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Sample records for acid metallic carbides

  1. METHOD OF JOINING CARBIDES TO BASE METALS

    DOEpatents

    Krikorian, N.H.; Farr, J.D.; Witteman, W.G.

    1962-02-13

    A method is described for joining a refractory metal carbide such as UC or ZrC to a refractory metal base such as Ta or Nb. The method comprises carburizing the surface of the metal base and then sintering the base and carbide at temperatures of about 2000 deg C in a non-oxidizing atmosphere, the base and carbide being held in contact during the sintering step. To reduce the sintering temperature and time, a sintering aid such as iron, nickel, or cobait is added to the carbide, not to exceed 5 wt%. (AEC)

  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. Carbide-reinforced metal matrix composite by direct metal deposition

    NASA Astrophysics Data System (ADS)

    Novichenko, D.; Thivillon, L.; Bertrand, Ph.; Smurov, I.

    Direct metal deposition (DMD) is an automated 3D laser cladding technology with co-axial powder injection for industrial applications. The actual objective is to demonstrate the possibility to produce metal matrix composite objects in a single-step process. Powders of Fe-based alloy (16NCD13) and titanium carbide (TiC) are premixed before cladding. Volume content of the carbide-reinforced phase is varied. Relationships between the main laser cladding parameters and the geometry of the built-up objects (single track, 2D coating) are discussed. On the base of parametric study, a laser cladding process map for the deposition of individual tracks was established. Microstructure and composition of the laser-fabricated metal matrix composite objects are examined. Two different types of structures: (a) with the presence of undissolved and (b) precipitated titanium carbides are observed. Mechanism of formation of diverse precipitated titanium carbides is studied.

  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. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

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

    DOEpatents

    Beatty, Ronald L.

    1977-01-01

    An improved process for producing porous spheroidal particles consisting of a metal carbide phase dispersed within a carbon matrix is described. According to the invention metal-loaded ion-exchange resin microspheres which have been carbonized are coated with a buffer carbon layer prior to conversion of the oxide to carbide in order to maintain porosity and avoid other adverse sintering effects.

  17. 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.

  18. 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.

  19. Ultrafine-grained Aluminm and Boron Carbide Metal Matrix Composites

    NASA Astrophysics Data System (ADS)

    Vogt, Rustin

    Cryomilling is a processing technique used to generate homogenously distributed boron carbide (B4C) particulate reinforcement within an ultrafine-grained aluminum matrix. The motivation behind characterizing a composite consisting of cryomilled aluminum B4C metal matrix composite is to design and develop a high-strength, lightweight aluminum composite for structural and high strain rate applications. Cryomilled Al 5083 and B4C powders were synthesized into bulk composite by various thermomechanical processing methods to form plate and extruded geometries. The effects of processing method on microstructure and mechanical behavior for the final consolidated composite were investigated. Cryomilling for extended periods of time in liquid nitrogen has shown to increase strength and thermal stability. The effects associated with cryomilling with stearic acid additions (as a process-control agent) on the degassing behavior of Al powders is investigated and results show that the liberation of compounds associated with stearic acid were suppressed in cryomilled Al powders. The effect of thermal expansion mismatch strain on strengthening due to geometrically necessary dislocations resulting from quenching is investigated and found not to occur in bulk cryomilled Al 5083 and B 4C composites. Previous cryomilled Al 5083 and B4C composites have exhibited ultrahigh strength associated with considerable strain-to-failure (>14 pct.) at high strain rates (>103/s) during mechanical testing, but only limited strain-to-failure (˜0.75 pct.) at quasi-static strain rates (10-3/s). The increased strain to failure at high strain rates is attributed to micro-flaw developments, including kinking, extensive axial splitting, and grain growth were observed after high strain rate deformation, and the significance of these mechanisms is considered.

  20. 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.

  1. 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.

  2. New catalysts for hydroprocessing: Transition metal carbides and nitrides

    SciTech Connect

    Ramanathan, S.; Oyama, S.T. |

    1995-11-02

    A series of moderate surface area transition metal carbides and nitrides of molybdenum, tungsten, vanadium, niobium, and titanium were prepared by temperature-programmed reaction of the oxide precursor with a reactant gas (20% CH{sub 4}/H{sub 2} for the carbides and 100% NH{sub 3} for the nitrides). The phase purity and composition of the samples were established by X-ray diffraction photoelectron spectroscopy (XPS), while surface properties were determined by N{sub 2} BET and CO chemisorption measurements. The catalysts were tested in three-phase trickle-bed reactor for their activity in hydrodenitrogenation (HDN), hydrodesulfurization, and hydrodeoxygenation, with particular emphasis on HDN. The catalytic tests were carried out using a model liquid feed mixture containing 3000 ppm sulfur (dibenzothiophene), 2000 ppm nitrogen (quinoline), 500 ppm oxygen (benzofuran), 20 wt% aromatics (tetralin), and balance aliphatics (tetradecane). The carbides and nitrides were found to be active for HDN of quinoline with activity following the order group 6 > group 5 > group 4. Notably, Mo{sub 2}C showed superior areal HDN activity than a commercial sulfided Ni-Mo/Al{sub 2} O{sub 3} catalyst (shell 324). The XRD analysis of the spent catalysts indicated no change in the bulk structure, while XPS results showed little incorporation of sulfur in the surface region of the catalysts, suggesting that these materials are tolerant of sulfur. 42 refs., 11 figs., 7 tabs.

  3. 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.

  4. 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).

  5. A Study of Current Chopping Characteristics in Metal-Carbide Composite Contact Materials

    NASA Astrophysics Data System (ADS)

    Yamamoto, Atsushi; Kusano, Takashi; Okutomi, Tsutomu; Yokokura, Kunio; Homma, Mitsutaka

    To clarify the effect of carbides on current chopping characteristics chopping current was evaluated for various metalcarbide contact materials. As a result, it was found that the chopping current of metal-carbide contacts was related to the vapor pressure of metals and the work function of carbides. It was also found that the chopping current was reduced by the heat treatment when the melting point of contacts is lower than the temperature of heat teatment.

  6. 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.

  7. 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).

  8. 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.

  9. 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.

  10. Hydrogen adsorption in metal-decorated silicon carbide nanotubes

    NASA Astrophysics Data System (ADS)

    Singh, Ram Sevak; Solanki, Ankit

    2016-09-01

    Hydrogen storage for fuel cell is an active area of research and appropriate materials with excellent hydrogen adsorption properties are highly demanded. Nanotubes, having high surface to volume ratio, are promising storage materials for hydrogen. Recently, silicon carbide nanotubes have been predicted as potential materials for future hydrogen storage application, and studies in this area are ongoing. Here, we report a systematic study on hydrogen adsorption properties in metal (Pt, Ni and Al) decorated silicon carbide nanotubes (SiCNTs) using first principles calculations based on density functional theory. The hydrogen adsorption properties are investigated by calculations of adsorption energy, electronic band structure, density of states (DOS) and Mulliken charge population analysis. Our findings show that hydrogen adsorptions on Pt, Ni and Al-decorated SiCNTs undergo spontaneous exothermic reactions with significant modulation of electronic structure of SiCNTs in all cases. Importantly, according to the Mulliken charge population analysis, dipole-dipole interaction causes chemisorptions of hydrogen in Pt, Ni and Al decorated SiCNTs with formation of chemical bonds. The study is a platform for the development of metal decorated SiCNTs for hydrogen adsorption or hydrogen storage application.

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

    NASA Astrophysics Data System (ADS)

    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.

  12. 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.

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

    PubMed

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

    2015-03-11

    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.

  16. 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.

  17. Replacing precious metals with carbide catalysts for hydrogenation reactions

    DOE PAGES

    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

  18. 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.

  19. Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes).

    PubMed

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

    2015-10-27

    The higher the chemical diversity and structural complexity of two-dimensional (2D) materials, the higher the likelihood they possess unique and useful properties. Herein, density functional theory (DFT) is used to predict the existence of two new families of 2D ordered, carbides (MXenes), M'2M″C2 and M'2M″2C3, where M' and M″ are two different early transition metals. In these solids, M' layers sandwich M″ carbide layers. By 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.

  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. Radiation damage of transition metal carbides. Final technical report

    SciTech Connect

    Dixon, G.

    1991-12-31

    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.

  2. Transition Metal Carbides and Nitrides in Energy Storage and Conversion

    PubMed Central

    Zhong, Yu; Shi, Fan; Zhan, Jiye; Tu, Jiangping

    2016-01-01

    High‐performance electrode materials are the key to advances in the areas of energy conversion and storage (e.g., fuel cells and batteries). In this Review, recent progress in the synthesis and electrochemical application of transition metal carbides (TMCs) and nitrides (TMNs) for energy storage and conversion is summarized. Their electrochemical properties in Li‐ion and Na‐ion batteries as well as in supercapacitors, and electrocatalytic reactions (oxygen evolution and reduction reactions, and hydrogen evolution reaction) are discussed in association with their crystal structure/morphology/composition. Advantages and benefits of nanostructuring (e.g., 2D MXenes) are highlighted. Prospects of future research trends in rational design of high‐performance TMCs and TMNs electrodes are provided at the end. PMID:27812464

  3. 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.

  4. Rapid accurate isotopic measurements on boron in boric acid and boron carbide.

    PubMed

    Duchateau, N L; Verbruggen, A; Hendrickx, F; De Bièvre, P

    1986-04-01

    A procedure is described whereby rapid and accurate isotopic measurements can be performed on boron in boric acid and boron carbide after fusion of these compounds with calcium carbonate. It allows the determination of the isotopic composition of boron in boric acid and boron carbide and the direct assay of boron or the (10)B isotope in boron carbide by isotope-dilution mass spectrometry.

  5. 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

  6. 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.

  7. 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.

  8. 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

  9. 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)

  10. Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts.

    PubMed

    Hunt, Sean T; Milina, Maria; Alba-Rubio, Ana C; Hendon, Christopher H; Dumesic, James A; Román-Leshkov, Yuriy

    2016-05-20

    We demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti(0.1)W(0.9)C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading, enhance the activity, and increase the stability of noble metal catalysts.

  11. Processing of mixed uranium/refractory metal carbide fuels for high temperature space nuclear reactors

    NASA Astrophysics Data System (ADS)

    Knight, Travis; Anghaie, Samim

    2000-01-01

    Single phase, solid-solution mixed uranium/refractory metal carbides have been proposed as an advanced nuclear fuel for high performance, next generation space power and propulsion systems. These mixed carbides such as the pseudo-ternary, (U, Zr, Nb)C, hold significant promise because of their high melting points (typically greater than 3200 K), thermochemical stability in a hot hydrogen environment, and high thermal conductivity. However, insufficient test data exist under nuclear thermal propulsion conditions of temperature and hot hydrogen environment to fully evaluate their performance. Various compositions of (U, Zr, Nb)C were processed with 5% and 10% metal mole fraction of uranium. Stoichiometric samples were processed from the constituent carbide powders while hypostoichiometric samples with carbon-to-metal (C/M) ratios of 0.95 were processed from uranium hydride, graphite, and constituent refractory carbide powders. Processing techniques of cold pressing, sintering, and hot pressing were investigated to optimize the processing parameters necessary to produce dense (low porosity), homogeneous, single phase, solid-solution mixed carbide nuclear fuels for testing. This investigation was undertaken to evaluate and characterize the performance of these mixed uranium/refractory metal carbides for space power and propulsion applications. .

  12. One-step synthesis of dispersed bimetallic carbides and nitrides from transition metals hexamethylenetetramine complexes

    SciTech Connect

    Chouzier, Sandra; Afanasiev, Pavel . E-mail: Pavel.Afanasiev@catalyse.cnrs.fr; Vrinat, Michel; Cseri, Tivadar; Roy-Auberger, Magalie

    2006-11-15

    Bimetallic nitrides and carbides Co(Ni)-Mo were obtained from the decomposition of transition metals complexes with hexamethylenetetramine (HMTA) under inert atmosphere. The precursor complexes were prepared by means of aqueous precipitation of ammonium molybdate with cobalt nitrate or nickel nitrate and HMTA. During the decomposition, HMTA acts at once as a reducing agent and as a source of carbon and nitrogen. The precursor's composition and the decomposition conditions are the key parameters to influence the nature of the obtained phases. The method developed provides a simple one-step way to highly divided bimetallic nitrides and carbides. -- Graphical abstract: Bimetallic nitrides and carbides Co(Ni)-Mo were obtained from the decomposition of metals complexes with hexamethylenetetramine (HMTA) under inert atmosphere. During the decomposition, HMTA acts at once as a reducing agent and as a source of carbon and nitrogen. The method provides a simple one-step way to highly divided nitrides and carbides. Display Omitted.

