysts has been repeated since its original publication.

  5. ADVANCES IN BIOTREATMENT OF ACID MINE DRAINAGE AND BIORECOVERY OF METALS: 2. MEMBRANE BIOREACTOR SYSTEM FOR SULFATE REDUCTION

    EPA Science Inventory

    Acid-mine drainage (AMD) is a severe pollution problem attributed to past mining activities. AMD is an acidic, metal-bearing wastewater generated by the oxidation of metal sulfides to sulfates by Thiobacillus bacteria in both the active and abandoned mining operations. The wastew...

  6. 40 CFR 60.52b - Standards for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... metals, acid gases, organics, and nitrogen oxides. 60.52b Section 60.52b Protection of Environment... § 60.52b Standards for municipal waste combustor metals, acid gases, organics, and nitrogen oxides. (a... (total mass), corrected to 7 percent oxygen. (d) The limits for nitrogen oxides are specified...

  7. 40 CFR 62.14103 - Emission limits for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... combustor metals, acid gases, organics, and nitrogen oxides. 62.14103 Section 62.14103 Protection of... combustor metals, acid gases, organics, and nitrogen oxides. (a) The emission limits for municipal waste... nitrogen oxides in excess of the emission limits listed in table 2 of this subpart for affected...

  8. 40 CFR 60.52b - Standards for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... metals, acid gases, organics, and nitrogen oxides. 60.52b Section 60.52b Protection of Environment... § 60.52b Standards for municipal waste combustor metals, acid gases, organics, and nitrogen oxides. (a... (total mass), corrected to 7 percent oxygen. (d) The limits for nitrogen oxides are specified...

  9. 40 CFR 60.33b - Emission guidelines for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... combustor metals, acid gases, organics, and nitrogen oxides. 60.33b Section 60.33b Protection of Environment..., acid gases, organics, and nitrogen oxides. (a) The emission limits for municipal waste combustor metals... limits for nitrogen oxides at least as protective as the emission limits listed in table 1 of...

  10. 40 CFR 60.33b - Emission guidelines for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... combustor metals, acid gases, organics, and nitrogen oxides. 60.33b Section 60.33b Protection of Environment..., acid gases, organics, and nitrogen oxides. (a) The emission limits for municipal waste combustor metals... limits for nitrogen oxides at least as protective as the emission limits listed in table 1 of...

  11. 40 CFR 62.14103 - Emission limits for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... combustor metals, acid gases, organics, and nitrogen oxides. 62.14103 Section 62.14103 Protection of... combustor metals, acid gases, organics, and nitrogen oxides. (a) The emission limits for municipal waste... nitrogen oxides in excess of the emission limits listed in table 2 of this subpart for affected...

  12. [Using kenaf (Hibiscus cannabinus) to reclaim multi-metal contaminated acidic soil].

    PubMed

    Yang, Yu-Xi; Lu, Huan-Liang; Zhan, Shu-Shun; Deng, Teng-hao-bo; Lin, Qing-Qi; Wang, Shi-Zhong; Yang, Xiu-Hong; Qiu, Rong-Liang

    2013-03-01

    A five-year field trial was conducted at the surrounding area of Dabao Mountain Mine to explore the feasibility and availability of using kenaf (Hibiscus cannabinus) , a fiber crop with strong heavy metals tolerance and potential economic value, to reclaim the multi-metal contaminated acidic farmland soil. Different amendments were applied prior to the kenaf planting to evaluate their effects on the soil properties and kenaf growth. After the amendments application, the kenaf could grow well on the heavy metals contaminated soil with the Pb, Zn, Cu, Cd, and As concentrations being 1600, 440, 640, 7. 6, and 850 mg . kg-1, respectively. Among the amendments, dolomite and fly ash had better effects than limestone and organic fertilizer. With the application of dolomite and fly ash, the aboveground dry mass production of kenaf reached 14-15 t . hm-2, which was similar to that on normal soils, and the heavy metal concentrations in the bast fiber and stem of kenaf decreased significantly, as compared with the control. The mass of the bast fiber accounted for 32% -38% of the shoot production, and the extractable heavy metal concentrations in the bast fiber could meet the standard of 'technical specifications of ecological textiles' in China, suggesting that the bast fiber had potential economic value. It was suggested that planting kenaf combining with dolomite/fly ash application could be an effective measure to reclaim the multi-metal contaminated acidic farmland soil. PMID:23755502

  13. Metals and Colloids in the Hyporheic Zone of an Acid Mine Drainage-Contaminated Stream

    NASA Astrophysics Data System (ADS)

    Norvell, A. S.; Ryan, J. N.; McKnight, D. M.; Ren, J.

    2009-12-01

    A key component of human and ecological risk assessments of acid mine drainage is predicting the fate and transport of metals in receiving streams. In order to learn more about the processes that control metal removal in the stream, we studied the role of colloids and the exchange of stream water with the hyporheic zone in Lefthand Creek, a stream contaminated by acid mine drainage in northwestern Boulder County, Colorado. We installed a set of mini-piezometers in the streambed and sampled the hyporheic pore waters along a 90 m reach of the creek for metals, colloids, and other geochemical parameters in the water and sediments. We conducted tracer dilution tests to determine the extent and time scale of hyporheic exchange. The results of these investigations showed that hyporheic exchange is a significant process in the attenuation of metals. The conservative tracer (bromide) concentration reached plateaus of up to 80 % of the surface concentration at depths of 40 cm and up to only 5% at depths of 100 cm. Hydraulic residence times in the upper 40 cm range from 20 minutes at 5 cm depths to under 3 hours at 40 cm depths. Colloidal transport of some metals is significant; large fractions of lead and copper were associated with colloids composed primarily of iron and aluminum, while zinc was not significantly associated with colloids. Sequential extractions of the sediments showed that trace metals were incorporated in iron and manganese oxide coatings found on the streambed sediments.

  14. Ion flotation behaviour of thirty-one metal ions in mixed hydrochloric/nitric acid solutions.

    PubMed

    Hualing, D; Zhide, H

    1989-06-01

    The ion flotation of 31 metal ions in hydrochloric/nitric acid solution with the cationic surfactant cetylpyridinium chloride was investigated. A 25-ml portion of 0.27-2.87 x 10(-4)M metal ion and 1.8-6.0 x 10(-4)M cetylpyridinium chloride solution in 0.17-3.4M acid mixture ([HCl]:[HNO(3)] = 2.4:1) was subjected to flotation in a cell, 22.5 cm high and 4.0 cm in diameter, for 5 min, with nitrogen bubbles. Ir(IV), Pt(IV), Ge(IV), Sn(IV), Bi(III), Au(III), Tl(III), Pd(II) and Sn(II) were floated from solution in 95-100% yield; Ru(III), Rh(III), Ir(III), Hg(II), Ag(I) and Tl(I) were partly floated, while Cr(VI), Ti(IV), Zr(IV), Ga(III), In(III), Fe(III), Sb(III), Al(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), CD(II) and Pb(II) were floated with less than 20% yield. The flotation behaviour of these metal ions in the mixed acid system was compared with that in hydrochloric acid. The flotation is more efficient in the mixed acid system. PMID:18964771

  15. Modified silicon carbide whiskers

    DOEpatents

    Tiegs, T.N.; Lindemer, T.B.

    1991-05-21

    Silicon carbide whisker-reinforced ceramic composites are fabricated in a highly reproducible manner by beneficating the surfaces of the silicon carbide whiskers prior to their usage in the ceramic composites. The silicon carbide whiskers which contain considerable concentrations of surface oxides and other impurities which interact with the ceramic composite material to form a chemical bond are significantly reduced so that only a relatively weak chemical bond is formed between the whisker and the ceramic material. Thus, when the whiskers interact with a crack propagating into the composite the crack is diverted or deflected along the whisker-matrix interface due to the weak chemical bonding so as to deter the crack propagation through the composite. The depletion of the oxygen-containing compounds and other impurities on the whisker surfaces and near surface region is effected by heat treating the whiskers in a suitable oxygen sparging atmosphere at elevated temperatures. Additionally, a sedimentation technique may be utilized to remove whiskers which suffer structural and physical anomalies which render them undesirable for use in the composite. Also, a layer of carbon may be provided on the surface of the whiskers to further inhibit chemical bonding of the whiskers to the ceramic composite material.

  16. Modified silicon carbide whiskers

    DOEpatents

    Tiegs, Terry N.; Lindemer, Terrence B.

    1991-01-01

    Silicon carbide whisker-reinforced ceramic composites are fabricated in a highly reproducible manner by beneficating the surfaces of the silicon carbide whiskers prior to their usage in the ceramic composites. The silicon carbide whiskers which contain considerable concentrations of surface oxides and other impurities which interact with the ceramic composite material to form a chemical bond are significantly reduced so that only a relatively weak chemical bond is formed between the whisker and the ceramic material. Thus, when the whiskers interact with a crack propagating into the composite the crack is diverted or deflected along the whisker-matrix interface due to the weak chemical bonding so as to deter the crack propagation through the composite. The depletion of the oxygen-containing compounds and other impurities on the whisker surfaces and near surface region is effected by heat treating the whiskers in a suitable oxygen sparaging atmosphere at elevated temperatures. Additionally, a sedimentation technique may be utilized to remove whiskers which suffer structural and physical anomalies which render them undesirable for use in the composite. Also, a layer of carbon may be provided on the surface of the whiskers to further inhibit chemical bonding of the whiskers to the ceramic composite material.

  17. Diffusion bonding of an aluminum-copper alloy reinforced with silicon carbide particles (AA2014/SiC/13p) using metallic interlayers

    SciTech Connect

    Urena, A.; Gomez de Salazar, J.M.; Escalera, M.D.

    1996-12-01

    In this work, the application of solid state diffusion bonding to a SiC particulate reinforced aluminium-copper alloy (AA2014) has been studied. The use of metallic interlayers such as an aluminum-lithium alloy and pure silver, has been tested. Bonding interfaces were microstructural characterized using scanning electron (SEM) and transmission electron microscopies (TEM). Joint strengths were evaluated by shear mechanical tests, completed with fractographic studies to determine the failure mechanisms of each kind of joint.

  18. Enhancing Metal-Support Interactions by Molybdenum Carbide: An Efficient Strategy toward the Chemoselective Hydrogenation of α,β-Unsaturated Aldehydes.

    PubMed

    He, Sina; Shao, Zheng-Jiang; Shu, Yijin; Shi, Zhangping; Cao, Xiao-Ming; Gao, Qingsheng; Hu, Peijun; Tang, Yi

    2016-04-11

    Metal-support interactions are desired to optimize the catalytic turnover on metals. Herein, the enhanced interactions by using a Mo2C nanowires support were utilized to modify the charge density of an Ir surface, accomplishing the selective hydrogenation of α,β-unsaturated aldehydes on negatively charged Ir(δ-) species. The combined experimental and theoretical investigations showed that the Ir(δ-) species derive from the higher work function of Ir (vs. Mo2C) and the consequently electron transfer. In crotonaldehyde hydrogenation, Ir/Mo2C delivered a crotyl alcohol selectivity as high as 80%, outperforming those of counterparts (<30%) on silica. Moreover, such electronic metal-support interactions were also confirmed for Pt and Au, as compared with which, Ir/Mo2C was highlighted by its higher selectivity as well as the better activity. Additionally, the efficacy for various substrates further verified our Ir/Mo2C system to be competitive for chemoselective hydrogenation. PMID:26934305

  19. Metal effect on the supramolecular structure, photophysics, and acid-base character of trinuclear pyrazolato coinage metal complexes.

    PubMed

    Omary, Mohammad A; Rawashdeh-Omary, Manal A; Gonser, M W Alexander; Elbjeirami, Oussama; Grimes, Tom; Cundari, Thomas R; Diyabalanage, Himashinie V K; Gamage, Chammi S Palehepitiya; Dias, H V Rasika

    2005-11-14

    Varying the coinage metal in cyclic trinuclear pyrazolate complexes is found to significantly affect the solid-state packing, photophysics, and acid-base properties. The three isoleptic compounds used in this study are [[3,5-(CF3)2Pz]M]3 with M = Cu, Ag, and Au (i.e., Cu3, Ag3, and Au3, respectively). They form isomorphous crystals and exist as trimers featuring nine-membered M3N6 rings with linear two-coordinate metal sites. On the basis of the M-N distances, the covalent radii of two-coordinate Cu(I), Ag(I), and Au(I) were estimated as 1.11, 1.34, and 1.25 angstroms, respectively. The cyclic [[3,5-(CF3)2Pz]M]3 complexes pack as infinite chains of trimers with a greater number of pairwise intertrimer M...M interactions upon proceeding to heavier coinage metals. However, the intertrimer distances are conspicuously short in Ag3 (3.204 angstroms) versus Au3 (3.885 angstroms) or Cu3 (3.813 angstroms) despite the significantly larger covalent radius of Ag(I). Remarkable luminescence properties are found for the three M3 complexes, as manifested by the appearance of multiple unstructured phosphorescence bands whose colors and lifetimes change qualitatively upon varying the coinage metal and temperature. The multiple emissions are assigned to different phosphorescent excimeric states that exhibit enhanced M...M bonding relative to the ground state. The startling luminescence thermochromic changes in crystals of each compound are related to relaxation between the different phosphorescent excimers. The trend in the lowest energy phosphorescence band follows the relative triplet energy of the three M(I) atomic ions. DFT calculations indicate that [[3,5-(R)2Pz]M]3 trimers with R = H or Me are bases with the relative basicity order Ag < Cu < Au while fluorination (R = CF3) renders even the Au trimer acidic. These predictions were substantiated experimentally by the isolation of the first acid-base adduct, [[Au3]2:toluene]infinity, in which a trinuclear Au(I) complex acts as

  20. Acidity and metal (Mg2+, Ca2+, Zn2+) affinity of L-γ-carboxyglutamic acid and its peptide analog

    NASA Astrophysics Data System (ADS)

    Remko, Milan; Broer, Ria; Remková, Anna; Van Duijnen, Piet Th.

    2014-10-01

    Density functional theory methods with the B3LYP and B97D functionals with triple-zeta 6-311++G(d,p) basis set have been used to study the acidity, basicity and metal affinity of L-γ-carboxyglutamic acid (GLA) and its peptide derivative [2-acetylamino-3-(methylamino)-3-oxopropyl]malonic acid (AMD-GLA). The Gibbs interaction energies of the GLA2-…M2+ and AMD-GLA2-…M2+ (M = Mg, Ca, Zn) complexes show an increasing binding affinity in the order Ca2+ < Mg2+ < Zn2+ The transition metal Zn2+ is most effectively recognized by the dianions of GLA and AMD-GLA. Of the dianions studied the AMD-GLA dianion is the strongest Lewis base. Computations that include the effect of solvation showed that in water the relative stability of GLA2-…M2+ and AMD-GLA2-…M2+ ionic bonds is rapidly diminished. The computed interaction Gibbs energy in water is small and negative.

  1. New ternary rare-earth metal boride carbides R{sub 15}B{sub 4}C{sub 14} (R=Y, Gd-Lu) containing BC{sub 2} units: Crystal and electronic structures, magnetic properties

    SciTech Connect

    Babizhetskyy, Volodymyr; Simon, Arndt; Mattausch, Hansjuergen; Hiebl, Kurt; Zheng Chong

    2010-10-15

    The ternary rare-earth boride carbides R{sub 15}B{sub 4}C{sub 14} (R=Y, Gd-Lu) were prepared from the elements by arc-melting followed by annealing in silica tubes at 1270 K for 1 month. The crystal structures of Tb{sub 15}B{sub 4}C{sub 14} and Er{sub 15}B{sub 4}C{sub 14} were determined from single crystal X-ray diffraction data. They crystallize in a new structure type in space group P4/mnc (Tb{sub 15}B{sub 4}C{sub 14}: a=8.1251(5) A, c=15.861(1) A, Z=2, R{sub 1}=0.041 (wR{sub 2}=0.088) for 1023 reflections with I{sub o}>2{sigma}(I{sub o}); Er{sub 15}B{sub 4}C{sub 14}: a=7.932(1) A, c=15.685(2) A, Z=2, R{sub 1}=0.037 (wR{sub 2}=0.094) for 1022 reflections with I{sub o}>2{sigma}(I{sub o})). The crystal structure contains discrete carbon atoms and bent CBC units in octahedra and distorted bicapped square antiprisms, respectively. In both structures the same type of disorder exists. One R atom position needs to be refined as split atom position with a ratio 9:1 indicative of a 10% substitution of the neighboring C{sup 4-} by C{sub 2}{sup 4-}. The actual composition has then to be described as R{sub 15}B{sub 4}C{sub 14.2}. The isoelectronic substitution does not change the electron partition of R{sub 15}B{sub 4}C{sub 14} which can be written as (R{sup 3+}){sub 15}(C{sup 4-}){sub 6}(CBC{sup 5-}){sub 4{center_dot}}e{sup -}. The electronic structure was studied with the extended Hueckel method. The investigated compounds Tb{sub 15}B{sub 4}C{sub 14}, Dy{sub 15}B{sub 4}C{sub 14} and Er{sub 15}B{sub 4}C{sub 14} are hard ferromagnets with Curie temperatures T{sub C}=145, 120 and 50 K, respectively. The coercive field B{sub C}=3.15 T for Dy{sub 15}B{sub 4}C{sub 14} is quite remarkable. - Graphical abstract: The ternary rare earth boride carbides R{sub 15}B{sub 4}C{sub 14} (R=Y, Gd-Lu) were prepared from the elements by arc-melting followed by annealing in silica tubes at 1270 K for 1 month. Tb{sub 15}B{sub 4}C{sub 14} is a new member of the rare-earth metal boride carbide

  2. Metal release from fly ash upon leaching with sulfuric acid or acid mine drainage

    SciTech Connect

    Skousen, J.; Bhumbla, D.K.