  13. Synthesis and characterization of transition metal carbides and their catalytic applications

    NASA Astrophysics Data System (ADS)

    Wan, Cheng

    Transition metal (both monometallic and bimetallic) carbides have been synthesized by an amine-metal oxide composite (AMOC) method. The composite reduces the diffusion distances among each element and allows the formation of carbides to take place as low as 610°C, which is significantly lower than traditional carbide synthesis methods (above 1500°C). Additionally, amines act not only as carbon sources and reducing agents, but also morphological templates which helps to make uniform transition metal carbide (TMC) nanocrystals with various shapes. Beyond morphology control, AMOC method can also help to synthesize multiple phases of monometallic carbides, which includes four phases of molybdenum carbides (alpha-MoC1-x, beta-Mo2C, eta-MoC, and gamma-MoC), two phases of tungsten carbides (W2C and WC), and three phases of chromium carbides (Cr3C2-x, Cr7C3, and Cr3C2). Molybdenum carbide has been proposed as a possible alternative to platinum for catalyzing the hydrogen evolution reaction (HER). Previous studies were limited to only one phase, which is beta-Mo2C with an Fe 2N structure. Here, four molybdenum carbide materials including gamma-MoC with a WC type structure which was stabilized for the first time as a phase pure nanomaterial. Moreover, a wide range of magnetic iron-doped molybdenum carbide (Mo2-xFexC) nanomaterials were also synthesized, which exhibits a better HER activity to non-doped beta-Mo2C. A group of (CrxFe1-x)7C3 (0.2< x<1) solid solutions have also been synthesized for the first time as nanomaterials via AMOC method, which demonstrate excellent catalytic activities for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Other carbides/nitrides made from AMOCs include WN1-x, Fe3C, Fe3-xN, Fe3Mo3C, N 2Mo3C, Ni3Mo3C, Ni6Mo 6C, and Mo0.5W0.5C.

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Evaluation of titanium carbide metal matrix composites deposited via laser cladding

    NASA Astrophysics Data System (ADS)

    Cavanaugh, Daniel Thomas

    Metal matrix composites have been widely studied in terms of abrasion resistance, but a particular material system may behave differently as particle size, morphology, composition, and distribution of the hardening phase varies. The purpose of this thesis was to understand the mechanical and microstructural effects of combining titanium carbide with 431 series stainless steel to create a unique composite via laser cladding, particularly regarding wear properties. The most predominant effect in increasing abrasion resistance, measured via ASTM G65, was confirmed to be volume fraction of titanium carbide addition. Macrohardness was directly proportional to the amount of carbide, though there was an overall reduction in individual particle microhardness after cladding. The reduction in particle hardness was obscured by the effect of volume fraction carbide and did not substantially contribute to the wear resistance changes. A model evaluating effective mean free path of the titanium carbide particles was created and correlated to the measured data. The model proved successful in linking theoretical mean free path to overall abrasion resistance. The effects of the titanium carbide particle distributions were limited, while differences in particle size were noticeable. The mean free path model did not correlate well with the particle size, but it was shown that the fine carbides were completely removed by the coarse abrasive particles in the ASTM G65 test. The particle morphology showed indications of influencing the wear mode, but no statistical reduction was observed in the volume loss figures. Future studies may more specifically focus on particle morphology or compositional effects of the carbide particles.

  1. QM/MD simulation of SWNT nucleation on transition-metal carbide nanoparticles.

    PubMed

    Page, Alister J; Yamane, Honami; Ohta, Yasuhito; Irle, Stephan; Morokuma, Keiji

    2010-11-10

    The mechanism and kinetics of single-walled carbon nanotube (SWNT) nucleation from Fe- and Ni-carbide nanoparticle precursors have been investigated using quantum chemical molecular dynamics (QM/MD) methods. The dependence of the nucleation mechanism and its kinetics on environmental factors, including temperature and metal-carbide carbon concentration, has also been elucidated. It was observed that SWNT nucleation occurred via three distinct stages, viz. the precipitation of the carbon from the metal-carbide, the formation of a "surface/subsurface" carbide intermediate species, and finally the formation of a nascent sp(2)-hybidrized carbon structure supported by the metal catalyst. The SWNT cap nucleation mechanism itself was unaffected by carbon concentration and/or temperature. However, the kinetics of SWNT nucleation exhibited distinct dependences on these same factors. In particular, SWNT nucleation from Ni(x)C(y) nanoparticles proceeded more favorably compared to nucleation from Fe(x)C(y) nanoparticles. Although SWNT nucleation from Fe(x)C(y) and Ni(x)C(y) nanoparticle precursors occurred via an identical route, the ultimate outcomes of these processes also differed substantially. Explicitly, the Ni(x)-supported sp(2)-hybridized carbon structures tended to encapsulate the catalyst particle itself, whereas the Fe(x)-supported structures tended to form isolated SWNT cap structures on the catalyst surface. These differences in SWNT nucleation kinetics were attributed directly to the relative strengths of the metal-carbon interaction, which also dictates the precipitation of carbon from the nanoparticle bulk and the longevity of the resultant surface/subsurface carbide species. The stability of the surface/subsurface carbide was also influenced by the phase of the nanoparticle itself. The observations agree well with experimentally available data for SWNT growth on iron and nickel catalyst particles.

  2. Unintentional carbide formation evidenced during high-vacuum magnetron sputtering of transition metal nitride thin films

    NASA Astrophysics Data System (ADS)

    Greczynski, G.; Mráz, S.; Hultman, L.; Schneider, J. M.

    2016-11-01

    Carbide signatures are ubiquitous in the surface analyses of industrially sputter-deposited transition metal nitride thin films grown with carbon-less source materials in typical high-vacuum systems. We use high-energy-resolution photoelectron spectroscopy to reveal details of carbon temporal chemical state evolution, from carbide formed during film growth to adventitious carbon adsorbed upon contact with air. Using in-situ grown Al capping layers that protect the as-deposited transition metal nitride surfaces from oxidation, it is shown that the carbide forms during film growth rather than as a result of post deposition atmosphere exposure. The XPS signature of carbides is masked by the presence of adventitious carbon contamination, appearing as soon as samples are exposed to atmosphere, and eventually disappears after one week-long storage in lab atmosphere. The concentration of carbon assigned to carbide species varies from 0.28 at% for ZrN sample, to 0.25 and 0.11 at% for TiN and HfN, respectively. These findings are relevant for numerous applications, as unintentionally formed impurity phases may dramatically alter catalytic activity, charge transport and mechanical properties by offsetting the onset of thermally-induced phase transitions. Therefore, the chemical state of C impurities in PVD-grown films should be carefully investigated.

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

    DOE PAGES

    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

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

    PubMed

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

    2015-05-22

    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.

  5. Investigation of Fixed Points Exceeding 2500 °C Using Metal Carbide-Carbon Eutectics

    NASA Astrophysics Data System (ADS)

    Sasajima, N.; Yamada, Y.; Sakuma, F.

    2003-09-01

    The melting and freezing plateaus of four metal carbide-carbon (MC-C) eutectics, B4C-C, δ(Mo carbide)-C, TiC-C and ZrC-C eutectics were investigated by radiation thermometry for the first time. The observed melting temperatures were 2386 °C, 2583 °C, 2761 °C and 2883 °C, respectively. The plateau shapes of δ(Mo carbide)-C, TiC-C and ZrC-C eutectics are relatively flat compared to the quite rounded plateau shape of the B4C-C eutectic. The results indicate that MC-C eutectics can establish a new series of high-temperature fixed points above 2500 °C.

  6. 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

  7. 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

  8. 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.

  9. 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.

  10. 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.

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

    DOE PAGES

    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

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. The organometallic chemical vapor deposition of transition metal carbides: The use of homoleptic alkyls

    SciTech Connect

    Healy, M.D.; Smith, D.C.; Springer, R.W.; Rubiano, R.R.; Springer, R.W.; Parmeter, J.E.

    1993-12-31

    The organometallic chemical vapor deposition of transition metal carbides (M = Ti, Zr, Hf, and Cr) from tetraneopentyl-metal precursors has been carried out. Metal carbides can be deposited on Si, Al{sub 2}O{sub 3}, and stainless steel substrates from M[CH{sub 2}C(CH{sub 3}){sub 3}]{sub 4} at temperatures in the range of 300 to 750 C and pressures from 10{sup {minus}2} to 10{sup {minus}4} Torr. Thin films have also been grown using a carrier gas (Ar, H{sub 2}). The effects of variation of the metal center, deposition conditions, and reactor design on the resulting material have been examined by SEM, XPS, XRD, ERD and AES. Hydrocarbon fragments generated in the deposition chamber have been studied in by in-situ mass spectrometry. Complementary studies examining the UHV surface decomposition of Zr[CH{sub 2}C(CH{sub 3}){sub 3}]{sub 4} have allowed for a better understanding of the mechanism leading to film growth.

  19. 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.

  20. A metallic superhard boron carbide: first-principles calculations.

    PubMed

    Ma, Mengdong; Yang, Bingchao; Li, Zihe; Hu, Meng; Wang, Qianqian; Cui, Lin; Yu, Dongli; He, Julong

    2015-04-21

    A monoclinic BC3 phase (denoted M-BC3) has been predicted using first principles calculations. The M-BC3 structure is formed by alternately stacking sequences of metallic BC-layers and insulating C atom layers, thus, the structure exhibits two-dimensional conductivity. Its stability has been confirmed by our calculations of the total energy, elastic constants, and phonon frequencies. The pressure of phase transition from graphite-like BC3 to M-BC3 is calculated to be 9.3 GPa, and the theoretical Vickers hardness of M-BC3 is 43.8 GPa, this value indicates that the compound is a potentially superhard material. By comparing Raman spectral calculations of M-BC3 and previously proposed structures with the experimental data, we speculate that the experimentally synthesized BC3 crystal may simultaneously contain M-BC3 and Pmma-b phases.

  1. 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

  2. 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.

  3. Dry Sliding Wear behaviour of Aluminium-Red mud- Tungsten Carbide Hybrid metal matrix composites

    NASA Astrophysics Data System (ADS)

    Devi Chinta, Neelima; Selvaraj, N.; Mahesh, V.

    2016-09-01

    Red mud is an industrial waste obtained during the processing of alumina by Bayer's process. An attempt has been made to utilize the solid waste by using it as the reinforcement material in metal matrix composites. Red mud received from NALCO has been subjected for sieve analysis and milled to 42 nanometers using high energy ball mill. Red mud is used as a reinforcement material in Pure Aluminium matrix composite at 2%, 4%, and 6% weight at 100 microns level as well as 42 nano meters along with 4%Tungsten carbide by weight. Micro and Nano structured red mud powders, Tungsten carbide powder and Aluminium is mixed in a V-Blender, compacted at a pressure of 40 bar and samples are prepared by conventional sintering with vacuum as medium. In this current work, dry sliding wear characteristics at normal and heat treatment conditions are investigated with optimal combination of Aluminium, Tungsten carbide and different weight fractions of micro and nano structured red mud powder.

  4. 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.

  5. A structural diagnostics diagram for metallofullerenes encapsulating metal carbides and nitrides.

    PubMed

    Maki, Sachiko; Nishibori, Eiji; Terauchi, Ikuya; Ishihara, Masayuki; Aoyagi, Shinobu; Sakata, Makoto; Takata, Masaki; Umemoto, Hisashi; Inoue, Takashi; Shinohara, Hisanori

    2013-01-16

    Systematic structural studies of 24 different kinds of endohedral metallofullerenes, M(x)C(2n) (M = La, Y, Sc, Lu, Ti, Eu, Er, Hf, Sc(3)N; 34 ≤ n ≤ 43), as 1:1 cocrystals with solvent toluene molecules have been carried out using synchrotron radiation powder diffraction. Thirteen of the 24 molecular structures, including five metal carbides, one metal nitride endohedral fullerene, and one hollow fullerene, have been determined by a combination of the maximum entropy method and Rietveld refinement of the X-ray diffraction data obtained. We have found that the volume for one fullerene and one toluene molecule depends linearly on the number of carbon atoms in the fullerene cage. Fifteen different kinds of metal carbide endohedral fullerenes have been identified, which can be structurally characterized from the obtained lattice constants using only this linear dependence. The linear dependence found in the present study provides a metallofullerene diagnostics diagram that may have universal importance for structural characterization of the so-called cluster endohedral fullerenes.

  6. 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

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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

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

    DOE PAGES

    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

  15. 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

  16. New catalysts for coal processing: metal carbides and nitrides. Semiannual report, November 1, 1995 - July 17, 1996

    SciTech Connect

    Oyama, S. T.; Cox, D. F.

    1996-04-01

    Work involving the synthesis of monometallic transition metal carbides supported on alumina is described. The catalysts have excellent initial activity in the hydrodechlorination of CCl{sub 2}F{sub 2} (CFC 12), but deactivate with time by the deposition of carbon. Initial work on the preparation of unsupported bimetallic oxynitrides is also described.

  17. On dynamic and elastic stability of group IIIB metal carbides: Ab-initio calculations

    NASA Astrophysics Data System (ADS)

    Sahoo, B. D.; Mukherjee, D.; Joshi, K. D.; Gupta, Satish C.

    2012-06-01

    The elastic and dynamic stabilities of IIIB metal carbides in NaCl (B1 phase) type fcc structure have been investigated at zero pressure by first-principles calculations using the plane-wave pseudopotential method. The analysis of elastic moduli and phonon dispersion relations in ScC and YC suggest that the B1 phase is stable both elastically as well as dynamically at zero pressure. In contrast, for LaC, we find that the shear elastic modulus C' (=(C11-C12)/2) is negative at zero pressure and also the phonon frequencies in various directions of the Brillouin zone are imaginary, indicative of elastic as well as dynamic instability of B1 phase at zero pressure in this compound.

  18. 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.

  19. 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.

  20. Matrix isolation FTIR spectroscopic and DFT studies of metal-carbide clusters

    NASA Astrophysics Data System (ADS)

    Bejjani, Micheline

    2011-01-01

    Several metal containing molecules, including MgCN, NaCN, KCl, AlOH, and AlF have been observed in the interstellar medium. Additionally, transition metals have been observed. Many carbon containing molecules have also been observed in astrophysical sources. The purpose of the present research is to provide information on the spectral properties of metal carbide molecules that are potentially observable in space. Additional interest for studying small metal carbide molecules is the understanding of larger clusters including metallofullerenes and metallocarbohedrenes, and the catalytic growth of carbon nanotubes. FTIR spectra were obtained by condensing the vapor produced by dual laser ablation of metal and carbon rods in an argon matrix at ˜12K. Comparison of the observed 13C enriched vibrational spectra to the DFT simulated isotopic spectra has enabled the identification of vibrational fundamentals of linear MnC3, linear MgC3-, and chain ZnC3. The linear MnC3 has been detected for the first time. Its nu 1(sigma) vibrational fundamental has been observed at 1846.9 cm -1. Although previous photoelectron studies by Wang and Li have reported evidence for the cyclic isomer of MnC3, their assignment was inconclusive since the linear and fanlike structures have been found to lie very close in energy, and the observed PE frequency matched the frequencies predicted for the vibrational fundamentals of both the linear and the fanlike isomers of MnC3. Theoretical investigations of MgC3 - have indicated that the bent, linear, fan and kite structures are close in energy, and thus are potentially observables. In the present work, the nu1(sigma) asymmetric carbon stretching mode of linear MgC3- has been observed at 1797.5 cm-1. A second absorption at 1190.1 cm-1 which is correlated in intensity to the nu1(sigma) has tentatively been assigned to the nu2(sigma) vibrational fundamental. Although DFT calculations on ZnC3 have indicated that the linear, bent and kite structures are

  1. 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

  2. Formation Mechanism of Titanium Carbide Crystal in Laser Synthesized Metal-Ceramic Composite Coating

    NASA Astrophysics Data System (ADS)

    Du, Baoshuai; Zhang, Zhongwen; Wang, Xinhong; Zou, Zengda

    In situ titanium carbide reinforced iron-based composite coating was deposited on mild carbon steel using laser surface engineering (LSE) with ferrotitanium and graphite as precursor. The microstructure and phase constituents of the deposited coating were characterized. Formation mechanism of titanium carbide crystal in the composite coating was elucidated by correlating the morphology of titanium carbide and the thermal cycle experienced by the precursor during the laser treatment. It was demonstrated that titanium carbide was formed in situ as a result of the metallurgical reaction between ferrotitanium and graphite following a liquid-precipitation route. Different morphologies of titanium carbide crystal (dendrite and fishbone) correspond to the primary and eutectic titanium carbide respectively.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. SHORT COMMUNICATION: Metal carbide-carbon peritectic systems as high-temperature fixed points in thermometry

    NASA Astrophysics Data System (ADS)

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

    2006-10-01

    WC-C, Cr3C2-C and Mn7C3-C peritectic systems were investigated for their potential of serving as high-temperature reference points in thermometry. Mixtures of high-purity graphite powder with W, Cr and Mn powder of 99.99%, 99.9% and 99.95% purity by mass, respectively, were placed in graphite blackbody crucibles and melting/freezing plateaus were observed by means of a radiation thermometer. The observed melting temperatures were 2749 °C (WC-C), 1826 °C (Cr3C2-C) and 1331 °C (Mn7C3-C), with a repeatability—in each case—of 0.02 K. The melting range for WC-C and Cr3C2-C peritectics was roughly 0.1 K. WC-C showed a flat freezing plateau that agreed with the melting plateau within the repeatability. The three fixed points are possible candidates, like the metal (carbide)-carbon eutectic fixed points, in the realization of an improved high-temperature scale above the copper point.

  13. 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.

  14. 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.

  15. Fatigue behavior of silicon carbide reinforced titanium (Ti/SCS-6) metal matrix composites

    SciTech Connect

    Liaw, P.K.; Diaz, E.S.; Chiang, K.T.; Loh, D.H.

    1995-05-15

    Flexure fatigue behavior was investigated on titanium (Ti-15V-3Cr) metal matrix composites reinforced with cross-poly, continuous silicon carbide (SiC) fibers. The Ti/SCS-6 composites had an 8-ply, (0{degree}, 90{degree}, +45{degree}, {minus}45{degree}), symmetric lay-up. During fatigue testing, four stages of flexure deflection behavior were observed. The deflection at stage 1 increased slightly with fatigue cycling, while that at stage 2 increased significantly with cycling. Interestingly, the deflection at stage 3 again increased negligibly with fatigue cycling. Stage 4 was associated with final failure, and the deflection increased abruptly. In the stage 1 region of the deflection behavior, no cracks were observed, the Ti/SiC interface debonding could be present, and the deflection changed slightly with cycling. When the stage 2 region commenced, cracks began to initiate. As stage 2 progressed, both crack density and crack length increased. The increased crack density and crack length contributed to the great increase in the deflection during stage 2. In stage 3, significant crack deflection and branching, and fiber bridging occurred, and crack density remained relatively constant. Crack deflection and branching, and fiber bridging slowed down crack driving force, and little crack extension was observed, which resulted in an insignificant amount of increase in the stage 3 deflection. The breakage of fibers in stage 4 significantly increased deflection.

  16. Solid Oxide Membrane (SOM) Process for Facile Electrosynthesis of Metal Carbides and Composites

    NASA Astrophysics Data System (ADS)

    Zou, Xingli; Chen, Chaoyi; Lu, Xionggang; Li, Shangshu; Xu, Qian; Zhou, Zhongfu; Ding, Weizhong

    2016-09-01

    Metal carbides (MCs) and composites including TiC, SiC, TaC, ZrC, NbC, Ti5Si3/TiC, and Nb/Nb5Si3 have been directly electrosynthesized from their stoichiometric metal oxides/carbon (MOs/C) mixture precursors by an innovative solid oxide membrane (SOM)-assisted electrochemical process. MOs/C mixture powders including TiO2/C, SiO2/C, Ta2O5/C, ZrO2/C, Nb2O5/C, TiO2/SiO2/C, Nb2O5/SiO2 were pressed to form porous pellets and then served as cathode precursors. A SOM-based anode, made from yttria-stabilized zirconia (YSZ)-based membrane, was used to control the electroreduction process. The SOM electrochemical process was performed at 1273 K (1000 °C) and 3.5 to 4.0 V in molten CaCl2. The oxygen component contained in the MOs/C precursors was gradually removed during electroreduction process, and thus, MOs/C can be directly converted into MCs and composites at the cathode. The reaction mechanism of the electroreduction process and the characteristics of the obtained MCs and composites products were systematically investigated. The results show that the electrosynthesis process typically involves compounding, electroreduction, dissolution-electrodeposition, and in situ carbonization processes. The products can be predesigned and controlled to form micro/nanostructured MCs and composites. Multicomponent multilayer composites (MMCs) have also been tried to electrosynthesize in this work. It is suggested that the SOM-assisted electroreduction process has great potential to be used for the facile and green synthesis of various MCs and composites.

  17. 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

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

    DOE PAGES

    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

  19. 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

  20. 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.

  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. Molybdenum carbide as alternative catalysts to precious metals for highly selective reduction of CO2 to CO.

    PubMed

    Porosoff, Marc D; Yang, Xiaofang; Boscoboinik, J Anibal; Chen, Jingguang G

    2014-06-23

    Rising atmospheric CO2 is expected to have negative effects on the global environment from its role in climate change and ocean acidification. Utilizing CO2 as a feedstock to make valuable chemicals is potentially more desirable than sequestration. A substantial reduction of CO2 levels requires a large-scale CO2 catalytic conversion process, which in turn requires the discovery of low-cost catalysts. Results from the current study demonstrate the feasibility of using the non-precious metal material molybdenum carbide (Mo2C) as an active and selective catalyst for CO2 conversion by H2.

  3. 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...

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Origins of the high temperature increase of the thermal conductivity of transition metal carbides from atomistic simulations.

    PubMed

    Crocombette, Jean-Paul

    2013-12-18

    To understand the unexpected increase of the thermal conductivity of transition metal carbides at high temperatures, we calculate, with atomistic simulations, the thermal conductivity of zirconium carbide (ZrC). To account for the common substoichiometry of this material, various numbers of carbon vacancies are considered. The vibrational part of the conductivity is calculated by empirical potential molecular dynamics while the electronic part is calculated from density functional theory electronic structure with the Kubo-Greenwood formula on selected atomic configurations generated by the same empirical potential. We find that the vibrational part of the conductivity is negligible at temperatures higher than 1500 K. The increase of thermal conductivity with temperature is quantitatively reproduced in the calculations. It appears for all compositions and proves to rely entirely on its electronic component. Three phenomena are found responsible for the rise of the thermal conductivity with temperature: the semi-metallic shape of the electronic density of states, the additional electrical resistivity induced by carbon vacancies and the rise of the density of states with either temperature or the concentration of vacancies.

  9. 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.

  10. 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.

  11. Theoretical Analysis of the Adsorption of Late Transition Metal Atoms on the (001) Surface of Early Transition Metal Carbides

    SciTech Connect

    Rodriguez, J.A.; Gómez, T.; Florez, E.; Illas, F.

    2010-01-28

    The interaction of atoms of Groups 9, 10, and 11 with the (001) surface of TiC, ZrC, VC, and {delta}-MoC has been studied by means of periodic density functional calculations using slab models. The calculated values of the adsorption energy are rather large, especially for Groups 9 and 10 elements (E{sub ads} = 3-6 eV), but without clear trends along the series. Nevertheless, the analysis of the interaction at different sites indicates that the adsorbed atoms will be relatively mobile. Many of the admetals are electronically perturbed upon interaction with the carbide surfaces. Co, Ni, Cu, and Rh adatoms get positively or negatively charged, depending on the nature of the carbide substrate. Ir, Pd, Pt, and Au adatoms are always negatively charged. An analysis of the Bader charges for the most stable sites provides strong evidence that the most negative charge on the adatoms corresponds to the interaction with ZrC, followed by TiC. In the case of VC and {delta}-MoC, the charge on the adsorbed atoms may be slightly positive and of the same order for both carbides. The effect of the underlying carbide is large, with ZrC and TiC being predicted as the supports with the largest effect on the electronic structure of the adsorbed atoms with direct implications for the use of these systems in catalysis.

  12. Electron Microscopy Studies of Carbon Nanotubes, Metal Encapsulation, Fullerides, and Dispersed Carbide.

    NASA Astrophysics Data System (ADS)

    Liu, Mingqi

    The structures and morphologies of some carbon -related nanometer-size particles, including carbon nanotubes, nanoparticles, palladium (Pa) fullerides, hafnium carbide (HfC) dispersoids, and encapsulated lanthanum carbide (LaC _2), yttrium carbide (YC _2), cobalt carbide (Co_2 C), and manganese carbides (Mn_3 C, Mn_5C_2, Mn_7C_3, and Mn _{23}C_6), have been studied with high-resolution electron microscopy (HREM), scanning transmission electron microscopy (STEM), electron energy-loss spectroscopy (EELS), and electron diffraction. The formation mechanisms and growth behavior of these small particles have been examined based upon their images and diffraction patterns. A wide variety of nanotube morphologies have been observed, such as helical, nonhelical, circular cylindrical, and polygonal tubes. The helix angle within a tube changes every 3 to 5 sheets by a stepwise rotation of the hexagons. The neighboring sheets within a sheet group maintain the same helix angle by increasing the pitch number so that the helix angles existing in a tube are limited to some well -defined values. The most probable nucleation sites of tubes are the apex of nanoparticles and the half-domes of C_{60} molecules. Several tube growth defects have been identified, such as incomplete carbon sheets, U-turn growth, disordered sheet stacking, growth step, dividing wall, and tube bends. Encapsulation of LaC_2, YC_2, Mn_3C _, Mn_5C_2, Mn_7C_3, Mn _{23}C_6, and Co _2C nanocrystals have been observed within nanotubes and nanoparticles. Most encapsulated materials are perfect single crystals but some twins, faults, polycrystals, and incomplete carbides have also been found. Partial filling is the most typical growth characteristic for encapsulated LaC_2 and YC_2 while complete or near-complete filling is most often seen for manganese carbides and Co_2C. Several unique features are found in encapsulated manganese carbides, such as modulated structure, encapsulation-induced tube distortion, and carbon

  13. 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

  14. 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.