    1998-12-31

    Generation of electricity by coal-fired power plants produces large quantities of bottom ash and fly ash. New power plants commonly use fluidized bed combustion (FBC) boilers, which create ashes with high neutralization potential (NP). These ashes, due to their alkaline nature, are often used in surface mine reclamation to neutralize acidity and reduce hydraulic conductivity of disturbed overburdens. Conventional fly ashes from older power plants exhibit a range of pH and NP, with some ashes having neutral or acidic pH and low NP values, and may not be good candidates for supplying alkalinity in reclamation projects. In this study, the authors used two acidic solutions to leach a low NP fly ash (LNP ash) and two FBC ashes (FBC1 and FBC2). After passing 78 pore volumes of sulfuric acid and 129 pore volumes of acid mine drainage (AMD) through these ash materials several trace elements were found at high levels in the leachates. LNP fly ash leachates had high arsenic and selenium concentrations with sulfuric acid leaching, but showed low arsenic and selenium concentrations after leaching with AMD. Leaching with AMD caused the iron and aluminum inherent in AMD to complex these elements and make them unavailable for leaching. Lead, cadmium, and barium concentrations in fly ash leachates were not high enough to cause water pollution problems with either leaching solution. For both leaching solutions, manganese was released from LNP ash at a constant level, FBC1 ash did not release manganese, and FBC2 ash released manganese only after the NP had been exhausted by >60 pore volumes of leaching.

  3. The influence of humic acid on the biological effects of selected trace metals

    SciTech Connect

    Stackhouse, R.A.

    1988-01-01

    The influence of humic acid (HA) on the biological effects of cadmium, hexavalent chromium, and two forms of trivalent chromium was assessed using common freshwater invertebrates. The acute toxicity was determined using Daphnia pulex, while D. magna was used in bioaccumulation studies. Final concentrations of HA tested were 0, 0.5, 5, and 50 mg/l. Humic acid was observed to significantly increase, decrease, or not influence both the acute toxicity and bioaccumulation of cadmium depending on HA concentration and time point examined. Additionally, dialysis studies were used to determine the influence of HA on the bioavailability of the metals. As with the biological effects, HA had little influence on the bioavailability of hexavalent chromium, while having a greater influence on cadmium and chromic chloride. There was a HA concentration dependent pattern of binding (a maximal decrease in percent free metal followed by metal release from HA) observed with cadmium and chromic chloride. This metal release from HA may have resulted from an associated time dependent decrease in pH of the surrounding water. Humic acid had little influence on the bioavailability of chrome lignosulfonate.

  4. Additive Manufacturing and Characterization of Polylactic Acid (PLA) Composites Containing Metal Reinforcements

    NASA Technical Reports Server (NTRS)

    Kuentz, Lily; Salem, Anton; Singh, M.; Halbig, M. C.; Salem, J. A.

    2016-01-01

    Additive manufacturing of polymeric systems using 3D printing has become quite popular recently due to rapid growth and availability of low cost and open source 3D printers. Two widely used 3D printing filaments are based on polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS) systems. PLA is much more environmentally friendly in comparison to ABS since it is made from renewable resources such as corn, sugarcane, and other starches as precursors. Recently, polylactic acid-based metal powder containing composite filaments have emerged which could be utilized for multifunctional applications. The composite filaments have higher density than pure PLA, and the majority of the materials volume is made up of polylactic acid. In order to utilize functionalities of composite filaments, printing behavior and properties of 3-D printed composites need to be characterized and compared with the pure PLA materials. In this study, pure PLA and composite specimens with different metallic reinforcements (Copper, Bronze, Tungsten, Iron, etc) were 3D printed at various layer heights and resulting microstructures and properties were characterized. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) behavior of filaments with different reinforcements were studied. The microscopy results show an increase in porosity between 3-D printed regular PLA and the metal composite PLA samples, which could produce weaker mechanical properties in the metal composite materials. Tensile strength and fracture toughness behavior of specimens as a function of print layer height will be presented.

  5. Humic Acid Metal Cation Interaction Studied by Spectromicroscopy Techniques in Combination with Quantum Chemical Calculations

    SciTech Connect

    Plaschke, M.; Rothe, J; Armbruster, M; Denecke, M; Naber, A; Geckeis, H

    2010-01-01

    Humic acids (HA) have a high binding capacity towards traces of toxic metal cations, thus affecting their transport in aquatic systems. Eu(III)-HA aggregates are studied by synchrotron-based scanning transmission X-ray microscopy (STXM) at the carbon K-edge and laser scanning luminescence microscopy (LSLM) at the {sup 5}D{sub 0} {yields} {sup 7}F{sub 1,2} fluorescence emission lines. Both methods provide the necessary spatial resolution in the sub-micrometre range to resolve characteristic aggregate morphologies: optically dense zones embedded in a matrix of less dense material in STXM images correspond to areas with increased Eu(III) luminescence yield in the LSLM micrographs. In the C 1s-NEXAFS of metal-loaded polyacrylic acid (PAA), used as a HA model compound, a distinct complexation effect is identified. This effect is similar to trends observed in the dense fraction of HA/metal cation aggregates. The strongest complexation effect is observed for the Zr(IV)-HA/PAA system. This effect is confirmed by quantum chemical calculations performed at the ab initio level for model complexes with different metal centres and complex geometries. Without the high spatial resolution of STXM and LSLM and without the combination of molecular modelling with experimental results, the different zones indicating a 'pseudo'-phase separation into strong complexing domains and weaker complexing domains of HA would never have been identified. This type of strategy can be used to study metal interaction with other organic material.

  6. Synthesis and characterization of 2D molybdenum carbide (MXene)

    DOE PAGESBeta

    Halim, Joseph; Kota, Sankalp; Lukatskaya, Maria R.; Naguib, Michael; Zhao, Meng -Qiang; Moon, Eun Ju; Pitock, Jeremy; Nanda, Jagjit; May, Steven J.; Gogotsi, Yury; et al

    2016-02-17

    Large scale synthesis and delamination of 2D Mo2CT x (where T is a surface termination group) has been achieved by selectively etching gallium from the recently discovered nanolaminated, ternary transition metal carbide Mo2Ga2C. Different synthesis and delamination routes result in different flake morphologies. The resistivity of free-standing Mo2CT x films increases by an order of magnitude as the temperature is reduced from 300 to 10 K, suggesting semiconductor-like behavior of this MXene, in contrast to Ti3C2T x which exhibits metallic behavior. At 10 K, the magnetoresistance is positive. Additionally, changes in electronic transport are observed upon annealing of the films.more » When 2 μm thick films are tested as electrodes in supercapacitors, capacitances as high as 700 F cm–3 in a 1 m sulfuric acid electrolyte and high capacity retention for at least 10,000 cycles at 10 A g–1 are obtained. Free-standing Mo2CT x films, with ≈8 wt% carbon nanotubes, perform well when tested as an electrode material for Li-ions, especially at high rates. In conclusion, at 20 and 131 C cycling rates, stable reversible capacities of 250 and 76 mAh g–1, respectively, are achieved for over 1000 cycles.« less

  7. Bioavailability of heavy metals in strongly acidic soils treated with exceptional quality biosolids

    SciTech Connect

    Basta, N.T.; Sloan, J.J.

    1999-03-01

    New federal regulations may increase application of exceptional quality (EQ) biosolids to acidic soils, and information on the effect of this practice on bioavailability of heavy metal is limited. The objective of this study was to compare bioavailability of heavy metal in soil treated with nonalkaline or alkaline EQ biosolids with limestone-treated soils. Three acidic soils (pH 3.7--4.3) were treated with three amounts of lime-stabilized biosolids (LS), anaerobic-digested biosolids (AN), or agricultural limestone (L), and incubated at 25 C. Soil solution Cd, Zn, and other chemical constituents were measured at 1, 30, 90, and 180 d incubation. Soil solution Cd and Zn were AN > LS {ge} L, C. Soil solution Cd and Zn increased with AN applied but decreased wit h LS applied. The high application of LS had soil solution Zn dramatically decreased at soil pH > 5.5 and >5.1, respectively. Soil solution Cd and Zn increases were AN > LS with incubation time. Biosolids treatments increased heavy metal in Ca(NO{sub 3}){sub 2} and NaOAc fractions. Except for Cd, most metal from biosolids were in EDTA and HNO{sub 3} fractions. Heavy metal bioavailability, measured using lettuce (Latuca sativa L.), was AN > LS {ge} L, C. Although state regulations prohibiting application of nonalkaline EQ biosolids to acidic soil is a prudent practice, application of EQ alkaline biosolids that achieves soil pH > 5 minimizes risk from soil solution Cd and Zn and plant uptake of heavy metal.

  8. Sulfation of metal-organic framework: Opportunities for acid catalysis and proton conductivity

    SciTech Connect

    Goesten, M.G.; Stavitski, E.; Juan-Alcaniz, J.; Ramos-Fernandez, E.V.; Sai Sankar Gupta, K.B.; van Bekkum, H.; Gascon, J. and Kapteijn, F.

    2011-05-24

    A new post-functionalization method for metal-organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Broensted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion{reg_sign} display in the esterification of n-butanol with acetic acid (TOF {approx} 1 min{sup -1} {at} 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Broensted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

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

    NASA Astrophysics Data System (ADS)

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

    2008-08-01

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

  10. The Effect of Metal Composition on Fe-Ni Partition Behavior between Olivine and FeNi-Metal, FeNi-Carbide, FeNi-Sulfide at Elevated Pressure

    NASA Technical Reports Server (NTRS)

    Holzheid, Astrid; Grove, Timothy L.

    2005-01-01

    Metal-olivine Fe-Ni exchange distribution coefficients were determined at 1500 C over the pressure range of 1 to 9 GPa for solid and liquid alloy compositions. The metal alloy composition was varied with respect to the Fe/Ni ratio and the amount of dissolved carbon and sulfur. The Fe/Ni ratio of the metal phase exercises an important control on the abundance of Ni in the olivine. The Ni abundance in the olivine decreases as the Fe/Ni ratio of the coexisting metal increases. The presence of carbon (up to approx. 3.5 wt.%) and sulfur (up to approx. 7.5 wt.%) in solution in the liquid Fe-Ni-metal phase has a minor effect on the partitioning of Fe and Ni between metal and olivine phases. No pressure dependence of the Fe-Ni-metal-olivine exchange behavior in carbon- and sulfur-free and carbon- and sulfur-containing systems was found within the investigated pressure range. To match the Ni abundance in terrestrial mantle olivine, assuming an equilibrium metal-olivine distribution, a sub-chondritic Fe/Ni-metal ratio that is a factor of 17 to 27 lower than the Fe/Ni ratios in estimated Earth core compositions would be required, implying higher Fe concentrations in the core forming metal phase. A simple metal-olivine equilibrium distribution does not seem to be feasible to explain the Ni abundances in the Earth's mantle. An equilibrium between metal and olivine does not exercise a control on the problem of Ni overabundance in the Earth's mantle. The experimental results do not contradict the presence of a magma ocean at the time of terrestrial core formation, if olivine was present in only minor amounts at the time of metal segregation.

  11. Precipitation of heavy metals from acid mine drainage and their geochemical modeling

    NASA Astrophysics Data System (ADS)

    Petrilakova, Aneta; Balintova, Magdalena; Holub, Marian

    2014-06-01

    Geochemical modeling plays an increasingly vital role in a number of areas of geoscience, ranging from groundwater and surface water hydrology to environmental preservation and remediation. Geochemical modeling is also used to model the interaction processes at the water - sediment interface in acid mine drainage (AMD). AMD contains high concentrations of sulfate and dissolved metals and it is a serious environmental problem in eastern Slovakia. The paper is focused on comparing the results of laboratory precipitation of metal ions from AMD (the Smolnik creek, Slovakia) with the results obtained by geochemical modeling software Visual Minteq 3.0.

  12. Potentiometric Determination of Phytic Acid and Investigations of Phytate Interactions with Some Metal Ions.

    PubMed

    Marolt, Gregor; Pihlar, Boris

    2015-01-01

    Determination of correct amount (concentration) of phytic acid is of vital importance when dealing with protonation and/or metal complexation equilibria. A novel approach for precise and reliable assay of phytic acid, based on the difference between end points by potentiometric titration, has been presented. Twelve phytic acid protons are classified into three groups of acidity, which enables detection of 2 to 3 distinct equivalent points (EPs) depending on experimental conditions, e.g. counter-ion concentration. Using the differences between individual EPs enables correct phytate determination as well as identification of potential contamination and/or determination of initial protonation degree. Impact of uncertainty of phytate amount on the calculation of protonation constants has been evaluated using computer simulation program (Hyperquad2013). With the analysis of titration curves different binding sites on phytate ligand have been proposed for complexation of Ca2+ and Fe3+ ions. PMID:26085413

  13. Modulation by Amino Acids: Toward Superior Control in the Synthesis of Zirconium Metal-Organic Frameworks.

    PubMed

    Gutov, Oleksii V; Molina, Sonia; Escudero-Adán, Eduardo C; Shafir, Alexandr

    2016-09-12

    The synthesis of zirconium metal-organic frameworks (Zr MOFs) modulated by various amino acids, including l-proline, glycine, and l-phenylalanine, is shown to be a straightforward approach toward functional-group incorporation and particle-size control. High yields in Zr-MOF synthesis are achieved by employing 5 equivalents of the modulator at 120 °C. At lower temperatures, the method provides a series of Zr MOFs with increased particle size, including many suitable for single-crystal X-ray diffraction studies. Furthermore, amino acid modulators can be incorporated at defect sites in Zr MOFs with an amino acid/ligand ratio of up to 1:1, depending on the ligand structure and reaction conditions. The MOFs obtained through amino acid modulation exhibit an improved CO2 -capture capacity relative to nonfunctionalized materials. PMID:27482849

  14. Sulfonic acids: catalysts for the liquid-liquid extraction of metals

    SciTech Connect

    Osseo-Asare, K.; Keeney, M.E.

    1980-05-01

    Three sulfonic acid extractants, dinonylnaphthalene sulfonic acid (HDNNS), didodecylnaphthalene sulfonic acid (HDDNS) and di-(2-ethyl-hexyl) sodium sulfosuccinate (Aerosol OT, AOT) are compared as to their effects on the extraction of nickel with LIX63. The acidic extractants interact synergistically with the oxime. Interfacial tension results are presented which demonstrate that the sulfonates form reversed micelles in non-polar organic solvents. It is proposed that the reversed micelles catalyze the extraction by specific solubilization of both the metal and the extractant, resulting in an increase in the interfacial concentration of the reacting species. The ability of LIX63 to chelate with nickel without deprotonating permits the synergism to occur at low pH.

  15. Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and...

  16. Microbial biofilms control economic metal mobility in an acid-sulfate hydrothermal system

    NASA Astrophysics Data System (ADS)

    Phillips-Lander, C. M.; Roberts, J. A.; Hernandez, W.; Mora, M.; Fowle, D. A.

    2012-12-01

    Trace metal cycling in hydrothermal systems has been the subject of a variety of geochemical and economical geology studies. Typically in these settings these elements are sequestered in sulfide and oxide mineral fractions, however in near-surface low-temperature environments organic matter and microorganisms (typically in mats) have been implicated in their mobility through sorption. Here we specifically examine the role of microbial biofilms on metal partitioning in an acid-sulfate hydrothermal system. We studied the influence of microorganisms and microbial biofilms on trace metal adsorption in Pailas de Aguas I, an acid-sulfate hot spring on the southwest flank of Rincon de la Vieja, a composite stratovolcano in the Guanacaste Province, Costa Rica. Spring waters contain high suspended loads, and are characterized by high T (79.6-89.3oC), low pH (2.6-4), and high ionic strengths (I= 0.5-0.8). Waters contain high concentrations of the biogeochemically active elements Fe (4-6 mmol/l) and SO42- (38 mmol/l), but PO43- are below detection limits (bdl). Silver, Ni, and Mo concentrations are bdl; however other trace metals are present in solution in concentrations of 0.1-0.2 mg/l Cd, 0.2-0.4 mg/l Cr and V, 0.04-1 mg/l Cu,. Preliminary 16S rRNA analyses of microorganisms in sediments reveal several species of algae, including Galderia sp., Cyanidium sp, γ-proteobacteria, Acidithiobacillus caldus, Euryarcheota, and methanogens. To evaluate microbial biofilms' impact on trace metal mobility we analyzed a combination of suspended, bulk and biofilm associated sediment samples via X-ray diffraction (XRD) and trace element sequential extractions (SE). XRD analysis indicated all samples were primarily composed of Fe/Al clay minerals (nontronite, kaolinite), 2- and 6-line ferrihydrite, goethite, and hematite, quartz, and opal-α. SE showed the highest concentrations of Cu, Mo, and V were found in the suspended load. Molybdenum was found primarily in the residual and organic

  17. Ordering in non-stoichiometric carbides of niobium and tantalum

    SciTech Connect

    Markhasev, B.I.; Pilipovskii, Yu. L.; Shamatov, Yu. M.; Svintsova, S.E.

    1986-03-01

    Ordering processes were studied in the nonstoichiometric carbides of Nb and Ta. A mechanism of slip transition was proposed for the ordering of NbC/sub 2/, accompanied by precipitation of niobium metal. A diagram of the restructuring of the fcc lattice of NbC to the bcc lattice of Nb is presented.

  18. Carbide-fluoride-silver self-lubricating composite

    NASA Technical Reports Server (NTRS)

    Sliney, Harold E. (Inventor)

    1987-01-01

    A self-lubricating, friction and wear reducing composite material is described for use over a wide temperature spectrum from cryogenic temperature to about 900 C in a chemically reactive environment comprising silver, barium fluoride/calcium fluoride eutectic, and metal bonded chromium carbide.

  19. Carbide/fluoride/silver self-lubricating composite

    NASA Technical Reports Server (NTRS)

    Sliney, Harold E. (Inventor)

    1988-01-01

    A self-lubricating, friction and wear reducing composite material for use over a wide temperature spectrum from cryogenic temperature to about 900.degree. C. in a chemically reactive environment comprising silver, barium fluoride/calcium fluoride eutectic, and metal bonded chromium carbide.

  20. Evaluation of the role of reactive oxygen species in the interactive toxicity of carbide-cobalt mixtures on macrophages in culture.