  15. An X-Ray Photoelectron Spectroscopy Study of Multilayered Transition Metal Carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Halim, Joseph

    Recently, a new family of two-dimensional (2D) early transition metal carbides and carbonitrides, labeled MXenes, was discovered at Drexel University. MXenes are produced by selectively etching mostly Al from Al-containing MAX phases and replacing Al with surface termination groups. Theoretically it has been predicted that changing the nature of the surface terminations, T, can change MXenes' properties, such as electronic and optical, resulting in changes in performance in various applications such as electrodes for Li-ion batteries. Prior to this work, there had been little systematic effort devoted to carefully identifying and quantifying the exact nature of T. In this work, high resolution XPS spectra of multilayered Ti3C2T x, Ti2CTx, Ti3CNTx, Nb 2CTx, Nb4C3Tx, V2CT x, Mo2CTx, Mo2TiC2T x, and Mo2Ti2C2Tx were acquired and analyzed. The influence of the M and X elements, the order of MXene, n, aging, Ar+ sputtering, and the concentration/nature of the etchants on the amounts of --O, --OH and --F, were systematically investigated. XPS analysis confirmed the intercalation of Li+ ions upon etching Ti3AlC2 using a mixture of LiF and HCl or LiCl and HF; when Ti3C2Tx multilayers is immersed in RbCl or NaCl solutions, cation exchange resulted in the replacement of Li+ ions with Rb+ or Na+ , respectively. Similar cation intercalations were confirmed when treating HF-etched Ti3C2Tx samples with Ti 3C2Tx with alkali metal hydroxides, such as NaOH and KOH. Based on quantification of the various chemical species before and after treatment, a mechanism was suggested where the reduction of -F terminations took place by exchanging with -OH and -O terminations and/or complete removal of Ti-F species and converting them to TiO2-Fx. From XPS peak fits for all MXene samples in this study, it was established that x was ≈ 2.0+/-0.2. Both -F and -OH terminations are formed during etching through the reaction of MXene with HF or H2O, respectively. However, for the -O terminations to

  16. Prediction of the quantum spin Hall effect in monolayers of transition-metal carbides MC (M = Ti, Zr, Hf)

    NASA Astrophysics Data System (ADS)

    Zhou, Liujiang; Shao, Bin; Shi, Wujun; Sun, Yan; Felser, Claudia; Yan, Binghai; Frauenheim, Thomas

    2016-09-01

    We report the existence of the quantum spin Hall effect (QSHE) in monolayers of transition-metal carbides MC (M = Zr, Hf). Under ambient conditions, the ZrC monolayer exhibits QSHE with an energy gap of 54 meV, in which topological helical edge states exist. Enhanced d xy -d xy interaction induces band inversion, resulting in nontrivial topological features. By applying in-plane strain, the HfC monolayer can be tuned from a trivial insulator to a quantum spin Hall insulator with an energy gap of 170 meV, three times that of the ZrC monolayer. The strong stability of MC monolayers provides a new platform for QSHE and spintronic applications.

  17. 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.

  18. 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.

  19. 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.

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

    DOE PAGES

    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

  1. 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.

  2. 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.

  3. 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.

  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. 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.

  6. Characterization of anisotropie elastic constants of silicon-carbide participate reinforced aluminum metal matrix composites: Part I. Experiment

    NASA Astrophysics Data System (ADS)

    Jeong, Hyunjo; Hsu, David K.; Shannon, Robert E.; Liaw, Peter K.

    1994-04-01

    The anisotropic elastic properties of silicon-carbide particulate (SiC p ) reinforced Al metal matrix composites were characterized using ultrasonic techniques and microstructural analysis. The composite materials, fabricated by a powder metallurgy extrusion process, included 2124, 6061, and 7091 Al alloys reinforced by 10 to 30 pct of α-SiC p by volume. Results were presented for the assumed orthotropic elastic constants obtained from ultrasonic velocities and for the microstructural data on particulate shape, aspect ratio, and orientation distribution. All of the composite samples exhibited a systematic anisotropy: the stiffness in the extrusion direction was the highest, and the stiffness in the out-of-plane direction was the lowest. Microstructural analysis suggested that the observed anisotropy could be attributed to the preferred orientation of SiC p . The ultrasonic velocity was found to be sensitive to internal defects such as porosity and intermetallic compounds. It has been observed that ultrasonics may be a useful, nondestructive technique for detecting small directional differences in the overall elastic constants of the composites since a good correlation has been noted between the velocity and microstructure and the mechanical test. By incorporating the observed microstructural characteristics, a theoretical model for predicting the anisotropic stiffnesses of the composites has been developed and is presented in a companion article (Part II).

  7. 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.

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

    DOE PAGES

    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

  9. 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

  10. 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.

  11. 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

  12. High-Performance Metal/Carbide Composites with Far-From-Equilibrium Compositions and Controlled Microstructures

    PubMed Central

    Hu, Liangfa; O’Neil, Morgan; Erturun, Veysel; Benitez, Rogelio; Proust, Gwénaëlle; Karaman, Ibrahim; Radovic, Miladin

    2016-01-01

    The prospect of extending existing metal-ceramic composites to those with the compositions that are far from thermodynamic equilibrium is examined. A current and pressure-assisted, rapid infiltration is proposed to fabricate composites, consisting of reactive metallic and ceramic phases with controlled microstructure and tunable properties. An aluminum (Al) alloy/Ti2AlC composite is selected as an example of the far-from-equilibrium systems to fabricate, because Ti2AlC exists only in a narrow region of the Ti-Al-C phase diagram and readily reacts with Al. This kind of reactive systems challenges conventional methods for successfully processing corresponding metal-ceramic composites. Al alloy/Ti2AlC composites with controlled microstructures, various volume ratios of constituents (40/60 and 27/73) and metallic phase sizes (42–83 μm, 77–276 μm, and 167–545 μm), are obtained using the Ti2AlC foams with different pore structures as preforms for molten metal (Al alloy) infiltration. The resulting composites are lightweight and display exceptional mechanical properties at both ambient and elevated temperatures. These structures achieve a compressive strength that is 10 times higher than the yield strength of the corresponding peak-aged Al alloy at ambient temperature and 14 times higher at 400 °C. Possible strengthening mechanisms are described, and further strategies for improving properties of those composites are proposed. PMID:27752106

  13. 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.

  14. 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.

  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. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  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.

  2. Materials characterization of silicon carbide reinforced titanium (Ti/SCS-6) metal matrix composites. Part 1: Tensile and fatigue behavior

    SciTech Connect

    Liaw, P.K.; Diaz, E.S.; Chiang, K.T.; Loh, D.H.

    1995-12-01

    Flexural fatigue behavior was investigated on titanium (Ti-15V-3Cr) metal matrix composites reinforced with cross-ply, continuous silicon carbide (SiC) fibers. The titanium composites had an eight-ply (0, 90, +45, {minus}45 deg) symmetric layup. Fatigue life was found to be sensitive to fiber layup sequence. Increasing the test temperature from 24 C to 427 C decreased fatigue life. Interface debonding and matrix and fiber fracture were characteristic of tensile behavior regardless of test temperature. In the tensile fracture process, interface debonding between SiC and the graphite coating and between the graphite coating and the carbon core could occur. A greater amount of coating degradation at 427 C than at 24 C reduced the Ti/SiC interface bonding integrity, which resulted in lower tensile properties at 427 C. During tensile testing, a crack could initiate from the debonded Ti/SiC interface and extend to the debonded interface of the neighboring fiber. The crack tended to propagate through the matrix and the interface. Dimpled fracture was the prime mode of matrix fracture. Interface debonding, matrix cracking, and fiber bridging were identified as the prime modes of fatigue mechanisms. To a lesser extent, fiber fracture was observed during fatigue. However, fiber fracture was believed to occur near the final stage of fatigue failure. In fatigued specimens, facet-type fracture appearance was characteristic of matrix fracture morphology. Theoretical modeling of the fatigue behavior of Ti/SCS-6 composites is presented in Part 2 of this series of articles.

  3. 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.

  4. 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.

  5. Subcell Structure and Two Different Superstructures of the Rare Earth Metal Silicide Carbides Y

    SciTech Connect

    Jeitschko, Wolfgang; Gerdes, Martin H.; Witte, Anne M.; Rodewald, Ute Ch.

    2001-01-01

    be represented by the formula (R{sup +3}){sub 3}(Si{sup {minus}3}){sub 2}(C{sub 2}){sup {minus}3}. A more detailed analysis of the interatomic distances showed that the shortest R-R distances are comparable with the R-R distances in the structures of the rare earth elements, thus indicating some R-R bonding. Therefore, the oxidation numbers of the rare earth atoms are slightly lower than +3, in agreement with the metallic conductivity of these compounds. As a consequence, considering the relatively short Si-Si bonds, the absolute value of the oxidation number of the silicon atoms may be lower than 3, resulting in a Si-Si bond order somewhat higher than 0.5.

  6. Developing scandium and zirconium containing aluminum boron carbide metal matrix composites for high temperature applications

    NASA Astrophysics Data System (ADS)

    Lai, Jing

    The study presented in this thesis focuses on developing castable, precipitation-strengthened Al--B4C metal matrix composites (MMCs) for high temperature applications. In the first part, B4C plates were immersed in liquid aluminum alloyed with Sc, Zr and Ti to investigate the interfacial reactions between B4C and liquid aluminum The influences of Sc, Zr and Ti on the interfacial microstructure in terms of individual and combined additions were examined. Results reveal that all three elements reacted with B4C and formed interfacial layers that acted as a diffusion barrier to limit the decomposition of B4C in liquid aluminum. The interfacial reactions and the reaction products in each system were identified. With the combined addition of Sc, Zr and Ti, most of the Ti was found to enrich at the interface, which not only offered appropriate protection of the B4C but also reduced the consumption of Sc and Zr at the interface. In the second part, Sc and Zr were introduced into Al-15vol.% B 4C composites presaturated by Ti, and eight experimental composites with different Sc and Zr levels were prepared via a conventional casting technique. It was found that Sc was involved in the interfacial reactions with B 4C that partially consume Sc. The Sc addition yielded considerable precipitation strengthening in the as-cast and peak aged conditions. To achieve an equivalent strengthening effect of Sc in binary Al-Sc alloys, approximately double the amount of Sc is required in Al-B4C composites. On the contrary, no major Zr reaction products were found at the interfaces and the major part of Zr remained in the matrix for the precipitation strengthening. The combination of Sc and Zr enhanced sthe precipitation strengthening. Two kinds of nanoscale precipitates, Al3Sc and Al3(Sc, Zr), were found in the as-cast microstructure and contributed to the increase in the matrix hardness. In the third part, all the experimental composites were isothermally aged at 300, 350, 400 and 450

  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. CORRELATED STRONTIUM AND BARIUM ISOTOPIC COMPOSITIONS OF ACID-CLEANED SINGLE MAINSTREAM SILICON CARBIDES FROM MURCHISON

    SciTech Connect

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

    2015-04-10

    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 {sup 88}Sr/{sup 86}Sr and {sup 138}Ba/{sup 136}Ba ratios in mainstream SiC grains, we are able to resolve the effect of {sup 13}C concentration from that of {sup 13}C-pocket mass on s-process nucleosynthesis, which points toward the existence of large {sup 13}C pockets with low {sup 13}C concentrations in asymptotic giant branch stars. The presence of such large {sup 13}C pockets with a variety of relatively low {sup 13}C concentrations seems to require multiple mixing processes in parent asymptotic giant branch stars of mainstream SiC grains.

  9. 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.

  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. 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.

  12. 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.

  13. 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.

  14. Structural prediction for scandium carbide monolayer sheet

    NASA Astrophysics Data System (ADS)

    Ma, Hong-Man; Wang, Jing; Zhao, Hui-Yan; Zhang, Dong-Bo; Liu, Ying

    2016-09-01

    A two-dimensional tetragonal scandium carbide monolayer sheet has been constructed and studied using density functional theory. The results show that the scandium carbide sheet is stable and exhibits a novel tetracoordinated quasiplanar structure, as favored by the hybridization between Sc-3d orbitals and C-2p orbitals. Calculations of the phonon dispersion as well as molecular dynamics simulations also demonstrate the structural stability of this scandium carbide monolayer sheet. Electronic properties show that the scandium carbide monolayer sheet is metallic and non-magnetic.

  15. Theoretical Analysis of the Adsorption of Late Transition-Metal Atoms on the (001) Surface of Early Transition-Metal Carbides

    SciTech Connect

    Gomez, T.; Florez, E; Rodriguez, J; Illas, F

    2010-01-01

    The interaction of atoms of Groups 9, 10, and 11 with the (001) surface of TiC, ZrC, VC, and {delta}-MoC has been studied by means of periodic density functional calculations using slab models. The calculated values of the adsorption energy are rather large, especially for Groups 9 and 10 elements (E{sub ads} = 3-6 eV), but without clear trends along the series. Nevertheless, the analysis of the interaction at different sites indicates that the adsorbed atoms will be relatively mobile. Many of the admetals are electronically perturbed upon interaction with the carbide surfaces. Co, Ni, Cu, and Rh adatoms get positively or negatively charged, depending on the nature of the carbide substrate. Ir, Pd, Pt, and Au adatoms are always negatively charged. An analysis of the Bader charges for the most stable sites provides strong evidence that the most negative charge on the adatoms corresponds to the interaction with ZrC, followed by TiC. In the case of VC and {delta}-MoC, the charge on the adsorbed atoms may be slightly positive and of the same order for both carbides. The effect of the underlying carbide is large, with ZrC and TiC being predicted as the supports with the largest effect on the electronic structure of the adsorbed atoms with direct implications for the use of these systems in catalysis.

  16. Characterization of metal ion-nucleic acid interactions in solution.

    PubMed

    Pechlaner, Maria; Sigel, Roland K O

    2012-01-01

    Metal ions are inextricably involved with nucleic acids due to their polyanionic nature. In order to understand the structure and function of RNAs and DNAs, one needs to have detailed pictures on the structural, thermodynamic, and kinetic properties of metal ion interactions with these biomacromolecules. In this review we first compile the physicochemical properties of metal ions found and used in combination with nucleic acids in solution. The main part then describes the various methods developed over the past decades to investigate metal ion binding by nucleic acids in solution. This includes for example hydrolytic and radical cleavage experiments, mutational approaches, as well as kinetic isotope effects. In addition, spectroscopic techniques like EPR, lanthanide(III) luminescence, IR and Raman as well as various NMR methods are summarized. Aside from gaining knowledge about the thermodynamic properties on the metal ion-nucleic acid interactions, especially NMR can be used to extract information on the kinetics of ligand exchange rates of the metal ions applied. The final section deals with the influence of anions, buffers, and the solvent permittivity on the binding equilibria between metal ions and nucleic acids. Little is known on some of these aspects, but it is clear that these three factors have a large influence on the interaction between metal ions and nucleic acids.

  17. 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.

  18. 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.

  19. 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.

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

    DOE PAGES

    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

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Meso/macroporous nitrogen-doped carbon architectures with iron carbide encapsulated in graphitic layers as an efficient and robust catalyst for the oxygen reduction reaction in both acidic and alkaline solutions.

    PubMed

    Xiao, Meiling; Zhu, Jianbing; Feng, Ligang; Liu, Changpeng; Xing, Wei

    2015-04-17

    Meso-/macroporous nitrogen-doped carbon architectures with iron carbide encapsulated in graphitic layers are fabricated by a facile approach. This efficient and robust material exhibits superior catalytic performance toward the oxygen reduction reaction in both acidic and alkaline solutions and is the most promising alternative to a Pt catalyst for use in electrochemical energy devices.

  7. Delivering carbide ligands to sulfide-rich clusters.

    PubMed

    Reinholdt, Anders; Herbst, Konrad; Bendix, Jesper

    2016-02-01

    The propensity of the terminal ruthenium carbide Ru(C)Cl2(PCy3)2 (RuC) to form carbide bridges to electron-rich transition metals enables synthetic routes to metal clusters with coexisting carbide and sulfide ligands. Electrochemical experiments show the Ru≡C ligand to exert a relatively large electron-withdrawing effect compared with PPh3, effectively shifting redox potentials.

  8. Ca2LiC3H: a new complex carbide hydride phase grown in metal flux.

    PubMed

    Lang, David A; Zaikina, Julia V; Lovingood, Derek D; Gedris, Thomas E; Latturner, Susan E

    2010-12-15

    The reaction of carbon and CaH2 in a calcium/lithium flux mixture produces crystals of the new compound Ca2LiC3H. This phase forms with a new structure type in tetragonal space group P4/mbm (a = 6.8236(1) Å, c = 3.7518(1) Å, Z = 2, R1 = 0.0151). This is a stuffed variant of the Cs2(NH2)N3 structure, containing hydride anions in octahedral sites; the structure determination by single-crystal X-ray diffraction surprisingly allowed the hydrogen to be detected. The Ca2LiC3H structure also features the rarely seen C3(4-) carbide anion; the protolysis reaction of this compound with ammonium chloride produces C3H4. The electronic properties of Ca2LiC3H were studied by quantum-chemical calculations including band structure and electron localization function (ELF) analysis; the phase is a charge-balanced semiconductor with a calculated band gap of 0.48 eV. This is in agreement with (7)Li, (13)C, and (1)H MAS NMR data, which show resonances in the ionic region instead of the Knight shifted region. ELF analysis of the theoretical nonhydrided Ca2LiC3 structure confirms the ability of these calculations to properly locate hydrides and supports the structural model based on X-ray diffraction data.

  9. 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.

  10. 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

  11. 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)

  12. 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.

  13. Materials characterization of silicon carbide reinforced titanium (Ti/SCS-6) metal matrix composites. Part 2: Theoretical modeling of fatigue behavior

    SciTech Connect

    Chiang, K.T.; Loh, D.H.; Liaw, P.K.; Diaz, E.S.

    1995-12-01

    Flexural fatigue behavior was investigated on titanium (Ti-15V-3Cr) metal matrix composites reinforced with cross-ply, continuous silicon carbide (SiC) fibers. The titanium composites had an eight-ply (0, 90, +45, {minus}45 deg) symmetric layup. Mechanistic investigation of the fatigue behavior is presented in Part 1 of this series. In Part 2, theoretical modeling of the fatigue behavior was performed using finite element techniques to predict the four stages of fatigue deflection behavior. On the basis of the mechanistic understanding, the fiber and matrix fracture sequence was simulated from ply to ply in finite element modeling. The predicted fatigue deflection behavior was found to be in good agreement with the experimental results. Furthermore, it has been shown that the matrix crack initiation starts in the 90 deg ply first, which is in agreement with the experimental observation. Under the same loading condition, the stress in the 90 deg ply of the transverse specimen is greater than that of the longitudinal specimen. This trend explains whey the longitudinal specimen has a longer fatigue life than the transverse specimen, as observed in Part 1.

  14. 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.

  15. 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.

  16. Selective etching of silicon carbide films

    DOEpatents

    Gao, Di; Howe, Roger T.; Maboudian, Roya

    2006-12-19

    A method of etching silicon carbide using a nonmetallic mask layer. The method includes providing a silicon carbide substrate; forming a non-metallic mask layer by applying a layer of material on the substrate; patterning the mask layer to expose underlying areas of the substrate; and etching the underlying areas of the substrate with a plasma at a first rate, while etching the mask layer at a rate lower than the first rate.

  17. 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.

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

    PubMed

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

    1985-11-01

    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

  19. Prealloyed catalyst for growing silicon carbide whiskers

    DOEpatents

    Shalek, Peter D.; Katz, Joel D.; Hurley, George F.

    1988-01-01

    A prealloyed metal catalyst is used to grow silicon carbide whiskers, especially in the .beta. form. Pretreating the metal particles to increase the weight percentages of carbon or silicon or both carbon and silicon allows whisker growth to begin immediately upon reaching growth temperature.

  20. [Application of gypsum-bonded investment containing niobium carbide on casting of alloy for metal-ceramic restoration].

    PubMed

    Tsuruta, S; Ban, S; Hasegawa, J; Hayashi, S; Iiyama, K; Yamamura, Y

    1990-07-01

    Experimental gypsum-bonded investments containing 0.5-5.0 wt% NbC were prepared by mechanical mixing of each powder. Setting and thermal expansion measurement, compressive strength and casting accuracy for Ni-Cr alloy for metal-ceramic restoration were investigated. Analysis of NbC during heating was carried out by X-ray diffraction, TG-DTA and SEM. NbC was oxidized to Nb2O5 with a volume change between 300-600 degrees C, as in the following equation: 2NbC + 4 1/2O2----Nb2O5 + 2CO2 The theoretical volume of 1/2Nb2O5 calculated from the lattice constants according to JCPDS file was approximately 4 times larger than that of NbC. The experimental investments of 70 wt% cristobalite and 30 wt% gypsum containing 2.0, 3.0 and 5.0 wt% NbC showed large thermal expansion of 7.0, 10.0 and 13.0% respectively. The investment containing 2.0 wt% NbC showed nearly the same casting accuracy for Ni-Cr alloys for metal-ceramic restoration as the commercial phosphate-bonded investment.

  1. 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.

  2. 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.

  3. 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.

  4. 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 PAGES

    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

  5. 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).

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Corrosion and wear resistance of tungsten carbide-cobalt and tungsten carbide-cobalt-chromium thermal spray coatings

    SciTech Connect

    Quets, J.; Alford, J.R.

    1999-07-01

    Tungsten carbide thermal spray coatings provide wear surfaces to new and overhauled components for various industries. Their wear resistance is obtained by incorporating small tungsten carbide particles into a metal matrix. This presentation will show what parameters influence their corrosion resistance in the ASTM B-117 Salt Spray Corrosion Test,

  12. 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.

  13. 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).

  14. 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...

  15. Microorganisms in subterranean acidic waters within Europe's deepest metal mine.

    PubMed

    Kay, Catherine M; Haanela, Anu; Johnson, D Barrie

    2014-11-01

    The Pyhäsalmi mine, central Finland, has operated as a deep metal mine since 1967. It currently reaches a depth of almost 1500 m, making it the deepest mining operation in Europe. Around 900,000 m(3) of metal-rich, extremely acidic water are pumped out of the mine each year. The near constant air temperature of ∼ 24 °C together with exposure of sulfidic rock surfaces to air and water, have created an environment that is highly suitable for colonization by acidophilic mineral-oxidizing microorganisms. Using a combined cultivation-dependent and molecular approach, indigenous bacteria in waters at two depths within the mine, and of an acid streamer sample were identified and isolated. Iron-oxidizing chemolithotrophs (Acidithiobacillus and Leptospirillum spp., and "Ferrovum myxofaciens" were the most abundant bacteria in mine water samples, whereas the acid streamer community contained a greater proportion of heterotrophic acidophiles (Ferrimicrobium acidiphilum and a gammaproteobacterium related to Metallibacterium scheffleri). The most abundant isolates obtained from both water and streamer samples were all strains of Acidithiobacillus Group IV, a proposed separate species of iron-oxidizing acidithiobacilli that has not yet been classified as such. Archaea were also detected in water and streamer samples using molecular methods, but most were not identified and no isolates were obtained.

  16. EXAFS of heavy metal coordination in acid mine drainage sediments

    SciTech Connect

    Carroll, S.; O`Day, P.; Waychunas, G.; Phillips, B.

    1995-12-01

    We use extended x-ray adsorption fine structure (EXAFS) spectroscopy to examine the chemical environment of zinc (1-2 wt. %), lead (300-600 ppm) and cadmium (50-200 ppm) in complex acid mine drainage sediments from the Tri-State Mining District (KS, MO, OK). The sediments in streams draining tailings piles and open mine shafts are dominated by quartz or amorphous iron hydroxides; accessory minerals include calcite. The bulk water chemistry is buffered by the limestone geology and is undersaturated with respect to pure heavy metal carbonates and hydroxides. EXAFS spectra of the sediment samples were taken at SSRL with a fluorescence detector at low temperature ({approximately}10 K). Heavy metals do not form pure carbonate or hydroxide phases, nor do they appear to sorb to quartz surfaces. In sediments near the mine source, the metals are present primarily as sulfides, the original host mineral. With increasing distance from the source, second-neighbor backscattering from Fe indicates that the metals leached from the sulfides are taken up with amorphous iron hydroxides.

  17. 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

  18. Metal ion-catalyzed nucleic acid alkylation and fragmentation.

    PubMed

    Browne, Kenneth A

    2002-07-10

    Nucleic acid microarrays are a growing technology in which high densities of known sequences are attached to a substrate in known locations (addressed). Hybridization of complementary sequences leads to a detectable signal such as an electrical impulse or fluorescence. This combination of sequence addressing, hybridization, and detection increases the efficiency of a variety of genomic disciplines including those that profile genetic expression, search for single nucleotide polymorphisms (SNPs), or diagnose infectious diseases by sequencing portions of microbial or viral genomes. Incorporation of reporter molecules into nucleic acids is essential for the sensitive detection of minute amounts of nucleic acids on most types of microarrays. Furthermore, polynucleic acid size reduction increases hybridization because of increased diffusion rates and decreased competing secondary structure of the target nucleic acids. Typically, these reactions would be performed as two separate processes. An improvement to past techniques, termed labeling-during-cleavage (LDC), is presented in which DNA or RNA is alkylated with fluorescent tags and fragmented in the same reaction mixture. In model studies with 26 nucleotide-long RNA and DNA oligomers using ultraviolet/visible and fluorescence spectroscopies as well as high-pressure liquid chromatography and mass spectrometry, addition of both alkylating agents (5-(bromomethyl)fluorescein, 5- or 6-iodoacetamidofluorescein) and select metal ions (of 21 tested) to nucleic acids in aqueous solutions was critical for significant increases in both labeling and fragmentation, with >or=100-fold increases in alkylation possible relative to metal ion-free reactions. Lanthanide series metal ions, Pb(2+), and Zn(2+) were the most reactive ions in terms of catalyzing alkylation and fragmentation. While oligonucleotides were particularly susceptible to fragmentation at sites containing phosphorothioate moieties, labeling and cleavage reactions

  19. Mixed metal phospho-sulfates for acid catalysis

    SciTech Connect

    Thoma, S.G.; Jackson, N.B.; Nenoff, T.M.; Maxwell, R.S.