    PubMed

    Lison, D; Lauwerys, R

    1993-01-01

    The lung toxicity of a carbide-cobalt mixture is more important than that of each individual component; the mechanism of this interaction is not understood. The capacity of cobalt metal particles alone and mixed with different carbides to generate hydroxyl radicals was examined with the deoxyribose assay. In a chemical system, cobalt ions and cobalt metal particles (Co) were found to catalyse the degradation of deoxyribose in the presence of hydrogen peroxide. Carbides were able to directly oxidize deoxyribose, but their respective activities did not support such a mechanism to explain the carbide-cobalt interactive toxicity, since there was no direct relationship between deoxyribose degradation ability and cytotoxicity toward macrophages. Tungsten, niobium, titanium and chromium carbides (interactive carbides) were only weak oxidants and conversely molybdenum, vanadium and silicon carbides (non-interactive carbides) were the most potent ones. The ability of cobalt metal to produce hydroxyl radicals in the presence of hydrogen peroxide was not increased by tungsten carbide. The role of reactive radical formation in the toxicity of these particles was further assessed in a macrophage culture model. Catalase (4000 U/ml), superoxide dismutase (300 U/ml), sodium azide (1 mM), sodium benzoate, mannitol, taurine and methionine (all 20 mM) were all unable to protect against the cytotoxic effects of cobalt ions and cobalt metal alone or mixed with tungsten carbide. In conclusion, no evidence was found that production of reactive oxygen species contributes to the elective toxicity of carbide-cobalt mixtures. PMID:8396391

  1. Boron carbide-aluminum cermets

    SciTech Connect

    Halverson, D.C.

    1986-09-03

    We have developed boron carbide-aluminum cermets by means of thermodynamic, kinetic, and processing studies. Our research indicates that boron carbide-aluminum cermets offer ''tailorable'' microstructures with designable properties through process control. This new class of cermets has the potential to become a very important material with wide industrial applications.

  2. Coordination Behavior of 3-Ethoxycarbonyltetronic Acid towards Cu(II) and Co(II) Metal Ions

    PubMed Central

    Athanasellis, Giorgos; Zahariou, Georgia; Kikionis, Stefanos; Igglessi-Markopoulou, Olga; Markopoulos, John

    2008-01-01

    Tetronic acids, 4-hydroxy-5H-furan-2-ones, constitute a class of heterocyclic compounds with potent biological and pharmacological activity. The β, β′-tricarbonyl moiety plays an integral role in biological systems and forms a variety of metal complexes. In this report, we present the complexation reactions of 3-ethoxycarbonyl tetronic acids with acetates and chlorides of Cu(II) and Co(II). These complexes have been studied by means of EPR spectroscopy and magnetic susceptibility measurements. From the obtained results, a preliminary complexation mode of the ligand is proposed. PMID:19197392

  3. Heavy metal speciation and acid treatment of activated sludge developed in a membrane bioreactor.

    PubMed

    Daskalakis, N; Katsou, E; Malamis, S; Haralambous, K J

    2013-01-01

    The aim of this study was to identify the heavy metals forms (exchangeable and bound to carbonate, Fe/Mn oxides, bound to organic matter and sulphide, and residual) associated with different fractions of excess sludge produced by a membrane bioreactor (MBR). Furthermore, the release of metals from the sludge to the liquid was investigated by applying acid treatment using 10% (v/v) H2SO4 (T = 25 degrees C, solid-liquid ratio 1:5 w/v) for contact time ranging from 15 min to 4 h. Metal partitioning in sludge, as determined by the sequential chemical extraction showed that the dominant form of both Ni and Zn was bound to the exchangeable and carbonate fraction; the latter were very unstable and sensitive to environmental conditions. The dominant Cu fraction was bound to organic matter and sulphide, while Pb was found to be mainly in the residual fraction which is very stable. Metal speciation after acidification with H2SO4 indicates changes of metal content in sludge and an increase of the exchangeable and bound to carbonate fraction for all metals except Cu. Acidification resulted in removal of 82% for Ni, 78% for Zn, 47% for Cu and 45% for Pb. PMID:24527621

  4. Processing of boron carbide-aluminum composites

    SciTech Connect

    Halverson, D.C. ); Pyzik, A.J.; Aksay, I.A. . Dept. of Materials Science and Engineering); Snowden, W.E. )

    1989-05-01

    The processing problems associated with boron carbide and the limitations of its mechanical properties can be significantly reduced when a metal phase (e.g., aluminum) is added. Lower densification temperatures and higher fracture toughness will result. Based on fundamental capillarity thermodynamics, reaction thermodynamics, and densification kinetics, we have established reliable criteria for fabricating B{sub 4}C-Al particulate composites. Because chemical reactions cannot be eliminated, it is necessary to process B{sub 4}C-Al by rapidly heating to near 1200{degrees} C (to ensure wetting) and subsequently heat-treating below 1200{degrees} C (for microstructural development).

  5. METHOD FOR COATING GRAPHITE WITH NIOBIUM CARBIDE

    DOEpatents

    Kane, J.S.; Carpenter, J.H.; Krikorian, O.H.

    1962-01-16

    A method is given for coating graphite with a hard, tenacious layer of niobium carbide up to 30 mils or more thick. The method makes use of the discovery that niobium metal, if degassed and heated rapidly below the carburization temperature in contact with graphite, spreads, wets, and penetrates the graphite without carburization. The method includes the obvious steps of physically contacting niobium powders or other physical forms of niobium with graphite, degassing the assembly below the niobium melting point, e.g., 1400 deg C, heating to about 2200 to 2400 deg C within about 15 minutes while outgassing at a high volume throughput, and thereafter carburizing the niobium. (AEC)

  6. Metal ion-humic acid nanoparticle interactions: role of both complexation and condensation mechanisms.

    PubMed

    Town, Raewyn M; van Leeuwen, Herman P

    2016-07-21

    Purely Donnan type models for electrostatic binding by humic acid (HA) nanoparticles are shown to be physically incomplete. To describe the extent of ion binding by HA, such models need to invoke parameters that are not consistent with experimental observations. These disparate parameters include anomalously high Donnan potentials, as well as intrinsic affinity constants for electrostatically associating ions such as Ca(2+). In contrast, the recently introduced counterion condensation - Donnan model (CCD) provides a physicochemically realistic description of the electrostatic contribution to metal ion binding by humic acid nanoparticles. The extent of Ca(2+)-HA association can be adequately described solely in terms of electrostatics only, including counterion condensation in the intraparticulate double layer in addition to Donnan partitioning in the remainder of the particle body. The binding of Cd(ii), Pb, (ii) and Cu(ii) by HA also involves inner-sphere complex formation leading to intraparticulate metal species distributions with major proportions of condensed and complexed ions. PMID:27327433

  7. Transition-Metal-Free ipso-Functionalization of Arylboronic Acids and Derivatives

    PubMed Central

    Zhu, Chen; Falck, John R.

    2014-01-01

    Arylboronic acids and their derivatives have been widely exploited as important synthetic precursors in organic synthesis, materials science, and pharmaceutical development. In addition to numerous applications in transition-metal-mediated cross-coupling reactions, transition-metal-free transformations involving arylboronic acids and derivatives have recently received a surge of attention for converting the C-B bond to C-C, C-N, C-O, and many other C-X bonds. Consequently, a wide range of useful compounds, e.g., phenols, anilines, nitroarenes, and haloarenes, have been readily synthesized. Amongst these efforts, many versatile reagents have been developed and a lot of practical approaches demonstrated. The research in this promising field is summarized in the current review and organized on the basis of the type of bonds being formed. PMID:25414624

  8. Secondary sulfate minerals associated with acid drainage in the eastern US: Recycling of metals and acidity in surficial environments

    USGS Publications Warehouse

    Hammarstrom, J.M.; Seal, R.R., II; Meier, A.L.; Kornfeld, J.M.

    2005-01-01

    spells. Despite the relatively humid climate of the eastern United States, where precipitation typically exceeds evaporation, salts form intermittently in open areas, persist in protected areas when temperature and relative humidity are appropriate, and contribute to metal loadings and acidity in surface waters upon dissolution, thereby causing short-term perturbations in water quality.

  9. Biogenic precipitation of manganese oxides and enrichment of heavy metals at acidic soil pH

    NASA Astrophysics Data System (ADS)

    Mayanna, Sathish; Peacock, Caroline L.; Schäffner, Franziska; Grawunder, Anja; Merten, Dirk; Kothe, Erika; Büchel, Georg

    2014-05-01

    The precipitation of biogenic Mn oxides at acidic pH is rarely reported and poorly understood, compared to biogenic Mn oxide precipitation at near neutral conditions. Here we identified and investigated the precipitation of biogenic Mn oxides in acidic soil, and studied their role in the retention of heavy metals, at the former uranium mining site of Ronneburg, Germany. The site is characterized by acidic pH, low carbon content and high heavy metal loads including rare earth elements. Specifically, the Mn oxides were present in layers identified by detailed soil profiling and within these layers pH varied from 4.7 to 5.1, Eh varied from 640 to 660 mV and there were enriched total metal contents for Ba, Ni, Co, Cd and Zn in addition to high Mn levels. Using electron microprobe analysis, synchrotron X-ray diffraction and X-ray absorption spectroscopy, we identified poorly crystalline birnessite (δ-MnO2) as the dominant Mn oxide in the Mn layers, present as coatings covering and cementing quartz grains. With geochemical modelling we found that the environmental conditions at the site were not favourable for chemical oxidation of Mn(II), and thus we performed 16S rDNA sequencing to isolate the bacterial strains present in the Mn layers. Bacterial phyla present in the Mn layers belonged to Firmicutes, Actinobacteria and Proteobacteria, and from these phyla we isolated six strains of Mn(II) oxidizing bacteria and confirmed their ability to oxidise Mn(II) in the laboratory. The biogenic Mn oxide layers act as a sink for metals and the bioavailability of these metals was much lower in the Mn layers than in adjacent layers, reflecting their preferential sorption to the biogenic Mn oxide. In this presentation we will report our findings, concluding that the formation of natural biogenic poorly crystalline birnessite can occur at acidic pH, resulting in the formation of a biogeochemical barrier which, in turn, can control the mobility and bioavailability of heavy metals in

  10. Formation Energies and Electronic Properties of Vanadium Carbides Found in High Strength Steel Alloys

    NASA Astrophysics Data System (ADS)

    Limmer, Krista; Medvedeva, Julia

    2013-03-01

    Carbide formation and stabilization in steels is of great interest owing to its effect on the microstructure and properties of the Fe-based alloys. The appearance of carbides with different metal/C ratios strongly depends on the carbon concentration, alloy composition as well as the heat treatment. Strong carbide-forming elements such as Ti, V, and Nb have been used in microalloyed steels; with VC showing an increased solubility in the iron matrix as compared with TiC and NbC. This allows for dissolution of the VC into the steel during heating and fine precipitation during cooling. In addition to VC, the primary vanadium carbide with cubic structure, a wide range of non-stoichiometric compositions VCy with y varying from 0.72 to 0.88, has been observed. This range includes two ordered compounds, V8C7 and V6C5. In this study, first-principles density functional theory (DFT) is employed to examine the stability of the binary carbides by calculating their formation energies. We compare the local structures (atomic coordination, bond distances and angles) and the density of states in optimized geometries of the carbides. Further, the effect of alloying additions, such as niobium and titanium, on the carbide stabilization is investigated. We determine the energetically preferable substitutional atom location in each carbide and study the impurity distribution as well as its role in the carbide formation energy and electronic structure.

  11. Extraterrestrial Amino Acids Identified in Metal-Rich CH and CB Carbonaceous Chondrites from Antarctica

    NASA Technical Reports Server (NTRS)

    Burton, Aaron S.; Elsila, Jamie E.; Hein, Jason E.; Glavin, Daniel P.; Dworkin, Jason P.

    2013-01-01

    Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondritesbut are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal-rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment(PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675(CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time-of-flight mass spectrometry and fluorescence, and gas chromatography isotope ratiomass spectrometry. The (delta D, delta C-13, delta N-15) ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (1316 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.22 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of beta-, gamma-, and delta-amino acids compared to the corresponding alpha-amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.

  12. Extraterrestrial amino acids identified in metal-rich CH and CB carbonaceous chondrites from Antarctica

    NASA Astrophysics Data System (ADS)

    Burton, Aaron S.; Elsila, Jamie E.; Hein, Jason E.; Glavin, Daniel P.; Dworkin, Jason P.

    2013-03-01

    Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondrites but are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal-rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment (PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675 (CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time-of-flight mass spectrometry and fluorescence, and gas chromatography isotope ratio mass spectrometry. The δ13C/12C ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (13-16 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.2-2 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of β-, γ-, and δ-amino acids compared to the corresponding α-amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.

  13. Acid neutralization mechanisms and metal release in mine tailings: a laboratory column experiment

    NASA Astrophysics Data System (ADS)

    Jurjovec, Jasna; Ptacek, Carol J.; Blowes, David W.

    2002-05-01

    Mining and milling of base metal ore deposits can result in the release of metals to the environment. When sulfide minerals contained in mine tailings are exposed to oxygen and water, they oxidize and dissolve. Two principal antagonistic geochemical processes affect the migration of dissolved metals in tailings impoundments: sulfide oxidation and acid neutralization. This study focuses on acid neutralization reactions occurring in the saturated zone of tailings impoundments. To simulate conditions prevailing in many tailings impoundments, 0.1 mol/L sulfuric acid was passed continuously through columns containing fresh, unoxidized tailings, collected at Kidd Creek metallurgical site. The results of this column experiment represent a detailed temporal observation of pH, Eh, and metal concentrations. The results are consistent with previous field observations, which suggest that a series of mineral dissolution-precipitation reactions control pH and metal mobility. Typically, the series consists of carbonate minerals, Al and Fe(III) hydroxides, and aluminosilicates. In the case of Kidd Creek tailings, the dissolution series consists of ankerite-dolomite, siderite, gibbsite, and aluminosilicates. In the column experiment, three distinct pH plateaus were observed: 5.7, 4.0, and 1.3. The releases of trace elements such as Cd, Co, Cr, Cu, Li, Ni, Pb, V, and Zn were observed to be related to the pH buffering zones. High concentrations of Zn, Ni, and Co were observed at the first pH plateau (pH 5.7), whereas Cd, Cr, Pb, As, V, and Al were released as the pH of the pore water decreased to 4.0 or less.

  14. Osteoinduction on acid and heat treated porous Ti metal samples in canine muscle.

    PubMed

    Kawai, Toshiyuki; Takemoto, Mitsuru; Fujibayashi, Shunsuke; Akiyama, Haruhiko; Tanaka, Masashi; Yamaguchi, Seiji; Pattanayak, Deepak K; Doi, Kenji; Matsushita, Tomiharu; Nakamura, Takashi; Kokubo, Tadashi; Matsuda, Shuichi

    2014-01-01

    Samples of porous Ti metal were subjected to different acid and heat treatments. Ectopic bone formation on specimens embedded in dog muscle was compared with the surface characteristics of the specimen. Treatment of the specimens by H2SO4/HCl and heating at 600 °C produced micrometer-scale roughness with surface layers composed of rutile phase of titanium dioxide. The acid- and heat-treated specimens induced ectopic bone formation within 6 months of implantation. A specimen treated using NaOH followed by HCl acid and then heat treatment produced nanometer-scale surface roughness with a surface layer composed of both rutile and anatase phases of titanium dioxide. These specimens also induced bone formation after 6 months of implantation. Both these specimens featured positive surface charge and good apatite-forming abilities in a simulated body fluid. The amount of the bone induced in the porous structure increased with apatite-forming ability and higher positive surface charge. Untreated porous Ti metal samples showed no bone formation even after 12 months. Specimens that were only heat treated featured a smooth surface composed of rutile. A mixed acid treatment produced specimens with micrometer-scale rough surfaces composed of titanium hydride. Both of them also showed no bone formation after 12 months. The specimens that showed no bone formation also featured almost zero surface charge and no apatite-forming ability. These results indicate that osteoinduction of these porous Ti metal samples is directly related to positive surface charge that facilitates formation of apatite on the metal surfaces in vitro. PMID:24520375

  15. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes.

    PubMed

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M Arif

    2016-05-15

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica. PMID:26945123

  16. Synthesis, spectral studies and biological evaluation of 2-aminonicotinic acid metal complexes

    NASA Astrophysics Data System (ADS)

    Nawaz, Muhammad; Abbasi, Muhammad Waseem; Hisaindee, Soleiman; Zaki, Muhammad Javed; Abbas, Hira Fatima; Mengting, Hu; Ahmed, M. Arif

    2016-05-01

    We synthesized 2-aminonicotinic acid (2-ANA) complexes with metals such as Co(II), Fe(III), Ni(II), Mn(II), Zn(II), Ag(I),Cr(III), Cd(II) and Cu(II) in aqueous media. The complexes were characterized and elucidated using FT-IR, UV-Vis, a fluorescence spectrophotometer and thermo gravimetric analysis (TGA). TGA data showed that the stoichiometry of complexes was 1:2 metal/ligand except for Ag(I) and Mn(II) where the ratio was 1:1. The metal complexes showed varied antibacterial, fungicidal and nematicidal activities. The silver and zinc complexes showed highest activity against Bacillus subtilis and Bacillus licheniformis respectively. Fusarium oxysporum was highly susceptible to nickel and copper complexes whereas Macrophomina phaseolina was completely inert to the complexes. The silver and cadmium complexes were effective against the root-knot nematode Meloidogyne javanica.

  17. Inhibition of iron corrosion in 0.5 M sulphuric acid by metal cations

    NASA Astrophysics Data System (ADS)

    Sathiyanarayanan, S.; Jeyaprabha, C.; Muralidharan, S.; Venkatachari, G.

    2006-09-01

    Corrosion inhibitors are widely used in acid solutions during pickling and descaling. Mostly organic compounds containing N, O, and S groups are employed as inhibitors. In this study, the inhibition performance of metal cations such as Zn 2+, Mn 2+ and Ce 4+ ions in the concentration range 1-10 × 10 -3 M has been found out. The corrosion behaviour of iron in 0.5 M H 2SO 4 in the presence of metal cations is studied using polarization and impedance methods. It is found that the addition of these metal cations inhibits the corrosion markedly. The inhibition effect is in the following order Ce 4+ ≫ Mn 2+ > Zn 2+.

  18. Influence of Source/Drain Residual Implant Lattice Damage Traps on Silicon Carbide Metal Semiconductor Field-Effect Transistor Drain I-V Characteristics

    NASA Astrophysics Data System (ADS)

    Adjaye, J.; Mazzola, M. S.