    1997-12-01

    Mixed metal phospho-sulfates have been prepared and evaluated for use as acid catalysts via 2-methyl-2-pentene isomerization and o-xylene isomerization. Particular members of this class of materials exhibit greater levels of activity than sulfated zirconia as well as lower rates and magnitudes of deactivation. {sup 31}P MAS NMR has been used to examine the role of phosphorus in contributing to the activity and deactivation behavior of these materials, while powder x-ray diffraction, BET surface area, IR, and elemental analysis were used to characterize the bulk catalysts.

  20. Inhibition studies of soybean (Glycine max) urease with heavy metals, sodium salts of mineral acids, boric acid, and boronic acids.

    PubMed

    Kumar, Sandeep; Kayastha, Arvind M

    2010-10-01

    Various inhibitors were tested for their inhibitory effects on soybean urease. The K(i) values for boric acid, 4-bromophenylboronic acid, butylboronic acid, and phenylboronic acid were 0.20 +/- 0.05 mM, 0.22 +/- 0.04 mM, 1.50 +/- 0.10 mM, and 2.00 +/- 0.11 mM, respectively. The inhibition was competitive type with boric acid and boronic acids. Heavy metal ions including Ag(+), Hg(2+), and Cu(2+) showed strong inhibition on soybean urease, with the silver ion being a potent inhibitor (IC(50) = 2.3 x 10(-8) mM). Time-dependent inhibition studies exhibited biphasic kinetics with all heavy metal ions. Furthermore, inhibition studies with sodium salts of mineral acids (NaF, NaCl, NaNO(3), and Na(2)SO(4)) showed that only F(-) inhibited soybean urease significantly (IC(50) = 2.9 mM). Competitive type of inhibition was observed for this anion with a K(i) value of 1.30 mM.

  1. 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.

  2. Power MOSFETs Formed In Silicon Carbide

    NASA Technical Reports Server (NTRS)

    Palmour, John W.

    1995-01-01

    High-performance power metal/oxide/semiconductor field-effect transistors (MOSFETs) fabricated in silicon carbide. Devices offer potential advantages over silicon-based MOSFETs, including lower "on" - state resistances at same rated voltages, ability to operate at higher temperatures, and higher thermal conductivity. Also more resistant to damage by ionizing radiation, an advantage for switching appications in nuclear facilities.

  3. 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...

  4. 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...

  5. 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...

  6. 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... 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...

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 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...

  12. 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... 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...

  13. 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.

  14. 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.

  15. 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.

  16. Development and characterization of solid solution tri-carbides

    NASA Astrophysics Data System (ADS)

    Knight, Travis; Anghaie, Samim

    2001-02-01

    Solid-solution, binary uranium/refractory metal carbide fuels have been shown to be capable of performing at high temperatures for nuclear thermal propulsion applications. More recently, tri-carbide fuels such as (U, Zr, Nb)C1+x with less than 10% metal mole fraction uranium have been studied for their application in ultra-high temperature, high performance space nuclear power systems. These tri-carbide fuels require high processing temperatures greater than 2600 K owing to their high melting points in excess of 3600 K. This paper presents the results of recent studies involving hypostoichiometric, single-phase tri-carbide fuels. Processing techniques of cold uniaxial pressing and sintering were investigated to optimize the processing parameters necessary to produce high density (low porosity), single phase, solid solution mixed carbide nuclear fuels for testing. Scanning electron microscopy and xray diffraction were used to analyze samples. Liquid phase sintering with UC1+x at temperatures near 2700 K was shown to be instrumental in achieving good densification in hyper- and near-stoichiometric mixed carbides. Hypostoichiometric carbides require even higher processing temperatures greater than 2800 K in order to achieve liquid phase sintering with a UC liquid phase and good densification of the final solid solution, tri-carbide fuel. .

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. The rare-earth metal carbide halide superconductors RE 2C 2X 2 (RE=Y, La; X=Cl, Br, I)

    NASA Astrophysics Data System (ADS)

    Kremer, R. K.; Ahn, K.; Henn, R. W.; Mattausch, Hj; Schnelle, W.; Stolovits, A.; Simon, A.

    1999-05-01

    Superconductivity in layered yttrium carbide bromides and iodides with transition temperatures ranging up to 11.6 K is achieved by adjusting the Br:I, ratio to ≈1:3 in phases of Y 2C 2(Br,I) 2. In our contribution, we compile basic physical and chemical properties of Y 2C 2X 2 (X=Cl, Br, I) and present new results of the La-based phases La 2C 2X 2 (X=Br, I).

  6. Gas-phase ion-molecule reactions of metal-carbide cations MCn+ (M=Y and La; n=2, 4, and 6) with benzene and cyclohexane investigated by FTICR mass spectrometry and DFT calculations.

    PubMed

    Zhang, Rui; Dinca, Adriana; Fisher, Keith J; Smith, Derek R; Willett, Gary D

    2005-01-13

    Yttrium- and lanthanum-carbide cluster cations YC(n)(+) and LaC(n)(+) (n = 2, 4, and 6) are generated by laser ablation of carbonaceous material containing Y(2)O(3) or La(2)O(3). YC(2)(+), YC(4)(+), LaC(2)(+), LaC(4)(+), and LaC(6)(+) are selected to undergo gas-phase ion-molecule reactions with benzene and cyclohexane. The FTICR mass spectrometry study shows that the reactions of YC(2)(+) and LaC(2)(+) with benzene produce three main series of cluster ions. They are in the form of M(C(6)H(4))(C(6)H(6))(n)(+), M(C(8)H(4))(C(6)H(6))(n)(+), and M(C(8)H(6))(C(6)H(6))(m)(+) (M = Y and La; n = 0-3; m = 0-2). For YC(4)(+), LaC(4)(+), and LaC(6)(+), benzene addition products in the form of MC(n)(C(6)H(6))(m)(+) (M = Y and La; n = 4, 6; m = 1, 2) are observed. In the reaction with cyclohexane, all the metal-carbide cluster ions are observed to form metal-benzene complexes M(C(6)H(6))(n)(+) (M = Y and La; n= 1-3). Collision-induced-dissociation experiments were performed on the major reaction product ions, and the different levels of energy required for the fragmentation suggest that both covalent bonding and weak electrostatic interaction exist in these organometallic complexes. Several major product ions were calculated using DFT theory, and their ground-state geometries and energies were obtained.

  7. 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.

  8. 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.

  9. 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...

  10. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 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...

  11. 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...

  12. 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...

  13. 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...

  14. 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)...

  15. 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...

  16. 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.

  17. 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.

  18. 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.

  19. MODIFICATION OF METAL PARTITIONING BY SUPPLEMENTING ACID VOLATILE SULFIDE IN FRESHWATER SEDIMENTS

    EPA Science Inventory

    Acid volatile sulfide is a component of sediments which complexes some cationic metals and thereby influences the toxicity of these metals to benthic organisms. EPA has proposed AVS as a key normalization phase for the development of sediment quality criteria for metals. Experime...

  20. 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...

  1. 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...

  2. 40 CFR 721.10097 - Disubstituted benzenesulfonic acid, alkali metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., 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...

  3. 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...

  4. 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...

  5. 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.

  6. 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.

  7. 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

  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. 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

  10. 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.

  11. 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

  12. Fungal production of citric and oxalic acid: importance in metal speciation, physiology and biogeochemical processes.

    PubMed

    Gadd, G M

    1999-01-01

    The production of organic acids by fungi has profound implications for metal speciation, physiology and biogeochemical cycles. Biosynthesis of oxalic acid from glucose occurs by hydrolysis of oxaloacetate to oxalate and acetate catalysed by cytosolic oxaloacetase, whereas on citric acid, oxalate production occurs by means of glyoxylate oxidation. Citric acid is an intermediate in the tricarboxylic acid cycle, with metals greatly influencing biosynthesis: growth limiting concentrations of Mn, Fe and Zn are important for high yields. The metal-complexing properties of these organic acids assist both essential metal and anionic (e.g. phosphate) nutrition of fungi, other microbes and plants, and determine metal speciation and mobility in the environment, including transfer between terrestrial and aquatic habitats, biocorrosion and weathering. Metal solubilization processes are also of potential for metal recovery and reclamation from contaminated solid wastes, soils and low-grade ores. Such 'heterotrophic leaching' can occur by several mechanisms but organic acids occupy a central position in the overall process, supplying both protons and a metal-complexing organic acid anion. Most simple metal oxalates [except those of alkali metals, Fe(III) and Al] are sparingly soluble and precipitate as crystalline or amorphous solids. Calcium oxalate is the most important manifestation of this in the environment and, in a variety of crystalline structures, is ubiquitously associated with free-living, plant symbiotic and pathogenic fungi. The main forms are the monohydrate (whewellite) and the dihydrate (weddelite) and their formation is of significance in biomineralization, since they affect nutritional heterogeneity in soil, especially Ca, P, K and Al cycling. The formation of insoluble toxic metal oxalates, e.g. of Cu, may confer tolerance and ensure survival in contaminated environments. In semi-arid environments, calcium oxalate formation is important in the formation and

  13. Effect of the combination of dithiooctanoate monomers and acidic adhesive monomers on adhesion to precious metals, precious metal alloys and non-precious metal alloys.

    PubMed

    Ikemura, Kunio; Kojima, Katsunori; Endo, Takeshi; Kadoma, Yoshinori

    2011-01-01

    This study investigated the effect of the combination of a dithiooctanoate monomer and an acidic adhesive monomer on adhesion to precious metals, precious and non-precious metal alloys. From a selection of four dithiooctanoate monomers and six acidic adhesive monomers, 14 experimental primers containing a combination of 5.0 wt% of a dithiooctanoate monomer and 1.0 wt% of an acidic adhesive monomer in acetone were prepared. Tensile bond strengths (TBSs) of MMA-PMMA/TBBO resin to nine kinds of precious metals, precious metal alloys, and non-precious metal alloys after 2,000 thermal cycles were measured. Results showed that there were no significant differences in TBS among the primers to all the precious and non-precious metal adherends tested (p>0.05). Highest TBS values (46.5-55.8 MPa) for bonding to Au alloy, Au-Ag-Pd alloy, Co-Cr alloy, and Ni-Cr alloy were achieved with the primer which contained 5.0 wt% 10-methacryloyloxydecyl 6,8-dithiooctanoate (10-MDDT) and 1.0 wt% 6-methacryloyloxyhexyl phosphonoacetate (6-MHPA). Therefore, 5.0 wt% 10-MDDT and 1.0 wt% 6-MHPA was determined as the optimal combination for bonding to precious metals, precious and non-precious metal alloys.

  14. Processes controlling metal ion attenuation in acid mine drainage streams

    NASA Astrophysics Data System (ADS)

    Chapman, B. M.; Jones, D. R.; Jung, R. F.

    1983-11-01

    Two acid mine drainage streams have been investigated by detailed analysis of their sediments and waters, to obtain an understanding of the dominant processes which control the transport and attenuation of heavy metals under conditions of chronic high-level pollutant input. One of the water-courses has a thick hydrous iron oxide crust on its bed, where biotically mediated oxidation of ferrous iron resulted in precipitation of amorphous ferric hydroxide, along with substantial quantities of adsorbed silica, sulphate and Al and lesser quantities of As. Small amounts of K and Pb (and possibly hydronium) jarosites were also present in the sediments. Changes in pH and in the concentrations of Cu, Zn, and Cd appear to be mainly the result of dilution by seeps and tributaries. Although no sediment was recovered during collection of water samples from the second stream, saturation index calculations imply that precipitation should have been occurring. The observed down-stream loss of a number of elements supported this conclusion. The solids predicted to be precipitating were A1(OH) 3, Cu 2(OH) 2CO 3, and Fe(OH) 3. Observed decreases in the concentrations of Cd, Zn and Mn can be accounted for on the basis of dilution alone. However, the additional mechanism of neutralization by higher pH inflows is required to account for the decrease in hydrogen ion concentration downstream. The basis for a potentially useful new technique (congruent element analysis) which enables the identification of conservative components in streams is presented. Comparison of logarithmic concentration versus distance plots delineates the point where chemical removal mechanisms become important for each element.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Status of advanced carbide fuels: Past, present, and future

    NASA Astrophysics Data System (ADS)

    Anghaie, Samim; Knight, Travis

    2002-01-01

    Solid solution, mixed uranium/refractory metal carbide fuels such as (U, Zr, Nb)C, so called ternary carbide or tri-carbide fuels have great potential for applications in next generation advanced nuclear power reactors. Because of their high melting points, high thermal conductivity, improved resistance to hot hydrogen corrosion, and good fission product retention, these advanced nuclear fuels have great potential for high performance reactors with increased safety margins. Despite these many benefits, some concerns regarding carbide fuels include compatibility issues with coolant and/or cladding materials and their endurance under the extreme conditions associated with nuclear thermal propulsion. The status of these fuels is reviewed to characterize their performance for space nuclear power applications. Results of current investigations are presented and as well as future directions of study for these advanced nuclear fuels. .

  20. 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.