    4H-SiC n-channel power metal semiconductor field-effect transistors (MESFETs) with nitrogen n+-implanted source/drain ohmic contact regions, with and without p-buffer layer fabricated on semi-insulating substrates exhibited hysteresis in the drain I-V characteristics of both types of devices at 300 K and 480 K due to traps. However, thermal spectroscopic measurements could detect the traps only in the devices without p-buffer. Device simulation and optical admittance spectroscopy (OAS) are used to resolve the discrepancy in the initial experimental characterization results. Device simulations and OAS suggest that, in addition to the semi-insulating (SI) substrate traps, acceptor traps due to source/drain residual implant lattice damage contribute to the hysteresis observed in the drain I-V characteristics of the devices. Simulations suggest these traps are contained in the lateral straggle of the implanted source and drain regions since the drain current largely flows between the un-gated edges of the source and drain through the volume of lateral straggle traps. Since hysteresis in I-V curves is a manifestation of the presence of defects in devices and since defects degrade carrier mobility and hence device performance, efforts should be made to minimize the source/drain lateral straggle implant damage.

  19. Solubilization of manganese and trace metals in soils affected by acid mine runoff.

    PubMed

    Green, C H; Heil, D M; Cardon, G E; Butters, G L; Kelly, E F

    2003-01-01

    Manganese solubility has become a primary concern in the soils and water supplies in the Alamosa River basin, Colorado due to both crop toxicity problems and concentrations that exceed water quality standards. Some of the land in this region has received inputs of acid and trace metals as a result of irrigation with water affected by acid mine drainage and naturally occurring acid mineral seeps. The release of Mn, Zn, Ni, and Cu following saturation with water was studied in four soils from the Alamosa River basin. Redox potentials decreased to values adequate for dissolution of Mn oxides within 24 h following saturation. Soluble Mn concentrations were increased to levels exceeding water quality standards within 84 h. Soluble concentrations of Zn and Ni correlated positively with Mn following reduction for all four soils studied. The correlation between Cu and Mn was significant for only one of the soils studied. The soluble concentrations of Zn and Ni were greater than predicted based on the content of each of these metals in the Mn oxide fraction only. Increases in total electrolyte concentration during reduction indicate that this may be the result of displacement of exchangeable metals by Mn following reductive dissolution of Mn oxides. PMID:12931888

  20. Impact of catalyst metal-acid balance in n-hexadecane hydroisomerization and hydrocracking

    SciTech Connect

    Girgis, M.J.; Tsao, Y.P.

    1996-02-01

    The reaction pathways and kinetics of n-hexadecane hydroisomerization and hydrocracking were determined in the presence of each of three platinum-containing dual-function catalysts: (a) Pt on a proprietary zeolite (Pt/Z), (b) Pt on silica-alumina (Pt/Si-Al), and (c) Pt on MCM-41 (Pt/MCM-41). The reaction networks were used to interpret differences in isomerization selectivity. The low isomerization selectivity observed in the presence of Pt/Si-Al was shown to be a consequence of changes in both relative isomerization/cracking rates and reaction pathways. Using the classical bifunctional reaction scheme, the changes in pathway were hypothesized to be consistent with changes in the relative concentrations of metal and acid sites (i.e., the metal-acid balance). On the basis of a recently proposed model of dual-function catalysis, the different observed pathways were subsequently shown to be those expected in two limiting cases of the metal-acid balance. The simplified quantitative picture given here provides a preliminary basis for relating catalyst preparation variables to catalyst performance for dual-function catalysts.

  1. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts.

    PubMed

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S; Kumta, Prashant N

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  2. Preparation of metal-resistant immobilized sulfate reducing bacteria beads for acid mine drainage treatment.

    PubMed

    Zhang, Mingliang; Wang, Haixia; Han, Xuemei

    2016-07-01

    Novel immobilized sulfate-reducing bacteria (SRB) beads were prepared for the treatment of synthetic acid mine drainage (AMD) containing high concentrations of Fe, Cu, Cd and Zn using up-flow anaerobic packed-bed bioreactor. The tolerance of immobilized SRB beads to heavy metals was significantly enhanced compared with that of suspended SRB. High removal efficiencies of sulfate (61-88%) and heavy metals (>99.9%) as well as slightly alkaline effluent pH (7.3-7.8) were achieved when the bioreactor was fed with acidic influent (pH 2.7) containing high concentrations of multiple metals (Fe 469 mg/L, Cu 88 mg/L, Cd 92 mg/L and Zn 128 mg/L), which showed that the bioreactor filled with immobilized SRB beads had tolerance to AMD containing high concentrations of heavy metals. Partially decomposed maize straw was a carbon source and stabilizing agent in the initial phase of bioreactor operation but later had to be supplemented by a soluble carbon source such as sodium lactate. The microbial community in the bioreactor was characterized by denaturing gradient gel electrophoresis (DGGE) and sequencing of partial 16S rDNA genes. Synergistic interaction between SRB (Desulfovibrio desulfuricans) and co-existing fermentative bacteria could be the key factor for the utilization of complex organic substrate (maize straw) as carbon and nutrients source for sulfate reduction. PMID:27058913

  3. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    DOE PAGESBeta

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-06

    We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM basedmore » systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.« less

  4. Adsorptions of some heavy metal ions in aqueous solutions by acrylamide/maleic acid hydrogels

    SciTech Connect

    Saraydin, D.; Karadag, E.; Gueven, O.

    1995-10-01

    In this study, acrylamide-maleic acid (AAm/MA) hydrogels in the form of rod have been prepared by {gamma}-radiation. They have been used for adsorption of some heavy metal ions such as uranium, iron, and copper. For the hydrogel containing 40 mg of maleic acid and irradiated at 3.73 kGy, maximum and minimum swellings in the aqueous solutions of the heavy metal ions have been observed with water (1480%) and the aqueous solution of iron(III) nitrate (410%), respectively. Diffusions of water and heavy metal ions onto hydrogels have been found to be of the non-Fickian type of diffusion. In experiments of uranyl ions adsorption, Type II adsorption has been found. One gram of AAa/MA hydrogels sorbed 14-86 mg uranyl ions from solutions of uranyl acetate, 14-90 mg uranyl ions from solutions of uranyl nitrate, 16-39 mg iron ions from solutions of iron(IV) nitrate, and 28-81 mg copper ions from solutions of copper acetate, while acrylamide hydrogel did not sorb any heavy metals ions.

  5. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    NASA Astrophysics Data System (ADS)

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.

  6. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    PubMed Central

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-01-01

    Identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Herein we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM based systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations. PMID:27380719

  7. Catalytic carbide formation at aluminium-carbon interfaces

    NASA Technical Reports Server (NTRS)

    Maruyama, B.; Rabenberg, L.; Ohuchi, F. S.

    1990-01-01

    X-ray photoelectron spectroscopy investigations of the reaction of several monolayer-thick films of aluminum with glassy carbon substrates are presented. The influence of molecular oxygen and water vapor on the rate of reaction is examined. It is concluded that water vapor catalyzed the formation of aluminum carbide from aluminum and carbon by forming active sites which weakened carbon-carbon bonds at the glassy carbon surface, thus assisting their cleavage. The rate of carbide formation for undosed and molecular oxygen-dosed examples was less as neither metallic aluminum nor oxygen-formed alumina could bond to the carbon atom with sufficient strength to dissociate it quickly.

  8. A case study in the treatment of spent pickling acids for fluoride compliance at a metals finishing facility

    SciTech Connect

    Francis, J.T.; Walters, J.; Evans, D.

    1995-12-31

    A metal finishing facility located in the Los Angeles area processes coiled steel sheets (300 and 400 series) and other sheet metal alloys by annealing, pickling and cold rolling operations. The facility acquires steel from large manufacturers or mills and finishes to a prescribed thickness, hardness, and grade depending on customers needs, for sale to metal product manufacturers such as can manufacturers and prefabricated steel building industries. Specialty metal alloys such as nickel-cobalt or titanium are also processed for use in aerospace industry applications. The facility produces about 10,000 tons of metal sheets per year and in the process generates about 40,000 gallons per day (gpd) of wastewater that is pretreated for metals removal and discharged to the sewer. About 30,000 gallons per month of spent acid are generated--much of which is used for pH adjustment in the pretreatment system. Acids of concern are sulfuric acid, hydrofluoric acid and nitric acid. The wastewater treatment system (WWTS) is equipped for chromium reduction and metals precipitation and handles the wastewater, the spent acids and other alkaline wastes generated at the facility. An estimated 50 tons of hazardous waste sludge are generated and disposed of on a monthly basis.

  9. Effect of amino acids on the toxicity of heavy metals to phytoplankton

    SciTech Connect

    Kosakowska, A.; Falkowski, L.; Lewandowska, J.

    1988-04-01

    Sea water contains free amino acids in concentrations ranging from 20 to 100 ..mu..g dm/sup -3/. The most abundant representatives of this group of compounds in the surface water were found to be glycine, serine and ornithine. The amino acids are utilized in the phytoplankton cells as the source of nitrogen as well as carbon in the case of slow rate of photosynthesis. Heavy metals distribution in the sea water can be indispensable or delitorious for the organisms living in that environment depending on their concentration and speciation. The bioavailability as well as toxicity of the elements are strongly influenced by the organic matter dissolved in water. The effect of a number of organic compounds, including amino acids, on the toxicity of heavy metals was tested, but there were no reports elucidating compounds representing various types of structure. This paper deals with the effect of amino acids representing various structure groups on the toxicity of copper, cadmium and mercury against to Chlorella vulgaris and Anabeana variabilis.

  10. Methods of producing continuous boron carbide fibers

    SciTech Connect

    Garnier, John E.; Griffith, George W.

    2015-12-01

    Methods of producing continuous boron carbide fibers. The method comprises reacting a continuous carbon fiber material and a boron oxide gas within a temperature range of from approximately 1400.degree. C. to approximately 2200.degree. C. Continuous boron carbide fibers, continuous fibers comprising boron carbide, and articles including at least a boron carbide coating are also disclosed.

  11. Environmental effects and desorption characteristics on heavy metal removal using carboxylated alginic acid.

    PubMed

    Jeon, Choong; Je Yoo, Young; Hoell, Wolfgang H

    2005-01-01

    Effects of ionic strength and organic materials on copper ion uptake capacity using carboxylated alginic acid which showed very high metal ion uptake capacity were investigated. The ionic strength only had a slight effect on the decrease of copper ion uptake capacity regardless of NaCl concentration. And, the effect of organic materials such as NTA (nitrilotriaceticacid) and sodium hypophosphite on the copper ion uptake capacity was negligible. When the lead ion adsorbed on carboxylated alginic acid was desorbed by NTA, which showed high desorption efficiency, the best optimum concentration of NTA was about 0.01 M. Also desorption efficiency decreased, however, concentration factor increased as S/L ratio which is defined as the ratio of adding amount of adsorbed and volume of desorbing agent increased. In sequential adsorption and desorption cycles, the lead uptake capacity on carboxylated alginic acid was relatively maintained through cycles 1-5. PMID:15364075

  12. Non-enzymic phosphorylation of polyphosphoinositides and phosphatidic acid is catalysed by bivalent metal ions.

    PubMed Central

    Gumber, S C; Lowenstein, J M

    1986-01-01

    Phosphatidylinositol 4-phosphate, phosphatidylinositol 4,5-bisphosphate and phosphatidic acid undergo non-enzymic phosphorylation by ATP in the presence of bivalent metal ions. The non-enzymic reaction is more rapid in a mixture of water, chloroform and methanol than in water alone. Chemical evidence indicates that the product formed from phosphatidylinositol 4-phosphate is the corresponding 4-pyrophosphate. This product shows an RF value very close to that of phosphatidylinositol 4,5-bisphosphate on t.l.c. with an acidic solvent commonly used to characterize and measure the latter; however, it can be separated readily with an alkaline solvent. Chemical evidence indicates that the products formed from phosphatidylinositol 4,5-bisphosphate and phosphatidic acid are also pyrophosphates. Images Fig. 1. Fig. 2. PMID:3017309

  13. Effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Hirai, Nobumitsu; Yamamoto, Yui

    2015-10-01

    The effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution has been investigated. It was found that "the specific anodic oxidation peak" appears at the cathodic scan in cyclic voltammogram of lead electrode in sulfuric acid solution containing Li2SO4, K2SO4, Na2SO4, Rb2SO4, or Cs2SO4. The height of the specific anodic oxidation peak varies with the alkaline sulfate in the solution; K2SO4 >> Na2SO4 > Cs2SO4 > Rb2SO4 > Li2SO4. It should be note that alkaline ions exist in lead sulfate formed on lead electrode in sulfuric acid solution containing potassium sulfate when the electrode was immersed in the solution at the rest potential for more than 1 h.

  14. Dissolution Process of Palladium in Hydrochloric Acid: A Route via Alkali Metal Palladates

    NASA Astrophysics Data System (ADS)

    Kasuya, Ryo; Miki, Takeshi; Morikawa, Hisashi; Tai, Yutaka

    2015-12-01

    To improve the safety of the Pd recovery processes that use toxic oxidizers, dissolution of Pd in hydrochloric acid with alkali metal palladates was investigated. Alkali metal palladates were prepared by calcining a mixture of Pd black and alkali metal (Li, Na, and K) carbonates in air. Almost the entire amount of Pd was converted into Li2PdO2 after calcination at 1073 K (800 °C) using Li2CO3. In contrast, PdO was obtained by calcination at 1073 K (800 °C) using Na and K carbonates. Our results indicated that Li2CO3 is the most active reagent among the examined alkali metal carbonates for the formation of palladates. In addition, dissolution of the resulting Li2PdO2 in HCl solutions was evaluated under various conditions. In particular, Li2PdO2 rapidly dissolved in diluted (0.1 M) HCl at ambient temperature. Solubility of Pd of Li2PdO2 was found to be 99 pct or larger after dissolution treatment at 353 K (80 °C) for 5 minutes; in contrast, PdO hardly dissolved in 0.1 M HCl. The dissolution mechanism of Li2PdO2 in HCl was also elucidated by analysis of crystal structures and particulate properties. Since our process is completely free from toxic oxidizers, the dissolution process via alkali metal palladates is much safer than currently employed methods.

  15. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity.

    PubMed

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-01-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment. PMID:26593782

  16. Effects of metal cations and fulvic acid on the adsorption of ciprofloxacin onto goethite.

    PubMed

    Tan, Yinyue; Guo, Yong; Gu, Xueyuan; Gu, Cheng

    2015-01-01

    Ciprofloxacin (CIP) can be strongly adsorbed by ferric oxides, but some influencing factors, such as multivalent cations and soil organic matter, have not been evaluated extensively. In this study, the interaction between CIP and four divalent metals (Ca, Cd, Cu, and Pb) was investigated using potentiometric titration and the results indicated that CIP can bind to the divalent metals in the following affinity order: Cu(II) > Pb(II) > Cd(II) > Ca(II). The effects of metals and fulvic acid (FA) on the adsorption behavior of CIP onto goethite surfaces were also examined using batch experiments. It was found that metal cations enhanced the CIP retention on goethite surfaces in the same order as the affinity order with CIP, indicating that metals likely increased CIP retention through cation bridging. FA was found to promote CIP sorption rather than compete with it, and the coexistence of FA and Cu(II) in the system exhibited an addictive effect with CIP sorption, indicating that they might influence the sorption separately under the studied loading condition. Taken together, our results suggested that the coexistence of divalent cations or soil organic matter will enhance CIP sorption on goethite surfaces, hence reducing its mobility and bioavailability in the environment. PMID:25096489

  17. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity

    PubMed Central

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-01-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment. PMID:26593782

  18. Heavy metal removal from sewage sludge ash by thermochemical treatment with gaseous hydrochloric acid.

    PubMed

    Vogel, Christian; Adam, Christian

    2011-09-01

    Sewage sludge ash (SSA) is a suitable raw material for fertilizers due to its high phosphorus (P) content. However, heavy metals must be removed before agricultural application and P should be transferred into a bioavailable form. The utilization of gaseous hydrochloric acid for thermochemical heavy metal removal from SSA at approximately 1000 °C was investigated and compared to the utilization of alkaline earth metal chlorides. The heavy metal removal efficiency increased as expected with higher gas concentration, longer retention time and higher temperature. Equivalent heavy metal removal efficiency were achieved with these different Cl-donors under comparable conditions (150 g Cl/kg SSA, 1000 °C). In contrast, the bioavailability of the P-bearing compounds present in the SSA after thermal treatment with gaseous HCl was not as good as the bioavailability of the P-bearing compounds formed by the utilization of magnesium chloride. This disadvantage was overcome by mixing MgCO(3) as an Mg-donor to the SSA before thermochemical treatment with the gaseous Cl-donor. A test series under systematic variation of the operational parameters showed that copper removal is more depending on the retention time than the removal of zinc. Zn-removal was declined by a decreasing ratio of the partial pressures of ZnCl(2) and water. PMID:21819089

  19. Pilot test of pollution control and metal resource recovery for acid mine drainage.

    PubMed

    Yan, Bo; Mai, Ge; Chen, Tao; Lei, Chang; Xiao, Xianming

    2015-01-01

    The study was undertaken in order to recover the metal resources from acid mine drainage (AMD). A 300 m(3)/d continuous system was designed and fractional precipitation technology employed for the main metals Fe, Cu, Zn, and Mn recovery. The system was operated for six months using actual AMD in situ. The chemicals' input and also the retention time was optimized. Furthermore, the material balance was investigated. With the system, the heavy metals of the effluent after the Mn neutralization precipitation were below the threshold value of the Chinese integrated wastewater discharge limit. The precipitates generated contained 42%, 12%, 31%, and 18% for Fe, Cu, Zn, and Mn, respectively, and the recovery rates of Fe, Cu, Zn, and Mn were 82%, 79%, 83%, and 83%, respectively. The yield range of the precipitate had significant correlation with the influent metal content. Using the X-ray diffraction analysis, the refinement for Fe, Cu, and Zn could be achieved through the processes of roasting and floatation. Cost-benefit was also discussed; the benefit from the recycled metal was able to pay for the cost of chemical reagents used. Most important of all, through the use of this technology, the frustrating sludge problems were solved. PMID:26676020

  20. Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity

    NASA Astrophysics Data System (ADS)

    Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

    2015-11-01

    Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

  1. Hydrogen-silicon carbide interactions

    NASA Technical Reports Server (NTRS)

    Eckel, Andrew J.; Jacobson, Nathan S.; Misra, Ajay K.; Humphrey, Donald L.