  1. Transition metal cation separations with a resorcinarene-based amino acid stationary phase.

    PubMed

    Li, Na; Allen, Lee J; Harrison, Roger G; Lamb, John D

    2013-03-01

    A resorcinarene-based macrocyclic ligand functionalized with alanine and undecyl groups (AUA) was synthesized and applied to ion chromatographic separations. The selectivity and separation of transition metal ions on a column packed with AUA adsorbed onto 55% cross-linked styrene-divinylbenzene resin are presented. The upper and lower rims of the resorcinarene were modified with amino acids and -C(11)H(23) alkyl chains, respectively. The four carboxylic acid groups on the upper rim act as cation-exchangers while the four -C(11)H(23) alkyl chains serve to anchor the ligand to the resin surface by the hydrophobic effect. A systematic study of the effect of different eluent components including non-metal-chelating (HNO(3)) and chelating acids (oxalic acid, succinic acid, dipicolinic acid, and citric acid) on the retention of transition metal ions was investigated. Six metal ions (Mn(2+), Co(2+), Ni(2+), Cd(2+), Cu(2+), and Zn(2+)) were separated on the AUA column within a reasonable time with a single eluent gradient using oxalic acid. The separation is compared to that obtained using a commercial column containing carboxylic acid functional groups. The AUA column containing four preorganized carboxylic acid groups showed selectivity for Cu(2+) when no chelating eluent was present, a selectivity which was not observed with the comparison column.

  2. 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.

  3. A study on the production of titanium carbide nano-powder in the nanostate and its properties

    NASA Astrophysics Data System (ADS)

    Shiryaeva, L. S.; Rudneva, S. V.; Galevsky, G. V.; Garbuzova, A. K.

    2016-09-01

    The plasma synthesis of titanium carbide nano-powder in the conditions close to industrial was studied. Titanium carbide TiC is a wear- and corrosion-resistant, hard, chemically inert material, demanded in various fields for the production of hard alloys, metal- ceramic tools, heat-resistant products, protective metal coatings. New perspectives for application titanium carbide in the nanostate can be found in the field of alloys modification with different composition and destination.

  4. 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

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Aqueous-phase hydrogenation of acetic acid over transition metal catalysts

    SciTech Connect

    Olcay, Hakan; Xu, Lijun; Xu, Ye; Huber, George

    2010-01-01

    Catalytic hydrogenation of acetic acid to ethanol has been carried out in aqueous phase on several metals, with ruthenium being the most active and selective. DFT calculations suggest that the initial CO bond scission yielding acetyl is the key step and that the intrinsic reactivity of the metals accounts for the observed activity.

  10. 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)

  11. Biological treatment of heavy metals in acid mine drainage using sulfate reducing bioreactors.

    PubMed

    Sierra-Alvarez, R; Karri, S; Freeman, S; Field, J A

    2006-01-01

    The uncontrolled release of acid mine drainage (AMD) from abandoned mines and tailing piles threatens water resources in many sites worldwide. AMD introduces elevated concentrations of sulfate ions and dissolved heavy metals as well as high acidity levels to groundwater and receiving surface water. Anaerobic biological processes relying on the activity of sulfate reducing bacteria are being considered for the treatment of AMD and other heavy metal containing effluents. Biogenic sulfides form insoluble complexes with heavy metals resulting in their precipitation. The objective of this study was to investigate the remediation of AMD in sulfate reducing bioreactors inoculated with anaerobic granular sludge and fed with an influent containing ethanol. Biological treatment of an acidic (pH 4.0) synthetic AMD containing high concentrations of heavy metals (100 mg Cu(2+)l(-1); 10 mg Ni(2+)l(-1), 10 mg Zn(2+)l(-1)) increased the effluent pH level to 7.0-7.2 and resulted in metal removal efficiencies exceeding 99.2%. The highest metal precipitation rates attained for Cu, Ni and Zn averaged 92.5, 14.6 and 15.8 mg metal l(-1) of reactor d(-1). The results of this work demonstrate that an ethanol-fed sulfidogenic reactor was highly effective to remove heavy metal contamination and neutralized the acidity of the synthetic wastewater.

  12. 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.

  13. Regional trends in soil acidification and exchangeable metal concentrations in relation to acid deposition rates.

    PubMed

    Stevens, Carly J; Dise, Nancy B; Gowing, David J

    2009-01-01

    The deposition of high levels of reactive nitrogen (N) and sulphur (S), or the legacy of that deposition, remain among the world's most important environmental problems. Although regional impacts of acid deposition in aquatic ecosystems have been well documented, quantitative evidence of wide-scale impacts on terrestrial ecosystems is not common. In this study we analysed surface and subsoil chemistry of 68 acid grassland sites across the UK along a gradient of acid deposition, and statistically related the concentrations of exchangeable soil metals (1 M KCl extraction) to a range of potential drivers. The deposition of N, S or acid deposition was the primary correlate for 8 of 13 exchangeable metals measured in the topsoil and 5 of 14 exchangeable metals in the subsoil. In particular, exchangeable aluminium and lead both show increased levels above a soil pH threshold of about 4.5, strongly related to the deposition flux of acid compounds.

  14. 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.

  15. 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.

  16. Selective encapsulation of the carbides of yttrium and titanium into carbon nanoclusters

    SciTech Connect

    Seraphin, S.; Zhou, D. ); Jiao, J. ); Withers, J.C.; Loutfy, R. )

    1993-10-11

    Characterization of the arc-discharge deposits at the cathode from anodes containing yttrium oxide and titanium by transmission electron microscopy and x-ray diffraction shows different results with respect to an encapsulation of the metal carbides into carbon clusters. Yttrium carbide is encapsulated into carbon nanoclusters in a crystalline phase. The formation of titanium carbide, on the other hand, preempts the formation of the carbon---carbon bonds necessary to form the carbon cages, so that only titanium carbide clusters are observed. Thermodynamic data support the interpretation of the results.

  17. Selective encapsulation of the carbides of yttrium and titanium into carbon nanoclusters

    NASA Astrophysics Data System (ADS)

    Seraphin, Supapan; Zhou, Dan; Jiao, Jun; Withers, James C.; Loutfy, Raouf

    1993-10-01

    Characterization of the arc-discharge deposits at the cathode from anodes containing yttrium oxide and titanium by transmission electron microscopy and x-ray diffraction shows different results with respect to an encapsulation of the metal carbides into carbon clusters. Yttrium carbide is encapsulated into carbon nanoclusters in a crystalline phase. The formation of titanium carbide, on the other hand, preempts the formation of the carbon—carbon bonds necessary to form the carbon cages, so that only titanium carbide clusters are observed. Thermodynamic data support the interpretation of the results.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  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. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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...

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

    USGS Publications Warehouse

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

    1998-01-01

    Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ 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 Ca2+ 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 13C NMR, 1H NMR, and FT-1R 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 Ca2+ 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.Fulvic acid, isolated from the Suwannee River, Georgia, was assessed for its ability to bind Ca2+, Cd2+, Cu2+, Ni2+, and Zn2+ 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 Ca2+ 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 13C NMR, 1H NMR, and FT-IR spectrometry and elemental, titrimetric, and molecular weight determinations. The characterization data revealed that

  10. 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.

  11. 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.

  12. 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.

  13. 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).

  14. Metal amides as the simplest acid/base catalysts for stereoselective carbon-carbon bond-forming reactions.

    PubMed

    Yamashita, Yasuhiro; Kobayashi, Shū

    2013-07-15

    In this paper, new possibilities for metal amides are described. Although typical metal amides are recognized as strong stoichiometric bases for deprotonation of inert or less acidic hydrogen atoms, transition-metal amides, namely silver and copper amides, show interesting abilities as one of the simplest acid/base catalysts in stereoselective carbon-carbon bond-forming reactions.

  15. Effect of metal ions on decomposition of chlorinated organic substances by ozonation in acetic acid.

    PubMed

    Okawa, Kiyokazu; Tsai, Tsung-Yueh; Nakano, Yoichi; Nishijima, Wataru; Okada, Mitsumasa

    2005-01-01

    The objective of this study is to find metal ions that enhance the ozone decomposition of chlorinated organic substances in acetic acid. Although the pseudo-first order degradation rate constant for 2,4-DCP by ozone in acetic acid in addition of Ca2+, Mg2+, Al3+ and Fe2+ were almost the same as that with no metal ion, the degradation rate in addition of Mn2+ and Fe3+ were 2.4 and 4.5 times as high as that with no metal ion, respectively. The presence of Fe3+ enhanced the degradation of 2,4-DCP by ozone in acetic acid because Fe3+-phenolate complex which have high reactivity with ozone was produced by the reaction between 2,4-DCP and Fe3+ in acetic acid. PMID:15620744

  16. 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

  17. [Influence of chosen metals on the citric acid cycle].

    PubMed

    Rojczyk-Gołebiewska, Ewa; Kucharzewski, Marek

    2013-03-01

    Industrial activity growth influenced not only technological progress, but also had negative effects on human natural environment. It results among others in increased human exposition to heavy metals. In case of detoxication mechanisms disturbance in organism, heavy metals cumulate in tissues causing mutations and disrupting metabolism, including Krebs cycle. Recent studies have revealed that iron, zinc and manganese have especially strong influence on Krebs cycle. These elements act as cofactors or inhibitors regulating activity of particular enzymes of this cycle, which has a reflection in cellular energy production disturbances.

  18. New multifunctional phosphonic acid for metal phosphonate synthesis

    NASA Astrophysics Data System (ADS)

    Garczarek, Piotr; Janczak, Jan; Zoń, Jerzy

    2013-03-01

    A new heterotopic phosphonic acid, 3-amino-5-(dihydroxyphosphoryl)benzoic acid (1) has been synthesized and obtained in the crystalline form. Second multifunctional phosphonic acid - namely 3-(dihydroxyphosphoryl)-5-nitrobenzoic acid (2) has also been obtained, following a different synthetic route than previously reported. Compound 1 crystallizes in a centrosymmetric space group of the triclinic system as monohydrate, sbnd C6H3(NH2)(COOH)PO3H2·H2O -1a. The molecule in the crystal exists in a zwitterionic form, in which one of the proton of the phosphonic group is transferred to the amine group. The zwitterionic molecules interact to each other and with water molecules via Nsbnd H…O and Osbnd H…O hydrogen bonds forming a three-dimensional network.

  19. Metal cation dependence of interactions with amino acids: bond dissociation energies of Rb(+) and Cs(+) to the acidic amino acids and their amide derivatives.

    PubMed

    Armentrout, P B; Yang, Bo; Rodgers, M T

    2014-04-24

    Metal cation-amino acid interactions are key components controlling the secondary structure and biological function of proteins, enzymes, and macromolecular complexes comprising these species. Determination of pairwise interactions of alkali metal cations with amino acids provides a thermodynamic vocabulary that begins to quantify these fundamental processes. In the present work, we expand a systematic study of such interactions by examining rubidium and cesium cations binding with the acidic amino acids (AA), aspartic acid (Asp) and glutamic acid (Glu), and their amide derivatives, asparagine (Asn) and glutamine (Gln). These eight complexes are formed using electrospray ionization and their bond dissociation energies (BDEs) are determined experimentally using threshold collision-induced dissociation with xenon in a guided ion beam tandem mass spectrometer. Analyses of the energy-dependent cross sections include consideration of unimolecular decay rates, internal energy of the reactant ions, and multiple ion-neutral collisions. Quantum chemical calculations are conducted at the B3LYP, MP2(full), and M06 levels of theory using def2-TZVPPD basis sets, with results showing reasonable agreement with experiment. At 0 and 298 K, most levels of theory predict that the ground-state conformers for M(+)(Asp) and M(+)(Asn) involve tridentate binding of the metal cation to the backbone carbonyl, amino, and side-chain carbonyl groups, although tridentate binding to the carboxylic acid group and side-chain carbonyl is competitive for M(+)(Asn). For the two longer side-chain amino acids, Glu and Gln, multiple structures are competitive. A comparison of these results to those for the smaller alkali cations, Na(+) and K(+), provides insight into the trends in binding energies associated with the molecular polarizability and dipole moment of the side chain. For all four metal cations, the BDEs are inversely correlated with the size of the metal cation and follow the order Asp < Glu

  20. 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…

  1. Role of Oxalic Acid Overexcretion in Transformations of Toxic Metal Minerals by Beauveria caledonica

    PubMed Central

    Fomina, M.; Hillier, S.; Charnock, J. M.; Melville, K.; Alexander, I. J.; Gadd, G. M.

    2005-01-01

    The fungus Beauveria caledonica was highly tolerant to toxic metals and solubilized cadmium, copper, lead, and zinc minerals, converting them into oxalates. This fungus was found to overexcrete organic acids with strong metal-chelating properties (oxalic and citric acids), suggesting that a ligand-promoted mechanism was the main mechanism of mineral dissolution. Our data also suggested that oxalic acid was the main mineral-transforming agent. Cadmium, copper, and zinc oxalates were precipitated by the fungus in the local environment and also in association with the mycelium. The presence of toxic metal minerals often led to the formation of mycelial cords, and in the presence of copper-containing minerals, these cords exhibited enhanced excretion of oxalic acid, which resulted in considerable encrustation of the cords by copper oxalate hydrate (moolooite). It was found that B. caledonica hyphae and cords were covered by a thick hydrated mucilaginous sheath which provided a microenvironment for chemical reactions, crystal deposition, and growth. Cryo-scanning electron microscopy revealed that mycogenic metal oxalates overgrew parental fungal hyphae, leaving a labyrinth of fungal tunnels within the newly formed mineral matter. X-ray absorption spectroscopy revealed that oxygen ligands played a major role in metal coordination within the fungal biomass during the accumulation of mobilized toxic metals by B. caledonica mycelium; these ligands were carboxylic groups in copper phosphate-containing medium and phosphate groups in pyromorphite-containing medium. PMID:15640211

  2. 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...