    1989-01-01

    A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamic maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of Region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicon carbide is the single stable solid phase in Region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4, and SiH. Analysis of the kinetics of reaction for Region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to Regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

  2. Hydrogen-silicon carbide interactions

    NASA Technical Reports Server (NTRS)

    Eckel, Andrew J.; Misra, Ajay K.; Humphrey, Donald L.; Jacobson, Nathan S.

    1990-01-01

    A study of the thermochemistry and kinetics of hydrogen environmental attack of silicon carbide was conducted for temperatures in the range from 1100 C to 1400 C. Thermodynamics maps based on the parameters of pressure and oxygen/moisture content were constructed. With increasing moisture levels, four distinct regions of attack were identified. Each region is defined by the thermodynamically stable solid phases. The theoretically stable solid phases of region 1 are silicon carbide and silicon. Experimental evidence is provided to support this thermodynamic prediction. Silicone carbide is the single stable solid phase in region 2. Active attack of the silicon carbide in this region occurs by the formation of gases of SiO, CO, CH4, SiH4 and SiH. Analyses of the kinetics of reaction for region 2 at 1300 C show the attack of the silicon carbide to be controlled by gas phase diffusion of H2O to the sample. Silicon carbide and silica are the stable phases common to regions 3 and 4. These two regions are characterized by the passive oxidation of silicon carbide and formation of a protective silica layer.

  3. Passive treatment of acid mine drainage with high metal concentrations using dispersed alkaline substrate.

    PubMed

    Rötting, Tobias S; Thomas, Robert C; Ayora, Carlos; Carrera, Jesús

    2008-01-01

    Passive treatment systems based on the dissolution of coarse calcite grains are widely used to remediate acid mine drainage (AMD). Unfortunately, they tolerate only low metal concentrations or acidity loads, because they are prone to passivation (loss of reactivity due to coating) and/or clogging (loss of permeability) by precipitates. To overcome these problems, a dispersed alkaline substrate (DAS) composed of a fine-grained alkaline reagent (calcite sand) mixed with a coarse inert matrix (wood chips) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate, whereas the dispersion of nuclei for precipitation on the inert surfaces retards clogging. Chemical and hydraulic performance of DAS was investigated in two laboratory columns fed at different flow rates with natural AMD of pH 2.3 to 3.5 and inflow net acidity 1350 to 2300 mg/L as CaCO(3). The DAS columns removed 900 to 1600 mg/L net acidity, 3 to 4.5 times more than conventional passive treatment systems. Regardless of the flow rate employed, Al, Fe(III), Cu, and Pb were virtually eliminated. Minor Zn, Ni, and Cd were removed at low flow rates. High acidity removal is possible because these metals accumulate intentionally in DAS, and their precipitation promotes further calcite dissolution. During 15 mo, DAS operated without clogging at 120 g acidity/m(2).d, four times the loading rate recommended for conventional passive systems; DAS may therefore be capable of treating AMD at sites where influent chemistry precludes the use of other passive systems. PMID:18689735

  4. Anelastic and thermal properties of ethylene/acrylic acid copolymers partially ionized with transition metals

    SciTech Connect

    Hoffman, D.M.; Matthews, F.M.; Riley, M.O.; Walkup, C.M.

    1988-01-01

    Ionomers of five 3d series transition metals (Mn, Fe, Co, Ni, and Cu), two Lanthanide series transition metals (Ce, Sm) and the IV and V series metals (Pb, Bi) were prepared by reaction with 25% solids dispersion of poly (ethylene-co-acrylic acid), EAA, in aqueous ammonia. The unreacted copolymer showed two mechanical relaxations, the glass transition at about 5C and a low temperature secondary relaxation at about -140C with 230 +- 10 kJ/mol and 50+-8 kJ/mol apparent activation energies, respectively. Typically three weight percent of the metal nitrate or acetate was reacted with the copolymer dispersion. After precipitation, drying and molding, the ionomers showed three mechanical relaxations. The low temperature ..gamma..-relaxation was quite strong and shifted about 5C higher compared to the EAA copolymer. The ..beta..-relaxation was extremely weak occurring at -62+-5C in the loss tangent at 1.0 Hz. The ..cap alpha..-relaxation or glass transition for 3% transition metal ionomers occurred at about 26+-3C for +3 oxidation states and Cu/sup +2/, but significantly higher for other +2 oxidation states (48 +- 2C for Co, Ni and 35C for Mn) based on G'' maxima at 1.0 Hz and the apparent activation energy was 220+-30kJ/mol. The two group IV and V metal ionomers were much higher loadings and had a much broader and stronger (..beta..') relaxation occurring at -6 +- 4C with 130+-10 kJ/mol activation energies. The lead ionomers were clear but the bismuth ionomer showed macroscopic phase separation. The 3d transition metal ionomers were clear and nicely colored characteristic of their ionization state except for iron which was somewhat cloudy. The Lanthanide ionomers were clear (Ce) or pale yellow (Sm) and also reasonably transparent. (16 refs., 12 figs., 5 tabs.)

  5. Quantifying Heavy Metals Sequestration by Sulfate-Reducing Bacteria in an Acid Mine Drainage-Contaminated Natural Wetland

    PubMed Central

    Moreau, John W.; Fournelle, John H.; Banfield, Jillian F.

    2013-01-01

    Bioremediation strategies that depend on bacterial sulfate reduction for heavy metals remediation harness the reactivity of these metals with biogenic aqueous sulfide. Quantitative knowledge of the degree to which specific toxic metals are partitioned into various sulfide, oxide, or other phases is important for predicting the long-term mobility of these metals under environmental conditions. Here we report the quantitative partitioning into sedimentary biogenic sulfides of a suite of metals and metalloids associated with acid mine drainage contamination of a natural estuarine wetland for over a century. PMID:23487496

  6. Trace metal mobilization from oil sands froth treatment thickened tailings exhibiting acid rock drainage.

    PubMed

    Kuznetsova, Alsu; Kuznetsov, Petr; Foght, Julia M; Siddique, Tariq

    2016-11-15

    Froth treatment thickened tailings (TT) are a waste product of bitumen extraction from surface-mined oil sands ores. When incubated in a laboratory under simulated moist oxic environmental conditions for ~450d, two different types of TT (TT1 and TT2) exhibited the potential to generate acid rock drainage (ARD) by producing acid leachate after 250 and 50d, respectively. We report here the release of toxic metals from TT via ARD, which could pose an environmental threat if oil sands TT deposits are not properly managed. Trace metal concentrations in leachate samples collected periodically revealed that Mn and Sr were released immediately even before the onset of ARD. Spikes in Co and Ni concentrations were observed both pre-ARD and during active ARD, particularly in TT1. For most elements measured (Fe, Cr, V, As, Cu, Pb, Zn, Cd, and Se), leaching was associated with ARD production. Though equivalent acidification (pH2) was achieved in leachate from both TT types, greater metal release was observed from TT2 where concentrations reached 10,000ppb for Ni, 5000ppb for Co, 3000ppb for As, 2000ppb for V, and 1000ppb for Cr. Generally, metal concentrations decreased in leachate with time during ARD and became negligible by the end of incubation (~450d) despite appreciable metals remaining in the leached TT. These results suggest that using TT for land reclamation purposes or surface deposition for volume reduction may unfavorably impact the environment, and warrants application of appropriate strategies for management of pyrite-enriched oil sands tailings streams. PMID:27443453

  7. Supported molybdenum carbide catalysts: Structure-function relationships for hydrodenitrogenation

    SciTech Connect

    Dolce, G.M.; Thompson, L.T.

    1997-12-31

    There continues to be a need for new catalysts that can efficiently upgrade petroleum crudes. Heavy oils and coal-derived liquids contain higher levels of nitrogen, sulfur, and oxygen than conventional light crudes, and therefore require more rigorous refining. Currently available commercial catalysts are not as active and efficient at hydrotreating these heavy oils compared to light crudes. Early transition metal carbides and nitrides have been shown to be active for the hydrotreatment of model compounds and petroleum crudes. In this paper the authors describe their investigations of the structural and compositional properties of {gamma}-Al{sub 2}O{sub 3}-supported molybdenum carbides and efforts to correlate these properties with their pyridine and quinoline hydrodenitrogenation (HDN) activities. The HDN activities of the materials scaled linearly with the loading and oxygen chemisorptive uptake. Oxygen chemisorption results also suggested that the molybdenum carbide particles were highly dispersed and perhaps raft-like. Using temperature programmed desorption and infrared spectroscopy of carbon monoxide, they were able to identify two types of sites on the carbides; sites on top of the particle and sites at the perimeter. They have tentatively concluded that the most active sites for HDN were on top of the supported carbide particles.

  8. Silicon Carbide Electronic Devices

    NASA Technical Reports Server (NTRS)

    Neudeck, P. G.

    2001-01-01

    The status of emerging silicon carbide (SiC) widebandgap semiconductor electronics technology is briefly surveyed. SiC-based electronic devices and circuits are being developed for use in high-temperature, high-power, and/or high-radiation conditions under which conventional semiconductors cannot function. Projected performance benefits of SiC electronics are briefly illustrated for several applications. However, most of these operational benefits of SiC have yet to be realized in actual systems, primarily owing to the fact that the growth techniques of SiC crystals are relatively immature and device fabrication technologies are not yet sufficiently developed to the degree required for widespread, reliable commercial use. Key crystal growth and device fabrication issues that limit the performance and capability of high-temperature and/or high-power SiC electronics are identified. The electrical and material quality differences between emerging SiC and mature silicon electronics technology are highlighted.

  9. ε-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst.

    PubMed

    Xu, Ke; Sun, Bo; Lin, Jun; Wen, Wen; Pei, Yan; Yan, Shirun; Qiao, Minghua; Zhang, Xiaoxin; Zong, Baoning

    2014-01-01

    ε-Iron carbide has been predicted to be promising for low-temperature Fischer-Tropsch synthesis (LTFTS) targeting liquid fuel production. However, directional carbidation of metallic iron to ε-iron carbide is challenging due to kinetic hindrance. Here we show how rapidly quenched skeletal iron featuring nanocrystalline dimensions, low coordination number and an expanded lattice may solve this problem. We find that the carbidation of rapidly quenched skeletal iron occurs readily in situ during LTFTS at 423-473 K, giving an ε-iron carbide-dominant catalyst that exhibits superior activity to literature iron and cobalt catalysts, and comparable to more expensive noble ruthenium catalyst, coupled with high selectivity to liquid fuels and robustness without the aid of electronic or structural promoters. This finding may permit the development of an advanced energy-efficient and clean fuel-oriented FTS process on the basis of a cost-effective iron catalyst. PMID:25503569

  10. Synthesis and Photoluminescence Property of Silicon Carbide Nanowires Via Carbothermic Reduction of Silica

    PubMed Central

    2010-01-01

    Silicon carbide nanowires have been synthesized at 1400 °C by carbothermic reduction of silica with bamboo carbon under normal atmosphere pressure without metallic catalyst. X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy and Fourier transformed infrared spectroscopy were used to characterize the silicon carbide nanowires. The results show that the silicon carbide nanowires have a core–shell structure and grow along <111> direction. The diameter of silicon carbide nanowires is about 50–200 nm and the length from tens to hundreds of micrometers. The vapor–solid mechanism is proposed to elucidate the growth process. The photoluminescence of the synthesized silicon carbide nanowires shows significant blueshifts, which is resulted from the existence of oxygen defects in amorphous layer and the special rough core–shell interface. PMID:20651911

  11. ɛ-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst

    NASA Astrophysics Data System (ADS)

    Xu, Ke; Sun, Bo; Lin, Jun; Wen, Wen; Pei, Yan; Yan, Shirun; Qiao, Minghua; Zhang, Xiaoxin; Zong, Baoning

    2014-12-01

    ɛ-Iron carbide has been predicted to be promising for low-temperature Fischer-Tropsch synthesis (LTFTS) targeting liquid fuel production. However, directional carbidation of metallic iron to ɛ-iron carbide is challenging due to kinetic hindrance. Here we show how rapidly quenched skeletal iron featuring nanocrystalline dimensions, low coordination number and an expanded lattice may solve this problem. We find that the carbidation of rapidly quenched skeletal iron occurs readily in situ during LTFTS at 423-473 K, giving an ɛ-iron carbide-dominant catalyst that exhibits superior activity to literature iron and cobalt catalysts, and comparable to more expensive noble ruthenium catalyst, coupled with high selectivity to liquid fuels and robustness without the aid of electronic or structural promoters. This finding may permit the development of an advanced energy-efficient and clean fuel-oriented FTS process on the basis of a cost-effective iron catalyst.

  12. Epsilon carbide - A low-temperature component of interplanetary dust particles

    NASA Technical Reports Server (NTRS)

    Christoffersen, R.; Buseck, P. R.

    1983-01-01

    Transmission electron microscope study of a chondritic interplanetary dust particle has revealed the presence of epsilon iron-nickel carbide, a low-temperature carbide previously encountered only in metallurgical studies. In these studies epsilon-carbide was synthesized by carburization of iron or nickel grains in a stream of carbon monoxide or carbon monoxide plus hydrogen. Similar carburization of an iron-nickel metal in situ may have produced epsilon-carbide during particle heating on atmospheric entry or in solar orbit. Alternatively, the epsilon-carbide may be a by-product of Fischer-Tropsch reactions in the solar nebula. Such reactions have been proposed as the mechanism of hydrocarbon formation in the early solar system.

  13. Synthesis and Photoluminescence Property of Silicon Carbide Nanowires Via Carbothermic Reduction of Silica

    NASA Astrophysics Data System (ADS)

    Luo, Xiaogang; Ma, Wenhui; Zhou, Yang; Liu, Dachun; Yang, Bin; Dai, Yongnian

    2010-01-01

    Silicon carbide nanowires have been synthesized at 1400 °C by carbothermic reduction of silica with bamboo carbon under normal atmosphere pressure without metallic catalyst. X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy and Fourier transformed infrared spectroscopy were used to characterize the silicon carbide nanowires. The results show that the silicon carbide nanowires have a core-shell structure and grow along <111> direction. The diameter of silicon carbide nanowires is about 50-200 nm and the length from tens to hundreds of micrometers. The vapor-solid mechanism is proposed to elucidate the growth process. The photoluminescence of the synthesized silicon carbide nanowires shows significant blueshifts, which is resulted from the existence of oxygen defects in amorphous layer and the special rough core-shell interface.

  14. Synthesis and Photoluminescence Property of Silicon Carbide Nanowires Via Carbothermic Reduction of Silica.

    PubMed

    Luo, Xiaogang; Ma, Wenhui; Zhou, Yang; Liu, Dachun; Yang, Bin; Dai, Yongnian

    2009-01-01

    Silicon carbide nanowires have been synthesized at 1400 degrees C by carbothermic reduction of silica with bamboo carbon under normal atmosphere pressure without metallic catalyst. X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy and Fourier transformed infrared spectroscopy were used to characterize the silicon carbide nanowires. The results show that the silicon carbide nanowires have a core-shell structure and grow along <111> direction. The diameter of silicon carbide nanowires is about 50-200 nm and the length from tens to hundreds of micrometers. The vapor-solid mechanism is proposed to elucidate the growth process. The photoluminescence of the synthesized silicon carbide nanowires shows significant blueshifts, which is resulted from the existence of oxygen defects in amorphous layer and the special rough core-shell interface. PMID:20651911

  15. Selective removal of transition metals from acidic mine waters by novel consortia of acidophilic sulfidogenic bacteria

    PubMed Central

    Ňancucheo, Ivan; Johnson, D. Barrie

    2012-01-01

    Summary Two continuous‐flow bench‐scale bioreactor systems populated by mixed communities of acidophilic sulfate‐reducing bacteria were constructed and tested for their abilities to promote the selective precipitation of transition metals (as sulfides) present in synthetic mine waters, using glycerol as electron donor. The objective with the first system (selective precipitation of copper from acidic mine water containing a variety of soluble metals) was achieved by maintaining a bioreactor pH of ∼2.2–2.5. The second system was fed with acidic (pH 2.5) synthetic mine water containing 3 mM of both zinc and ferrous iron, and varying concentrations (0.5–30 mM) of aluminium. Selective precipitation of zinc sulfide was possible by operating the bioreactor at pH 4.0 and supplementing the synthetic mine water with 4 mM glycerol. Analysis of the microbial populations in the bioreactors showed that they changed with varying operational parameters, and novel acidophilic bacteria (including one sulfidogen) were isolated from the bioreactors. The acidophilic sulfidogenic bioreactors provided ‘proof of principle’ that segregation of metals present in mine waters is possible using simple online systems within which controlled pH conditions are maintained. The modular units are versatile and robust, and involve minimum engineering complexity. PMID:21895996

  16. Leaching platinum-group metals in a sulfuric acid/chloride solution

    NASA Astrophysics Data System (ADS)

    Mahmoud, M. H. H.

    2003-04-01

    A leaching process was established based on the ability of platinum-group metals to form stable chloro-complexes in acidic chloride solutions. Industrial catalyst losses were examined for the recovery of platinum, palladium, and rhodium by leaching with a mixture of sulfuric acid and sodium chloride to avoid using aqua regia or autoclave conditions. Extraction of platinum and rhodium in 60% H2SO4 at 135°C steadily increased with increasing NaCl concentrations reaching 95% and 85%, respectively, at 0.1 M NaCl after two hours. By comparison, palladium was dissolved more quickly but also reached 85% under the same conditions. Extraction of each metal increased with temperatures up to 125°C but plateaued at higher temperatures. Similar behavior was observed with increasing H2SO4 concentrations up to 60%. More than 99% extraction of each metal was obtained after ten hours using 0.1 M NaCl and 60% H2SO4 at 125°C.

  17. Metal Ions Play an Essential Catalytic Role in the Mechanism of Ketol-Acid Reductoisomerase.

    PubMed

    Tadrowski, Sonya; Pedroso, Marcelo M; Sieber, Volker; Larrabee, James A; Guddat, Luke W; Schenk, Gerhard

    2016-05-23

    Ketol-acid reductoisomerase (KARI) is a Mg(2+) -dependent enzyme in the branched-chain amino acid biosynthesis pathway. It catalyses a complex two-part reaction: an alkyl migration followed by a NADPH-dependent reduction. Both reactions occur within the one active site, but in particular, the mechanism of the isomerisation step is poorly understood. Here, using a combination of kinetic, thermodynamic and spectroscopic techniques, the reaction mechanisms of both Escherichia coli and rice KARI have been investigated. We propose a conserved mechanism of catalysis, whereby a hydroxide, bridging the two Mg(2+) ions in the active site, initiates the reaction by abstracting a proton from the C2 alcohol group of the substrate. While the μ-hydroxide-bridged dimetallic centre is pre-assembled in the bacterial enzyme, in plant KARI substrate binding leads to a reduction of the metal-metal distance with the concomitant formation of a hydroxide bridge. Only Mg(2+) is capable of promoting the isomerisation reaction, likely to be due to non-competent substrate binding in the presence of other metal ions. PMID:27136273

  18. Heavy metals and acidic components in total deposited matter in Sibenik and National Park Kornati, Croatia.

    PubMed

    Cacković, Mirjana; Kalinić, Natasa; Vadjić, Vladimira; Pehnec, Gordana

    2009-01-01

    This article presents the results of 6 years (1999-2004) of monitoring acidic components (fluoride, chloride, nitrate, sulfate) and heavy metals (lead, cadmium, thallium) in total deposited matter (TDM) in the town of Sibenik and the National Park Kornati, Croatia, in order to determine their levels, spatial and temporal variations, and possible emission source. Bulk deposition samples were collected using the Bergerhoff samplers. TDM matter was determined gravimetrically. Acidic anions were analyzed using ion chromatography. Metallic components were determined by atomic absorption spectrometry. Results show that the levels of measured pollutants were relatively low compared to those reported in other investigations. Statistical analysis indicates that the measured pollutants originate from several sources such as resuspended soil, industry, road dust, traffic, and secondary aerosols as the most important. The levels of TDM show a slightly increasing trend at all sampling sites. A significant increasing trend in the levels of nitrate and sulfate in TDM could be the consequence of increasing traffic activity and urbanization. The significant increasing trend in the ratio between nitrate and sulfate in TDM indicates that the nitrate and sulfate relative contribution to acidification is increasing. The level of heavy metals in TDM was in order of lead > thallium > cadmium at all sampling sites with slightly decreasing trend. PMID:18414927

  19. Metal Interactions with Microbial Biofilms in Acidic and Neutral pH Environments

    PubMed Central

    Ferris, F. G.; Schultze, S.; Witten, T. C.; Fyfe, W. S.; Beveridge, T. J.

    1989-01-01

    Microbial biofilms were grown on strips of epoxy-impregnated filter paper submerged at four sites in water contaminated with metals from mine wastes. At two sample stations, the water was acidic (pH 3.1); the other sites were in a lake restored to a near neutral pH level by application of a crushed limestone slurry. During a 17-week study period, planktonic bacterial counts increased from 101 to 103 CFU/ml at all sites. Biofilm counts increased rapidly over the first 5 weeks and then leveled to 104 CFU/cm2 in the neutral pH system and 103 CFU/cm2 at the acidic sites. In each case, the biofilms bound Mn, Fe, Ni, and Cu in excess of the amounts adsorbed by control strips covered with nylon filters (pore size, 0.22 μm) to exclude microbial growth; Co bound under neutral conditions but not under acidic conditions. Conditional adsorption capacity constants, obtained graphically from the data, showed that biofilm metal uptake at a neutral pH level was enhanced by up to 12 orders of magnitude over acidic conditions. Similarly, adsorption strength values were usually higher at elevated pH levels. In thin sections of the biofilms, encapsulated bacterial cells were commonly found enmeshed together in microcolonies. The extracellular polymers often contained iron oxide precipitates which generated weak electron diffraction patterns with characteristic reflections for ferrihydrite (Fe2O3 · H2O) at d equaling 0.15 and 0.25 nm. At neutral pH levels, these deposits incorporated trace amounts of Si and exhibited a granular morphology, whereas acicular crystalloids containing S developed under acidic conditions. Images PMID:16347914

  20. Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory Study

    SciTech Connect

    Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter A.; Li, Sha; Mavrikakis, Manos

    2014-12-05

    We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxyl-mediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.

  1. Metal pollution of estuarine sediments caused by leaching of acid sulphate soils

    NASA Astrophysics Data System (ADS)

    Nordmyr, Linda; Åström, Mats; Peltola, Pasi

    2008-01-01

    This study tracks changes in metal distribution in estuarine sediments as a result of leakage from acid sulphate (AS) soil landscapes in the Boreal Zone (Finland). The main objective was to identify the impact of these nasty soils on sediment geochemistry in a biologically sensitive and shallow brackish-water estuary. In order to do this four sediment cores were sampled in a profile extending seawards from the mouth of the Vörå River, which is one of the most heavily AS soil-impacted rivers in Finland and Europe. Two of the cores were rather deep (2.5 m and 4.0 m) and the others were shallow (0.4 m and 0.8 m). The results showed that an appreciable amount of aluminium (Al), cobalt (Co), cadmium (Cd), copper (Cu), manganese (Mn), nickel (Ni) and zinc (Zn) were elevated in the surface and sub-surface of the sampled bottom sediments compared to the deeper sediment background levels. These metals are all known to be abundantly leached from the AS soils. At the site approximately 4 km away from the river mouth, the concentrations of Cd, Co, Mn, Ni and Zn were elevated 5-100 times as compared to the background levels and showed an intriguing cyclic pattern, most likely reflecting seasonal leaching dynamics in the AS soil landscapes. In contrast, metals that are not abundantly leached from AS soils, i.e. chromium (Cr), iron (Fe) and vanadium (V) had consistently low concentrations throughout all sediment cores. The elevated metal concentrations in the top layers of the sediments in the estuary are alarming. The continuous land uplift of the region combined with the episodic rapid declines in pH may result in short and long term extensive release of metals. This, in turn, may have significant effects on the trace-metal contents in the Gulf of Bothnia and the entire Baltic Sea.

  2. Facile synthesis and characterization of trimesic acid-Cu based metal organic frameworks

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Sel, Kivanc; Ozturk, Omer Faruk; Demirci, Sahin; Terzi, Gozde

    2014-09-01

    Metal-organic frameworks based on trimesic acid (TMA) as organic linker and Cu (II) as metal ions from different metal salts such as CuCl2, Cu(NO3)2, CuSO4 and Cu(CH3COOH)2 were prepared in relatively environmentally friendly media e.g., at room temperature in DI water and at the boiling point of ethanol. The prepared TMA-Cu MOFs showed very interesting porosity and optical coloring based on the source of the used metal salts and preparation medium. The prepared MOFs were characterized in terms of their porosity with BET measurements and it was found that about 850 m2/g for the MOF prepared from Cu(NO3)2 salt in ethanol. The amounts of metal ions connected to TMA were determined by atomic absorption spectroscopy measurements (AAS) after dissolution of TMA-Cu MOFs by concentrated HCl treatments. From AAS measurements the mole ratio of Cu(II) to TMA was found to vary between 1.5 and 2, depending on the source of metal ions and the solvent used during preparation. The structural analysis and thermal characterization of the prepared MOFs were done by using FT-IR and TGA analysis, respectively. Additionally, TMA-Cu based MOF disks were prepared and their conductivities were determined by I-V measurements. The conductivity of TMA-Cu MOFs was calculated to be between 8.26E-08 and 5.29E-11 S/cm.

  3. A study of silicon carbide synthesis from waste serpentine.

    PubMed

    Cheng, T W; Hsu, C W

    2006-06-01

    There are 60000 tons of serpentine wastes produced in year 2004 in Taiwan. This is due to the well-developed joints in the serpentine ore body as well as the stringent requirements of the particle size and chemical composition of serpentine by iron making company. The waste also creates considerable environmental problems. The purpose of this study is reutilization of waste serpentine to produce a high value silica powder after acid leaching. These siliceous microstructure products obtained from serpentine would be responsible for high reactivity and characteristic molecular sieving effect. In this study, the amorphous silica powder was then synthesized to silicon carbide with the C/SiO(2) molar ratio of 3. The experiment results show that silicon carbide can be synthesized in 1550 degrees C. The formed silicon carbide was whisker beta type SiC which can be used as raw materials for industry. PMID:16405956

  4. Heavy metals: confounding factors in the response of New Zealand freshwater fish assemblages to natural and anthropogenic acidity.

    PubMed

    Greig, Hamish S; Niyogi, Dev K; Hogsden, Kristy L; Jellyman, Phillip G; Harding, Jon S

    2010-07-15

    Acidification of freshwaters is a global phenomenon, occurring both through natural leaching of organic acids and through human activities from industrial emissions and mining. The West Coast of the South Island, New Zealand, has both naturally acidic and acid mine drainage (AMD) streams enabling us to investigate the response of fish communities to a gradient of acidity in the presence and absence of additional stressors such as elevated concentrations of heavy metals. We surveyed a total of 42 streams ranging from highly acidic (pH 3.1) and high in heavy metals (10 mg L(-)(1) Fe; 38 mg L(-)(1) Al) to circum-neutral (pH 8.1) and low in metals (0.02 mg L(-)(1) Fe; 0.05 mg L(-)(1) Al). Marked differences in pH and metal tolerances were observed among the 15 species that we recorded. Five Galaxias species, Anguilla dieffenbachii and Anguillaaustralis were found in more acidic waters (pH<5), while bluegill bullies (Gobiomorphus hubbsi) and torrentfish (Cheimarrichthys fosteri) were least tolerant of low pH (minimum pH 6.2 and 5.5, respectively). Surprisingly, the strongest physicochemical predictor of fish diversity, density and biomass was dissolved metal concentrations (Fe, Al, Zn, Mn and Ni) rather than pH. No fish were detected in streams with dissolved metal concentrations >2.7 mg L(-)(1) and nine taxa were only found in streams with metal concentrations <1 mg L(-)(1). The importance of heavy metals as critical drivers of fish communities has not been previously reported in New Zealand, although the mechanism of the metal effects warrants further study. Our findings indicate that any remediation of AMD streams which seeks to enable fish recolonisation should aim to improve water quality by raising pH above approximately 4.5 and reducing concentrations of dissolved Al and Fe to <1.0 mg L(-)(1). PMID:20478612

  5. Metals removal from an acid mine drainage: The Argo Tunnel experience

    SciTech Connect

    Cevaal, J.N.; Abel, R.J.; Rogers, S.E.

    1996-12-31

    The abandoned Argo Tunnel, located approximately 30 miles west of Denver in Idaho Springs, Colorado, is part of the Clear Creek/Central City Superfund Site and was identified as the most significant source of metals contamination to Clear Creek. More than 740 pounds of metals (including iron, manganese, zinc, copper and aluminum) are discharged from the Argo each day. During the course of bench-scale testing and preliminary design of the chemical precipitation treatment facility for the Argo Tunnel acid mine drainage, three treatment processes: conventional chemical precipitation, {open_quotes}high density sludge{close_quotes} precipitation arid membrane separation; and four chemical reagents: hydrated lime, caustic, magnesium hydroxide, and lime plus soda ash were evaluated. The result was the prepurchase of a {open_quotes}high density sludge{close_quotes} precipitation process using caustic as the reagent. The process was sized to treat the design average flow rate from the tunnel with additional capacity for potential future groundwater flows and for most surge events. The treatment facility was sited at the Argo Tunnel portal and adjacent to the Argo Mill, which is listed on the National Register of Historic Places. The nearby historic designation and strong local mining heritage led to null styled superstructure encompassing indigenous mining architecture. Improvements to the water quality within the basin include removal of most of the 740 pounds of metals the tunnel currently discharges to Clear Creek and a significant reduction in instream metal concentrations, notably zinc, manganese and copper.

  6. Removal of textile dyes and metallic ions using polyelectrolytes and macroelectrolytes containing sulfonic acid groups.

    PubMed

    Caldera Villalobos, M; Peláez Cid, A A; Herrera González, Ana M

    2016-07-15

    This work reports the removal of textile dyes and metallic ions by means of adsorption and coagulation-flocculation using two polyelectrolytes and two macroelectrolytes containing sulfonic acid groups. The adsorption of textile dyes was studied in aqueous solutions containing cationic dyes and in wastewater containing a vat dye. Also, removal of vat and naphthol dyes was studied using the process of coagulation-flocculation. The results show these materials possess elevated adsorption capacity, and they accomplished removal rates above 97% in aqueous solutions. The removal of the vat dye improved the quality of the wastewater notably, and an uncolored effluent was obtained at the end of the treatment. The treatment using adsorption decreased the values for coloration, conductivity, suspended solids, and pH. The removal of vat and naphthol dyes by means of coagulation-flocculation was studied as well, and removal rates of 90% were obtained. The polyelectrolytes and macroelectrolytes also proved effective in the adsorption of metallic ions in wastewater. The treatment using adsorption accomplished high removal rates of metallic ions, and it showed greater selectivity towards Cu(2+), Fe(3+) and Pb(2+). A decrease in the content of solids as well as the values for COD and conductivity was observed in the wastewater as well. The analyses of FT-IR indicated that cationic dyes and metallic ions were chemisorbed by means of ionic exchange. PMID:27082258

  7. Investigation of metal ion extraction and aggregate formation combining acidic and neutral organophosphorous reagents

    SciTech Connect

    Braatz, A.D.; Nilsson, M.; Ellis, R.; Antonio, M.

    2013-07-01

    In the present study, we investigate how varying mixtures of tri-n-butyl phosphate (TBP) and dibutyl phosphate (HDBP) results in enhanced extraction of lanthanum(III), La{sup 3+}, and dysprosium(III), Dy{sup 3+}. Water and metal ion extraction were carefully monitored as a function of TBP:HDBP mole ratio.In addition to these techniques, EXAFS was used to determine the coordination environment of the metal ion in this system. To produce the necessary signal, a concentration of 1.25*10{sup -3} M La{sup 3+} and Dy{sup 3+} was used. Although previous studies of synergistic extraction of metal cations using combinations of neutral and acidic reagents explain the enhanced extraction by increased dehydration of the metal ion and the formation of mixed extractant complexes, our evidence for the increased water extraction coupled with the aggregate formation suggests a reverse micellar aspect to synergism in the system containing TBP and HDBP. It is quite possible that both of these phenomena contribute to our system behavior. The EXAFS data shows that, based on coordination numbers alone, several possible structures may exist. From this study, we cannot provide a definitive answer as to the nature of extraction in this system or the exact complex formed during extraction.

  8. Heavy metals content in acid mine drainage at abandoned and active mining area

    NASA Astrophysics Data System (ADS)

    Hatar, Hazirah; Rahim, Sahibin Abd; Razi, Wan Mohd; Sahrani, Fathul Karim

    2013-11-01

    This study was conducted at former Barite Mine, Tasik Chini and former iron mine Sungai Lembing in Pahang, and also active gold mine at Lubuk Mandi, Terengganu. This study was conducted to determine heavy metals content in acid mine drainage (AMD) at the study areas. Fourteen water sampling stations within the study area were chosen for this purpose. In situ water characteristic determinations were carried out for pH, electrical conductivity (EC), redox potential (ORP) and total dissolved solid (TDS) using multi parameter YSI 556. Water samples were collected and analysed in the laboratory for sulfate, total acidity and heavy metals which follow the standard methods of APHA (1999) and HACH (2003). Heavy metals in the water samples were determined directly using Inductive Coupled Plasma Mass Spectrometry (ICP-MS). Data obtained showed a highly acidic mean of pH values with pH ranged from 2.6 ± 0.3 to 3.2 ± 0.2. Mean of electrical conductivity ranged from 0.57 ± 0.25 to 1.01 ± 0.70 mS/cm. Redox potential mean ranged from 487.40 ± 13.68 to 579.9 ± 80.46 mV. Mean of total dissolved solids (TDS) in AMD ranged from 306.50 ± 125.16 to 608.14 ± 411.64 mg/L. Mean of sulfate concentration in AMD ranged from 32.33 ± 1.41 to 207.08 ± 85.06 mg/L, whereas the mean of total acidity ranged from 69.17 ± 5.89 to 205.12 ± 170.83 mgCaCO3/L. Heavy metals content in AMD is dominated by Fe, Cu, Mn and Zn with mean concentrations range from 2.16 ± 1.61 to 36.31 ± 41.02 mg/L, 0.17 ± 0.13 to 11.06 ± 2.85 mg/L, 1.12 ± 0.65 to 7.17 ± 6.05 mg/L and 0.62 ± 0.21 to 6.56 ± 4.11 mg/L, respectively. Mean concentrations of Ni, Co, As, Cd and Pb were less than 0.21, 0.51, 0.24, 0.05 and 0.45 mg/L, respectively. Significant correlation occurred between Fe and Mn, Cu, Zn, Co and Cd. Water pH correlated negatively with all the heavy metals, whereas total acidity, sulfate, total dissolved solid, and redox potential correlated positively. The concentration of heavy metals in the AMD

  9. Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water

    PubMed Central

    Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng; Wang, Hai Feng; Yang, Zhen Zhong; Zheng, Li Rong; Hu, P.; Zhao, Hui Jun; Gu, Lin; Yang, Hua Gui

    2015-01-01

    Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry. PMID:26286479

  10. Recombinant D. radiodurans cells for bioremediation of heavy metals from acidic/neutral aqueous wastes.

    PubMed

    Misra, Chitra Seetharam; Appukuttan, Deepti; Kantamreddi, Venkata Siva Satyanarayana; Rao, Amara S; Apte, Shree Kumar

    2012-01-01

    The stability and superior metal bioremediation ability of genetically engineered Deinococcus radiodurans cells, expressing a non-specific acid phosphatase, PhoN in high radiation environment has already been established. The lyophilized recombinant DrPhoN cells retained PhoN activity and uranium precipitation ability. Such cells also displayed an extended shelf life of 6 months during storage at room temperature and showed surface associated precipitation of uranium as well as other metals like cadmium. Lyophilized cells, immobilized in polyacrylamide gels could be used for uranium bioprecipitation in a flow through system resulting in 70% removal from 1mM input uranium solution and a loading of 1 g uranium/g dry weight cells. Compared with a batch process which achieved a loading of 5.7 g uranium/g biomass, the efficiency of the column process was low due to clogging of the column by the precipitate. PMID:22179144

  11. Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water.

    PubMed

    Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng; Wang, Hai Feng; Yang, Zhen Zhong; Zheng, Li Rong; Hu, P; Zhao, Hui Jun; Gu, Lin; Yang, Hua Gui

    2015-01-01

    Modifications of local structure at atomic level could precisely and effectively tune the capacity of materials, enabling enhancement in the catalytic activity. Here we modulate the local atomic structure of a classical but inert transition metal oxide, tungsten trioxide, to be an efficient electrocatalyst for hydrogen evolution in acidic water, which has shown promise as an alternative to platinum. Structural analyses and theoretical calculations together indicate that the origin of the enhanced activity could be attributed to the tailored electronic structure by means of the local atomic structure modulations. We anticipate that suitable structure modulations might be applied on other transition metal oxides to meet the optimal thermodynamic and kinetic requirements, which may pave the way to unlock the potential of other promising candidates as cost-effective electrocatalysts for hydrogen evolution in industry. PMID:26286479

  12. Heavy metal removal from acid mine drainage by calcined eggshell and microalgae hybrid system.

    PubMed

    Choi, Hee-Jeong; Lee, Seung-Mok

    2015-09-01

    This study investigates the use of calcined eggshells and microalgae for the removal of heavy metals from acid mine drainage (AMD) and the simultaneous enhancement of biomass productivity. The experiment was conducted over a period of 6 days in a hybrid system containing calcined eggshells and the microalgae Chlorella vulgaris. The results show that the biomass productivity increased to ~8.04 times its initial concentration of 0.367 g/L as measured by an optical panel photobioreactor (OPPBR) and had a light transmittance of 95 % at a depth of 305 mm. On the other hand, the simultaneous percent removal of Fe, Cu, Zn, Mn, As, and Cd from the AMD effluent was found to be 99.47 to 100 %. These results indicate that the hybrid system with calcined eggshells and microalgae was highly effective for heavy metal removal in the AMD. PMID:25940497

  13. Neutrophil chemotaxis and arachidonic acid metabolism are not linked: evidence from metal ion probe studies

    SciTech Connect

    Turner, S.R.; Turner, R.A.; Smith, D.M.; Johnson, J.A.

    1986-03-05

    Heavy metal ions can inhibit arachidonic acid (AA) metabolism protect against ionophore cytotoxicity (ibid) and inhibit neutrophil chemotaxis. In this study they used Au/sup 3 +/, Zn/sup 2 +/, Cr/sup 3 +/, Mn/sup 2 +/ and Cu/sup 2 +/ as probes of the interrelationships among AA metabolism, ionophore-mediated cytotoxicity, and chemotaxis. Phospholipid deacylation was measured in ionophore-treated cells prelabeled with /sup 3/H-AA. Eicosanoid release from ionophore-treated cells was monitored by radioimmunoassay. Cytoprotection was quantitated as ability to exclude trypan blue. Chemotaxis toward f-met-leu-phe was measured by leading front analysis. The results imply that metal ions attenuate ionophore cytotoxicity by blocking phospholipid deacylation and eicosanoid release. In contrast to previous reports, no correlation between AA metabolism and chemotaxis was demonstrated, suggesting that these 2 processes are not linked.

  14. Metallamacrocycle formation through dimerization of metal bioconjugates derived from amino acids and peptides.

    PubMed

    Álvarez, Celedonio M; García-Rodríguez, Raúl; Miguel, Daniel

    2016-01-21

    Metallamacrocycles of 12, 16, and 22 members are obtained by deprotonation of the carboxylic group of the side chain of iminopyridine complexes derived from the amino acid β-alanine, and the peptides Gly-Gly and Gly-Gly-Gly. Instead of the expected intramolecular attack to give tridentate (N,N,O) ligands, the deprotonated carboxylate attacks in an inter-molecular manner to give dimers in which the ligand acts as a bridge bonded in a κ(2)(N,N') chelating fashion to one metal and as κ(O) to the other metal. The formation of the dimers is supported by NMR spectroscopy, mass spectrometry and X-ray crystallography. PMID:26645303

  15. Geochemical Controls on the Partitioning and Hydrological Transport of Metals in a Human Impacted, Non-Acidic, River System

    NASA Astrophysics Data System (ADS)

    Thorslund, J.; Jarsjo, J.; Wällstedt, T.; Morth, C. M.; Lychagin, M.; Chalov, S.

    2014-12-01

    The knowledge of coupled processes controlling the spreading and fate of metals in non-acidic river systems is currently much more limited than the knowledge of metal behavior under acidic conditions (e.g., in acid mine drainage systems). Critical geochemical controls governing metal speciation may thus differ substantially between acidic and non-acidic hydrological systems. We here aim at expanding the knowledge of metals in non-acidic river systems, by considering a high pH river, influenced by mining by the largest gold mining area in the Mongolian part of the transboundary Lake Baikal drainage basin. The combined impact of geochemical and hydrological processes is investigated, to be able to understand the solubility of various heavy metals, their partitioning between particulate and dissolved phase and its impact on overall transport. We show, through site specific measurements and a geochemical modelling approach, that the combined effects of precipitation of ferrihydrite and gibbsite and associated sorption complexes of several metals can explain the high impact of suspended transport relative to total transport often seen under non-acidic conditions. Our results also identifies the phosphate mineral Hydroxyapatite as a potential key sorption site for many metals, which has both site specific and general relevance for metal partitioning under non-acidic conditions. However, an adsorption database, which is currently unavailable for hydroxyapatite, needs to be developed for appropriate sorption quantification. Furthermore, Cd, Fe, Pb and Zn were particularly sensitive to increasing DOC concentrations, which increased the solubility of these metals due to metal-organic complexation. Modeling the sensitivity to changes in geochemical parameters showed that decreasing pH and increasing DOC concentrations in downstream regions would increase the dissolution and hence the toxicity and bioavailability of many pollutants of concern in the downstream ecosystem. In

  16. Supercritical Fluid Extraction of Toxic Heavy Metals and Uranium from Acidic Solutions with Sulfur-Containing Organophosphorus Reagents

    SciTech Connect

    Lin, Yuehe ); Liu, Chongxuan ); Wu, Hong ); Yak, H K.; Wai, Chien M.

    2003-03-02

    The feasibility of using sulfur-containing organophosphorus reagents for the chelation-supercritical fluid extraction (SFE) of toxic heavy metals and uranium from acidic media was investigated. The SFE experiments were conducted in a specially-designed flow-through liquid extractor. Effective extraction of the metal ions from various acidic media was demonstrated. The effect of ligand concentration in supercritical CO{sub 2} on the kinetics of metal extraction was studied. A simplified model is used to describe the extraction kinetics and the good agreement of experimental data with the equilibrium-based model is achieved.

  17. Predicting the toxicity of sediment-associated trace metals with simultaneously extracted trace metal: Acid-volatile sulfide concentrations and dry weight-normalized concentrations: A critical comparison

    USGS Publications Warehouse

    Long, E.R.; MacDonald, D.D.; Cubbage, J.C.; Ingersoll, C.G.

    1998-01-01

    The relative abilities of sediment concentrations of simultaneously extracted trace metal: acid-volatile sulfide (SEM:AVS) and dry weight- normalized trace metals to correctly predict both toxicity and nontoxicity were compared by analysis of 77 field-collected samples. Relative to the SEM:AVS concentrations, sediment guidelines based upon dry weight-normalized concentrations were equally or slightly more accurate in predicting both nontoxic and toxic results in laboratory tests.

  18. Harnessing Lewis acidic open metal sites of metal-organic frameworks: the foremost route to achieve highly selective benzene sorption over cyclohexane.

    PubMed

    Mukherjee, Soumya; Manna, Biplab; Desai, Aamod V; Yin, Yuefeng; Krishna, Rajamani; Babarao, Ravichandar; Ghosh, Sujit K

    2016-07-01

    π-Complexation triggered Lewis acid-base interactions between open metal sites (OMS) of metal-organic frameworks (MOFs), and π-e(-) rich adsorptive benzene (Bz) is exploited to establish M-MOF-74 as the best Bz-selective MOF sorbent, marking the first report of utilizing OMS behind benzene/cyclohexane separation; a key advance from the energy-economy standpoint of industrial separation. PMID:27188914

  19. Effect of metal ions in a heated nitric acid solution on the corrosion behavior of a titanium-5% tantalum alloy in the hot nitric acid condensate

    NASA Astrophysics Data System (ADS)

    Sano, Y.; Takeuchi, M.; Nakajima, Y.; Hirano, H.; Uchiyama, G.; Nojima, Y.; Fujine, S.; Matsumoto, S.

    2013-01-01

    For evaluating the application of titanium and its alloys as components of equipment for storing nitric acid condensate in spent nuclear fuel reprocessing plants, the corrosion behavior of titanium-5% tantalum alloy (Ti-5Ta) in a continuously renewed hot nitric acid condensate, and particularly the effect of metal ions in the heated nitric acid solution, was investigated. Corrosion experiments in an apparatus designed to renew the condensate at regular intervals showed that the corrosion rate of Ti-5Ta in the condensate increased linearly with the nitric acid concentration. The surface morphology of Ti-5Ta coupons after the corrosion experiments indicated uniform corrosion under any condition. The oxide film on the coupons had nearly constant thickness, and it was composed of mainly lower Ti oxides, such as TiO and Ti2O3, regardless of the nitric acid concentration in the condensate. The experimental results also showed that the addition of metal ions into the heated nitric acid solution increased the nitric acid concentration in the condensate, which resulted in a higher corrosion rate of Ti-5Ta. The corrosion rate increased noticeably as the valence of the metal ion increased and its ionic radius decreased. This effect of metal ions in the heated nitric acid solution on the corrosion rate of Ti-5Ta in the condensate was evaluated quantitatively based on the Gibbs free energy of hydration of the metal ions, and the calculated corrosion rates of Ti-5Ta in the condensate were found to be in good agreement with the experimental values.

  20. Generalized chemical route to develop fatty acid capped highly dispersed semiconducting metal sulphide nanocrystals

    SciTech Connect

    Patel, Jayesh D.; Mighri, Frej; Ajji, Abdellah

    2012-08-15

    Highlights: ► Chemical route for the synthesis of OA-capped CdS, ZnS and PbS at low temperature. ► Synthesized nanocrystals via thermolysis of their metal–oleate complexes. ► Size quantized nanocrystals were highly dispersed and stable at room temperature. -- Abstract: This work deals with the synthesis of highly dispersed semiconducting nanocrystals (NCs) of cadmium sulphide (CdS), zinc sulphide (ZnS) and lead sulphide (PbS) through a simple and generalized process using oleic acid (OA) as surfactant. To synthesize these NCs, metal–oleate (M–O) complexes were obtained from the reaction at 140 °C between metal acetates and OA in hexanes media. Subsequently, M–O complexes were sulphurized using thioacetamide at the same temperature. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) characterizations show that the synthesized products are of nanoscale-size with highly crystalline cubic phase. The optical absorption of OA-capped metal sulphide NCs confirms that their size quantization induced a large shift towards visible region. Photoluminescence (PL) spectrum of CdS NCs shows a broad band-edge emission with shallow and deep-trap emissions, while PL spectrum of ZnS NCs reveals a broad emission due to defects states on the surface. The thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy indicate that fatty acid monolayers were bound strongly on the nanocrystal surface as a carboxylate and the two oxygen atoms of the carboxylate were coordinated symmetrically to the surface of the NCs. The strong binding between the fatty acid and the NCs surface enhances the stability of NCs colloids. In general, this generalized route has a great potential in developing nanoscale metal sulphides for opto-electronic devices.

  1. SOLVENT EXTRACTION PROCESS FOR THE RECOVERY OF METALS FROM PHOSPHORIC ACID

    DOEpatents

    Bailes, R.H.; Long, R.S.

    1958-11-01

    > A solvent extraction process is presented for recovering metal values including uranium, thorium, and other lanthanide and actinide elements from crude industrial phosphoric acid solutions. The process conslsts of contacting said solution with an immisclble organic solvent extractant containing a diluent and a material selected from the group consisting of mono and di alkyl phosphates, alkyl phosphonates and alkyl phosphites. The uranlum enters the extractant phase and is subsequently recovered by any of the methods known to the art. Recovery is improved if the phosphate solution is treated with a reducing agent such as iron or aluminum powder prior to the extraction step.

  2. Metal-organic frameworks constructed from crown ether-based 1,4-benzenedicarboxylic acid derivatives.

    PubMed

    Chen, Teng-Hao; Schneemann, Andreas; Fischer, Roland A; Cohen, Seth M

    2016-02-21

    A series of unprecedented crown ether- and thiacrown ether-derivatized benzene dicarboxylic acid (H2bdc) ligands has been synthesized and incorporated into the prototypical isoreticular metal-organic framework (IRMOF) and UiO-66 materials. In the case of UiO-66, only MOFs comprised from a mixed-ligand composition, requiring both unsubstituted bdc and crown ether containing ligands, could be prepared. These are among the few ligand derivatives, and resulting MOFs, that incorporate a macrocyclic group directly on the bdc ligand, providing a new, modular platform for exploring new supramolecular and coordination chemistry within MOFs. PMID:26765588

  3. Mechanical properties of some silicon carbide reinforced aluminum composites

    SciTech Connect

    Tsangarakis, N.; Andrews, B.O.; Cavallaro, C.

    1987-05-01

    The mechanical properties of several particulate and continuous fiber silicon carbide-reinforced aluminum composites were examined. The tensile strength of a 47 percent silicon carbide fiber unidirectionally-reinforced aluminum composite was 1273 and 76 MPa parallel and normal to the fiber direction, respectively. The tensile strength of (0 deg/90 deg) 4s and (0/sub 2/90/0)s composites were 629 and 864 MPa, respectively. The tensile properties of a 30 percent silicon carbide particulate reinforced aluminum were found to depend on the chemistry of the metal matrix. The endurance limits of the fiber and the particulate reinforced aluminum were at the most 55 percent and 33 percent of the respective tensile strengths. The fracture toughness of the fiber reinforced composite varied with specimen width, while that of the particulate reinforced composite was 21-29 MPa sq rt m. The fatigue crack growth rate in the latter composite decreased with material thickness. There were indications that the fatigue crack growth rate in the silicon carbide particulate reinforced aluminum may be independent of variations in the chemistry of the metal matrix. 6 references.

  4. A preliminary study for removal of heavy metals from acidic synthetic wastewater by using pressmud-rice husk mixtures

    NASA Astrophysics Data System (ADS)

    Ahmad, H.; Ee, C. J.; Baharudin, N. S.

    2016-06-01

    The study was carried out to evaluate the effect of combining pressmud and rice husk in the removal efficiencies of heavy metals in acidic synthetic wastewater. The ratios of pressmud to rice husk were varied at different percentages of weight ratio (0%, 20%, 40%, 60% 80% and 100%) and removal of heavy metals concentrations was observed. The result showed that the removal efficiency was increased with the addition of pressmud by up to almost 100%. Pressmud alone was able to remove 95% to 100% of heavy metals while rice husk alone managed to remove only 10% to 20% of heavy metals. The study also demonstrated that pressmud behaved as a natural acid neutralizer. Hence, the initial pH of the synthetically prepared acidic wastewater which was below 2 also was increased to pH ranging from 6 to 8.

  5. Ag (I)-based 2D metal frameworks with helical structures decorated by the homochiral camphor-10-sulfonic acid

    NASA Astrophysics Data System (ADS)

    Guo, Peng; Wang, Jing; Wang, Jun; Pan, Daocheng; Xu, Guohai

    2010-12-01

    Two two-dimension homochiral Ag (I) metal frameworks constructed from enantiopure camphor-10-sulfonic acid and hexamethylenetetramine have been synthesized at the room temperature. These two complexes with (6, 3) topology decorated by the homochiral camphor-10-sulfonic acid possess the unique helical structures. The result of Circular Dichroism (CD) spectroscopy confirms that the bulk materials are homochiral and also indicates the handedness of the single crystals can be controlled by the chirality of the camphor-10-sulfonic acid.

  6. Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids

    SciTech Connect

    Carraher, Jack; Pestovsky, Oleg; Bakac, Andreja

    2012-03-14

    Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe3+ in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe2+. The photochemistry in the presence of halide ions (X− = Cl−, Br−) generates ethyl halides via halogen atom abstraction from FeXn3−n by ethyl radicals. Near-quantitative yields of C2H5X are obtained at ≥0.05 M X−. Competition experiments with Co(NH3)5Br2+ provided kinetic data for the reaction of ethyl radicals with FeCl2+ (k = (4.0 ± 0.5) × 106 M−1 s−1) and with FeBr2+ (k = (3.0 ± 0.5) × 107 M−1 s−1). Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu+. Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu+ to Cu2+, and removes gaseous olefins to prevent accumulation of Cu+(olefin) complexes and depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

  7. Investigation of metal binding sites on soil fulvic acid using Eu(III) luminescence spectroscopy

    SciTech Connect

    Yoon, T.H.; Moon, H. ); Park, Y.J.; Park, K.K. )

    1994-11-01

    The [sup 7]F[sub 0] [yields] [sup 5]D[sub 0] excitation spectra of Eu(III) complexed with soil fulvic acid (FA) were acquired over a range of solution pH (2.9-7.8) and FA concentrations (800-3200 mg L[sup [minus]1]) using a pulsed tunable dye laser system. The broad asymmetric excitation spectra were well-fitted to a sum of two conventional Lorentzian-shaped curves, revealing the existence of two types of carboxylate moieties for the binding of metal ions on FA which formed 1:1 (EuL[sup 2+]; L = carboxylate) and 1:2 complexes (EuL[sub 2][sup +]). The weaker binding species, EuL[sup 2+], seemed to be quite abundant and showed a rapid increase as the pH was raised from 2.9 to 6.3, but it was susceptible to hydrolysis at pH higher than 7 while the stronger binding species, EuL[sub 2][sup +], showed only a modest growth with an increase in pH. By contrast, on a more flexible synthetic linear polymer, poly(acrylic acid) (PAA) and poly(vinylbenzoic acid) (PVBA) as model polymers, EuL[sub 2][sup +] was seen as the dominant species except in acidic media. 28 refs., 10 figs., 3 tabs.

  8. Effect of pH and organic acids on nitrogen transformations and metal dissolution in soils

    SciTech Connect

    Fu, Minhong.

    1989-01-01

    The effect of pH (4, 6, and 8) on nitrogen mineralization was evaluated in three Iowa surface soils treated with crop residues (corn (Zea mays L.), soybean (Glycine max (L.) Merr.), and sorghum (Sorghum vulgare Pers.), or alfalfa (Medicago sativa L.)) and incubated in leaching columns under aerobic conditions at 30C for 20 weeks. In general, N mineralization was significantly depressed at soil pH 4, compared with pH 6 or 8. The types of crop residues added influenced the pattern and amount of N mineralization. A study on the effect of 19 trace elements on the nitrate red activity of four Iowa surface soils showed that most trace elements inhibited this enzyme in acid and neutral soils. The trace elements Ag(I), Cd(II), Se(IV), As(V), and W(VI) were the most effective inhibitors, with >75% inhibition. Mn(II) was the least effective inhibitor, with <10% inhibition. Other trace elements included Cu(I), Co(II), Cu(II), Fe(II), Ni(II), Pb(II), Zn(II), Al(III), As(III), Cr(III), Fe(III), V(IV), Mo(VI), and Se(VI). The application of high-performance liquid chromatography (HPLC) showed that, when coupled to a refractive index detector, it is a rapid, sensitive, and accurate method for determining organic acids in soils. Three organic acids, acetic (2-20 mM), propionic (0-3 mM), and n-butyric (0-1.4 mM), were identified with HPLC and confirmed by gas chromatography in crop-residue-treated soils incubated under waterlogged conditions at 25C for 72 h. No organic acids were detected under aerobic conditions. Four mineral acids and 29 organic acids were studied for their effect on N mineralization and metal dissolution in soils incubated under waterlogged conditions at 30C for 10 days.

  9. A preliminary study of the hydrolysis of hydroxamic acid complexants in the presence of oxidising metal ions

    NASA Astrophysics Data System (ADS)

    Andrieux, Fabrice P. L.; Boxall, Colin; May, Iain; Taylor, Robin J.

    2010-03-01

    Simple hydroxamic acids (XHAs) are salt free, organic compounds with affinities for cations such as Np4+, Pu4+ and Fe3+. As such they have been identified as suitable reagents for the separation of either Pu and/or Np from U in modified or single cycle Purex based solvent extraction processes designed to meet the emerging requirements of Advanced Fuel Cycles. Acid catalyzed hydrolysis of free XHAs is well known and may impact negatively on reprocessing applications. The hydrolysis of metal-bound XHAs within metal ion-XHA complexes is less understood. Using a model derived for the study of hydroxamic acid hydrolysis in the presence of non-oxidising metal ions (Np (IV) and Fe(III)), we review data pertaining to the hydrolysis of hydroxamic acids in the presence of the oxidising Pu4+ ion, under conditions where the influence of the redox processes may potentially be neglected.

  10. Colorimetric sensor array based on gold nanoparticles and amino acids for identification of toxic metal ions in water.

    PubMed

    Sener, Gulsu; Uzun, Lokman; Denizli, Adil

    2014-01-01

    A facile colorimetric sensor array for detection of multiple toxic heavy metal ions (Hg(2+), Cd(2+), Fe(3+), Pb(2+), Al(3+), Cu(2+), and Cr(3+)) in water is demonstrated using 11-mercaptoundecanoic acid (MUA)-capped gold nanoparticles (AuNPs) and five amino acids (lysine, cysteine, histidine, tyrosine, and arginine). The presence of amino acids (which have functional groups that can form complexes with metal ions and MUA) regulates the aggregation of MUA-capped particles; it can either enhance or diminish the particle aggregation. The combinatorial colorimetric response of all channels of the sensor array (i.e., color change in each of AuNP and amino acid couples) enables naked-eye discrimination of all of the metal ions tested in this study with excellent selectivity. PMID:25330256

  11. Carbon-protected bimetallic carbide nanoparticles for a highly efficient alkaline hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Liu, Yipu; Li, Guo-Dong; Yuan, Long; Ge, Lei; Ding, Hong; Wang, Dejun; Zou, Xiaoxin

    2015-02-01

    The hydrogen evolution reaction (HER) is one of the two important half reactions in current water-alkali and chlor-alkali electrolyzers. To make this reaction energy-efficient, development of highly active and durable catalytic materials in an alkaline environment is required. Herein we report the synthesis of carbon-coated cobalt-tungsten carbide nanoparticles that have proven to be efficient noble metal-free electrocatalysts for alkaline HER. The catalyst affords a current density of 10 mA cm-2 at a low overpotential of 73 mV, which is close to that (33 mV) required by Pt/C to obtain the same current density. In addition, this catalyst operates stably at large current densities (>30 mA cm-1) for as long as 18 h, and gives nearly 100% Faradaic yield during alkaline HER. The excellent catalytic performance (activity and stability) of this nanocomposite material is attributed to the cooperative effect between nanosized bimetallic carbide and the carbon protection layer outside the metal carbide. The results presented herein offer the exciting possibility of using carbon-armoured metal carbides for an efficient alkaline HER, although pristine metal carbides are not, generally, chemically stable enough under such strong alkaline conditions.The hydrogen evolution reaction (HER) is one of the two important half reactions in current water-alkali and chlor-alkali electrolyzers. To make this reaction energy-efficient, development of highly active and durable catalytic materials in an alkaline environment is required. Herein we report the synthesis of carbon-coated cobalt-tungsten carbide nanoparticles that have proven to be efficient noble metal-free electrocatalysts for alkaline HER. The catalyst affords a current density of 10 mA cm-2 at a low overpotential of 73 mV, which is close to that (33 mV) required by Pt/C to obtain the same current density. In addition, this catalyst operates stably at large current densities (>30 mA cm-1) for as long as 18 h, and gives nearly

  12. Combining Nitrilotriacetic Acid and Permeable Barriers for Enhanced Phytoextraction of Heavy Metals from Municipal Solid Waste Compost by and Reduced Metal Leaching.

    PubMed

    Zhao, Shulan; Jia, Lina; Duo, Lian

    2016-05-01

    Phytoextraction has the potential to remove heavy metals from contaminated soil, and chelants can be used to improve the capabilities of phytoextraction. However, environmentally persistent chelants can cause metal leaching and groundwater pollution. A column experiment was conducted to evaluate the viability of biodegradable nitrilotriacetic acid (NTA) to increase the uptake of heavy metals (Cd, Cr, Ni, Pb, Cu, and Zn) by L. in municipal solid waste (MSW) compost and to evaluate the effect of two permeable barrier materials, bone meal and crab shell, on metal leaching. The application of NTA significantly increased the concentrations and uptake of heavy metals in . The enhancement was more pronounced at higher dosages of NTA. In the 15 mmol kg NTA treatment using a crab shell barrier, the Cr and Ni concentrations in the plant shoots increased by approximately 8- and 10-fold, respectively, relative to the control. However, the addition of NTA also caused significant heavy metal leaching from the MSW compost. Bone meal and crab shell barriers positioned between the compost and the subsoil were effective in preventing metal leaching down through the soil profile by the retention of metals in the barrier. The application of a biodegradable chelant and the use of permeable barriers is a viable form of enhanced phytoextraction to increase the removal of metals and to reduce possible leaching. PMID:27136160

  13. Vibrational frequencies associated with the carbide ligand in iron butterfly clusters

    SciTech Connect

    Stanghellini, P.L.; Sailor, M.J.; Kuznesof, P.; Whitmire, K.H.; Hriljac, J.A.; Kolis, J.W.; Zheng, Y.; Shriver, D.F.

    1987-09-09

    The vibrational frequencies associated with the exposed carbon atom in several tetranuclear iron carbide clusters with a butterfly arrangement of atoms were investigated by infrared and Raman spectroscopy. Vibrational assignments were confirmed in most cases by /sup 13/C labeling of the carbide carbon atom. The characteristic feature of the iron butterfly carbides is a readily observed band in the infrared spectrum around 900 cm/sup -1/. An approximate normal-coordinate analysis on these molecules yields values of the metal-carbon force constant of about 250 N m/sup -1/. 29 references, 6 figures, 5 tables.

  14. Affordable Fabrication and Properties of Silicon Carbide-Based Interpenetrating Phase Composites

    NASA Technical Reports Server (NTRS)

    Singh, Mrityunjay

    1998-01-01

    An affordable processing technique for the fabrication of silicon carbide-based interpenetrating phase composites (IPCs) is presented. This process consists of the production of microporous carbon preforms and subsequent infiltration with liquid silicon or silicon-refractory metal alloys. The microporous preforms are made by the pyrolysis of a polymerized resin mixture for which methods to control pore volume and pore size have been established. The process gives good control of microstructure and morphology of silicon carbide-based composite materials. Room and high temperature mechanical properties (flexural strength, compressive strength, and flexural creep) of low and high silicon-silicon carbide composites will be discussed.

  15. Metal arsonate polymers of Cd, Zn, Ag and Pb supported by 4-aminophenylarsonic acid

    SciTech Connect

    Lesikar-Parrish, Leslie A.; Neilson, Robert H.; Richards, Anne F.

    2013-02-15

    The coordination preferences of 4-aminophenylarsonic acid, 4-NH{sub 2}C{sub 6}H{sub 4}AsO{sub 3}H{sub 2}, (p-arsanilic acid) with CdCl{sub 2}{center_dot}2.5H{sub 2}O, ZnCl{sub 2}, Ag(SO{sub 3}CF{sub 3}) and Pb(NO{sub 3}){sub 2} have been investigated affording five new metal arsonate polymers. The reaction between 4-aminophenylarsonic acid and CdCl{sub 2}{center_dot}2.5H{sub 2}O resulted in a one-dimensional polymer, [{l_brace}Cd(4-NH{sub 3}C{sub 6}H{sub 4}AsO{sub 3}H)(Cl){sub 2}{r_brace}(H{sub 2}O){sub 2}]{sub n}, 1, in which the polymeric chain is propagated by bridging chlorides. Exchange of CdCl{sub 2} for ZnCl{sub 2} afforded [{l_brace}Zn{sub 2}(4-NH{sub 3}C{sub 6}H{sub 4}AsO{sub 3})(Cl){sub 2}{r_brace}(H{sub 2}O){sub 2}(Cl)]{sub n}, 2, featuring interlinked 6- and 8-membered [Zn-O-As] ring systems. The reaction of Ag(SO{sub 3}CF{sub 3}) with 4-aminophenylarsonic acid, afforded polymeric 3, [Ag(4-NH{sub 2}C{sub 6}H{sub 4}AsO{sub 3}H)(4-NH{sub 2}C{sub 6}H{sub 4}AsO{sub 3}H{sub 2})]{sub n} where coordination of the amino group to the silver center is observed and [{l_brace}Ag{sub 2}(4-NH{sub 3}C{sub 6}H{sub 4}AsO{sub 3}H)(4-NH{sub 3}C{sub 6}H{sub 4}AsO{sub 3})({mu}2-SO{sub 3}CF{sub 3}){sub 2}{r_brace}(SO{sub 3}CF{sub 3}){sub 2}]{sub n}, 4. By comparison, the reaction of p-arsanilic acid with Pb(NO{sub 3}){sub 2} yielded a polymeric chain [Pb(4-NH{sub 3}C{sub 6}H{sub 4}AsO{sub 3}H)(NO{sub 3}){sub 2}]{sub n}, 5 of similar topology to 1. The structures of 1-5 have been indiscriminately characterized by single crystal X-ray diffraction and their composition supported by relevant spectroscopic techniques. A comparison of the structural features of these polymers is used to determine the coordination preference of the ligand and factors influencing structural motifs, for example, the role of the anion. - Graphical abstract: The reaction of 4-aminophenylarsonic acid, 4-NH{sub 2}C{sub 6}H{sub 4}AsO{sub 3}H{sub 2}, with cadmium, zinc, silver, and lead have resulted in

  16. High surface area silicon carbide-coated carbon aerogel

    DOEpatents

    Worsley, Marcus A; Kuntz, Joshua D; Baumann, Theodore F; Satcher, Jr, Joe H

    2014-01-14

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust. Carbon aerogels can be coated with sol-gel silica and the silica can be converted to silicone carbide, improved the thermal stability of the carbon aerogel.

  17. Silicon Carbide Growth

    NASA Technical Reports Server (NTRS)

    2005-01-01

    Andrew Trunek has focused on supporting the Sic team through the growth of Sic crystals, making observations and conducting research that meets the collective needs and requirements of the team while fulfilling program commitments. Cancellation of the Ultra Efficient Engine Technology (UEET) program has had a significant negative impact on resources and research goals. This report highlights advancements and achievements made with this cooperative agreement over the past year. NASA Glenn Research Center (GRC) continues to make advances in silicon carbide (SiC) research during the past year. Step free surfaces were used as substrates for the deposition of GaN epilayers that yielded very low dislocation densities. Defect free 3C- SiC was successfully nucleated on step free mesas and test diodes were fabricated. Web growth techniques were used to increase the usable surface area of dislocation free SiC by approximately equal to 40%. The greatest advancement has been attained on stepped surfaces of SiC. A metrology standard was developed using high temperature etching techniques titled "Nanometer Step Height Standard". This development culminated in being recognized for a 2004 R&D100 award and the process to produce the steps received a NASA Space Act award.

  18. Palladium interaction with silicon carbide

    NASA Astrophysics Data System (ADS)

    Gentile, M.; Xiao, P.; Abram, T.

    2015-07-01

    In this work the palladium interaction with silicon carbide is investigated by means of complementary analytical techniques such as thermogravimetry (TG), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Thermoscans were carried out on pellets of palladium, α-SiC and β-SiC high purity powders in the temperature range comprised between 293 K and 1773 K, in order to study the effect of temperature on the palladium-silicon carbide reaction. Thermoscans of α-SiC pellets containing 5 at.%Pd show that during differential calorimetry scans three exothermic peaks occurred at 773 K, 1144 K and 1615 K, while thermoscans of β-SiC pellets containing 3 at.%Pd and 5 at.%Pd do not show peaks. For the pellet α-SiC-5 at.%Pd XRD spectra reveal that the first peak is associated with the formation of Pd3Si and SiO2 phases, while the second peak and the third peak are correlated with the formation of Pd2Si phase and the active oxidation of silicon carbide respectively. Thermogravimetry scans show weight gain and weight loss peaks due to the SiO2 phase formation and the active oxidation. Additionally XPS fittings reveal the development of SiCxOy phase during the first exothermic peak up to the temperature of 873 K. The experimental data reveals that alpha silicon carbide is attacked by palladium at lower temperatures than beta silicon carbide and the reaction mechanism between silicon carbide and palladium is strongly affected by silicon carbide oxidation.

  19. DISSOLUTION OF PLUTONIUM METAL IN 8-10 M NITRIC ACID

    SciTech Connect

    Rudisill, T.; Pierce, R.

    2012-02-21

    The H-Canyon facility will be used to dissolve Pu metal for subsequent purification and conversion to plutonium dioxide (PuO{sub 2}) using Phase II of HB-Line. To support the new mission, the development of a Pu metal dissolution flowsheet which utilizes concentrated (8-10 M) nitric acid (HNO{sub 3}) solutions containing potassium fluoride (KF) is required. Dissolution of Pu metal in concentrated HNO{sub 3} is desired to eliminate the need to adjust the solution acidity prior to purification by anion exchange. The preferred flowsheet would use 8-10 M HNO{sub 3}, 0.015-0.07 M KF, and 0.5-1.0 g/L Gd to dissolve the Pu up to 6.75 g/L. An alternate flowsheet would use 8-10 M HNO{sub 3}, 0.1-0.2 M KF, and 1-2 g/L B to dissolve the Pu. The targeted average Pu metal dissolution rate is 20 mg/min-cm{sup 2}, which is sufficient to dissolve a 'standard' 2250-g Pu metal button in 24 h. Plutonium metal dissolution rate measurements showed that if Gd is used as the nuclear poison, the optimum dissolution conditions occur in 10 M HNO{sub 3}, 0.04-0.05 M KF, and 0.5-1.0 g/L Gd at 112 to 116 C (boiling). These conditions will result in an estimated Pu metal dissolution rate of {approx}11-15 mg/min-cm{sup 2} and will result in dissolution times of 36-48 h for standard buttons. The recommended minimum and maximum KF concentrations are 0.03 M and 0.07 M, respectively. The maximum KF concentration is dictated by a potential room-temperature Pu-Gd-F precipitation issue at low Pu concentrations. The purpose of the experimental work described in this report was two-fold. Initially a series of screening experiments was performed to measure the dissolution rate of Pu metal as functions of the HNO{sub 3}, KF, and Gd or B concentrations. The objective of the screening tests was to propose optimized conditions for subsequent flowsheet demonstration tests. Based on the rate measurements, this study found that optimal dissolution conditions in solutions containing 0.5-1.0 g/L Gd occurred in 8

  20. Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries.

    PubMed

    Chen, Xiangping; Chen, Yongbin; Zhou, Tao; Liu, Depei; Hu, Hang; Fan, Shaoyun

    2015-04-01

    Environmentally hazardous substances contained in spent Li-ion batteries, such as heavy metals and nocuous organics, will pose a threat to the environment and human health. On the other hand, the sustainable recycling of spent lithium-ion batteries may bring about environmental and economic benefits. In this study, a hydrometallurgical process was adopted for the comprehensive recovery of nickel, manganese, cobalt and lithium from sulfuric acid leaching liquor from waste cathode materials of spent lithium-ion batteries. First, nickel ions were selectively precipitated and recovered using dimethylglyoxime reagent. Recycled dimethylglyoxime could be re-used as precipitant for nickel and revealed similar precipitation performance compared with fresh dimethylglyoxime. Then the separation of manganese and cobalt was conducted by solvent extraction method using cobalt loaded D2EHPA. And McCabe-Thiele isotherm was employed for the prediction of the degree of separation and the number of extraction stages needed at specific experimental conditions. Finally, cobalt and lithium were sequentially precipitated and recovered as CoC2O4 ⋅ 2H2O and Li2CO3 using ammonium oxalate solution and saturated sodium carbonate solution, respectively. Recovery efficiencies could be attained as follows: 98.7% for Ni; 97.1% for Mn, 98.2% for Co and 81.0% for Li under optimized experimental conditions. This hydrometallurgical process may promise a candidate for the effective separation and recovery of metal values from the sulfuric acid leaching liquor. PMID:25619126