  3. Antioxidant responses to simulated acid rain and heavy metal deposition in birch seedlings.

    PubMed

    Koricheva, J; Roy, S; Vranjic, J A; Haukioja, E; Hughes, P R; Hänninen, O

    1997-01-01

    This study measured the responses of different anti-oxidants in 2-year-old birch (Betula pendula Roth) seedlings subjected to simulated acid rain (pH 4.0) and heavy metals (Cu/Ni), applied alone or in combination for 2 months. The applied concentrations of pollutants did not significantly affect seedling biomass or total glutathione levels. Acid rain alone increased superoxide dismutase (SOD) activity both in leaves and roots, while heavy metals alone inhibited SOD activity in roots. Both acid rain and heavy metals applied singly increased ascorbate peroxidase (APX) and guaiacol peroxidase (GPX) activities in leaves but decreased activities in roots. In contrast, acid rain and heavy metal treatments increased glutathione reductase (GR) activity in roots but not in leaves. Spraying birch seedlings with a mixture of acid rain and heavy metals increased SOD, APX and GPX activities in leaves and GR activity in roots. However, the effects of mixed pollutants on enzyme activities usually were less than the summed effects of individual pollutants. Enzyme responses also depended on where pollutants were applied: spraying pollutants onto the shoots initiated higher responses in SOD, APX and GPX than did application to the soil surface, while the opposite was true for GR.

  4. 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.

  5. Lightweight, durable lead-acid batteries

    SciTech Connect

    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).

  6. 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).

  7. Microscopic evaluation of trace metals in cloud droplets in an acid precipitation region.

    PubMed

    Li, Weijun; Wang, Yan; Collett, Jeffrey L; Chen, Jianmin; Zhang, Xiaoye; Wang, Zifa; Wang, Wenxing

    2013-05-01

    Mass concentrations of soluble trace metals and size, number, and mixing properties of nanometal particles in clouds determine their toxicity to ecosystems. Cloud water was found to be acidic, with a pH of 3.52, at Mt. Lu (elevation 1,165 m) in an acid precipitation region in South China. A combination of Inductively Coupled Plasma Mass Spectrometry (ICPMS) and Transmission Electron Microscopy (TEM) for the first time demonstrates that the soluble metal concentrations and solid metal particle number are surprisingly high in acid clouds at Mt. Lu, where daily concentrations of SO2, NO2, and PM10 are 18 μg m(-3), 7 μg m(-3), and 22 μg m(-3). The soluble metals in cloudwater with the highest concentrations were zinc (Zn, 200 μg L(-1)), iron (Fe, 88 μg L(-1)), and lead (Pb, 77 μg L(-1)). TEM reveals that 76% of cloud residues include metal particles that range from 50 nm to 1 μm diameter with a median diameter of 250 nm. Four major metal-associated particle types are Pb-rich (35%), fly ash (27%), Fe-rich (23%), and Zn-rich (15%). Elemental mapping shows that minor soluble metals are distributed within sulfates of cloud residues. Emissions of fine metal particles from large, nonferrous industries and coal-fired power plants with tall stacks were transported upward to this high elevation. Our results suggest that the abundant trace metals in clouds aggravate the impacts of acid clouds or associated precipitation on the ecosystem and human health.

  8. 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

  9. 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

  10. BIOLOGICAL RESPONSE TO VARIATION OF ACID-VOLATILE SULFIDES AND METALS IN FIELD-EXPOSED SPIKED SEDIMENTS

    EPA Science Inventory

    Vertical and temporal variations of acid-volatile sulfides (AVS) and simultaneously extracted metals (SEM) in sediment can control biological impacts of metals. To assess the significance of these variations in field sediments, sediments spiked with cadmium, copper, lead, nickel ...

  11. Anthropogenic and natural sources of acidity and metals and their influence on the structure of stream food webs.

    PubMed

    Hogsden, Kristy L; Harding, Jon S

    2012-03-01

    We compared food web structure in 20 streams with either anthropogenic or natural sources of acidity and metals or circumneutral water chemistry in New Zealand. Community and diet analysis indicated that mining streams receiving anthropogenic inputs of acidic and metal-rich drainage had much simpler food webs (fewer species, shorter food chains, less links) than those in naturally acidic, naturally high metal, and circumneutral streams. Food webs of naturally high metal streams were structurally similar to those in mining streams, lacking fish predators and having few species. Whereas, webs in naturally acidic streams differed very little from those in circumneutral streams due to strong similarities in community composition and diets of secondary and top consumers. The combined negative effects of acidity and metals on stream food webs are clear. However, elevated metal concentrations, regardless of source, appear to play a more important role than acidity in driving food web structure. PMID:22088498

  12. 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

  13. 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.

  14. 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.

  15. Synthesis and characterization of 2D molybdenum carbide (MXene)

    DOE PAGES

    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

  16. 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.

  17. 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

  18. 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.

  19. 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)

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. Protein-gold nanoclusters for identification of amino acids by metal ions modulated ratiometric fluorescence.

    PubMed

    Wang, Min; Mei, Qingsong; Zhang, Kui; Zhang, Zhongping

    2012-04-01

    Here we report that the dual fluorescence emissions from protein-gold (Au) nanoclusters can greatly be modulated by metal ions and the resultant fluorescence ratiometric responses provide a novel sensory method for the identification of amino acids. The protein-gold (Au) nanoclusters were simply synthesized by the reduction of chloroauric acid with bovine serum albumin (BSA), which exhibit dual emissions: the blue at 425 nm from the oxides of BSA, and the red at 635 nm from Au nanoclusters. It has been demonstrated that different metal ions react with BSA-Au nanoclusters and thus greatly affect the two emissions in different ways by fluorescence enhancement or quenching. Interestingly, the addition of amino acids leads to fluorescence ratiometric changes through the interactions with the bound metal ions. When BSA-Au nanocluster probes modulated by four different metal ions were used together to construct a sensor array, different amino acids were clearly discriminated by the distinctive patterns of four ratiometric fluorescence responses. Results and methods reported here provide a unique strategy for the determination of amino acids.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. Modeling the plant-soil interaction in presence of heavy metal pollution and acidity variations.

    PubMed

    Guala, Sebastián; Vega, Flora A; Covelo, Emma F

    2013-01-01

    On a mathematical interaction model, developed to model metal uptake by plants and the effects on their growth, we introduce a modification which considers also effects on variations of acidity in soil. The model relates the dynamics of the uptake of metals from soil to plants and also variations of uptake according to the acidity level. Two types of relationships are considered: total and available metal content. We suppose simple mathematical assumptions in order to get as simple as possible expressions with the aim of being easily tested in experimental problems. This work introduces modifications to two versions of the model: on the one hand, the expression of the relationship between the metal in soil and the concentration of the metal in plants and, on the other hand, the relationship between the metal in the soil and total amount of the metal in plants. The fine difference of both versions is fundamental at the moment to consider the tolerance and capacity of accumulation of pollutants in the biomass from the soil.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. The role of citric acid on the phytoremediation of heavy metal contaminated soil.

    PubMed

    Chen, Y X; Lin, Q; Luo, Y M; He, Y F; Zhen, S J; Yu, Y L; Tian, G M; Wong, M H

    2003-02-01

    Adsorption and hydroponics experiments were conducted to study the role of citric acid on the phytoremediation of heavy metal contaminated soil. The results show that addition of citric acid decreased the adsorption of both lead and cadmium, such an effect was bigger for cadmium than for lead. The decrease in the adsorption of Pb and Cd was mainly due to a decrease of pH in the presence of citric acid. The presence of citric acid could alleviate the toxicity of Pb and Cd to radish, and stimulate their transportation from root to shoot. The studies of heavy metal forms using sequential extraction demonstrated that lead was mainly existed as FHAC (a lower bioavailable form) in the root, while F(HCl) was the dominant form in the leaf. The addition of citric acid to the soil changed the concentration and relative abundance of all the forms. The detoxifying effect of citric acid to Pb in shoots might result from the transformation of higher toxic forms into lower toxic forms. Cadmium was mainly present as F(NaCl), therefore, it had higher toxicity than lead. The addition of citric acid increased the abundance of F(H2O) + F(NaCl), indicating that citric acid treatment could transform cadmium into more transportable forms.

  1. Structural chemistry of complex carbides and related compounds

    NASA Astrophysics Data System (ADS)

    Nowotny, Hans; Rogl, Peter; Schuster, Julius C.

    1982-08-01

    Complex carbides formed in ternary systems of a transition element ( M), a B-group element ( M'), and carbon and having a formula M2M'C (H-phase) or M3M'C (perovskite carbide) occur frequently. This reflects the simple geometry of the atomic arrangement of the metals and the filling mode by an interstitial stabilizer such as carbon or nitrogen. The phase relationship of the ternary combinations {Ti, Zr, Hf, V, Nb, Ta, Cr, Mn, and Ni}-aluminum-carbon was investigated. New complex carbides were found with the corresponding zirconium, hafnium, and tantalum combinations. The crystal structures in the case of Zr- and Hf-containing complex carbides can be characterized by a twelve-metal-layer sequence and by a ten-metal-layer sequence with carbon atoms again filling octahedral voids. The transition of structure types from TiC, Ti 2AlC, Ti 3SiC 2, ZrAlC 2, Zr 2Al 3C 5, to Al 4C 3 is also discussed.

  2. Fivefold twinned boron carbide nanowires.

    PubMed

    Fu, Xin; Jiang, Jun; Liu, Chao; Yuan, Jun

    2009-09-01

    Chemical composition and crystal structure of fivefold twinned boron carbide nanowires have been determined by electron energy-loss spectroscopy and electron diffraction. The fivefold cyclic twinning relationship is confirmed by systematic axial rotation electron diffraction. Detailed chemical analysis reveals a carbon-rich boron carbide phase. Such boron carbide nanowires are potentially interesting because of their intrinsic hardness and high temperature thermoelectric property. Together with other boron-rich compounds, they may form a set of multiply twinned nanowire systems where the misfit strain could be continuously tuned to influence their mechanical properties.

  3. Effect of citric acid and rhizosphere bacteria on metal plaque formation and metal accumulation in reeds in synthetic acid mine drainage solution.

    PubMed

    Guo, Lin; Cutright, Teresa J

    2014-06-01

    Many of regions in the world have been affected by acid mine drainage (AMD). The study assessed the effect of rhizosphere bacteria and citric acid (CA) on the metal plaque formation and heavy metal uptake in Phragmites australis cultured in synthetic AMD solution. Mn and Al plaque were not formed, but Fe plaque which was mediated by rhizosphere iron oxidizing bacteria (Fe(II)OB) was observed on the root system of reeds. Fe plaque did not significantly influence the uptake of Fe, Al and Mn into tissues of reeds. CA significantly (p<0.01) inhibited the growth of Fe(II)OB and decreased the formation of Fe plaque. CA also significantly improved (p<0.05) the accumulation of Fe, Mn and Al in all the tissues of reeds. Roots and rhizomes were the main organs to store metals. The roots contained 0.08±0.01mg/g Mn, 2.39±0.26mg/g Fe and 0.19±0.02mg/g Al, while the shoots accumulated 0.04±0.00mg/g Mn, 0.20±0.01mg/g Fe, 0.11±0.00mg/g Al in reeds cultured in solution amended with 2.101g/l CA and without inoculation of rhizosphere bacteria.

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

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... salts (generic). 721.10487 Section 721.10487 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10487 Alkylbenzenes sulfonic acids, metal salts (generic). (a)...

  6. 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...

  7. PRELIMINARY RESULTS: RELEASE OF METALS FROM ACID-MINE DRAINAGE CONTAMINATED STREAMBED SEDIMENTS UNDER ANOXIC CONDITIONS

    EPA Science Inventory

    Many miles of streams are contaminated with acid-mine drainage (AMD) from abandoned metal mines in the western U.S. Treatment of these streams may include dredging of the existing sediments, with subsequent burial. Burial of previously toxic sediments may result in release of met...

  8. 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...

  9. Croconic acid and alkali metal croconate salts: some new insights into an old story.

    PubMed

    Braga, Dario; Maini, Lucia; Grepioni, Fabrizia

    2002-04-15

    The solid-state structures of a series of alkali metal salts of the croconate dianion (C(5)O(5)(2-)) and of croconic acid (H(2)C(5)O(5)) have been determined. The alkali metal croconates were obtained by ring contraction of rhodizonic acid (H(2)C(6)O(6)), upon treatment with alkali metal hydroxides and recrystallisation from water. The novel species Na(2)C(5)O(5) x 2H(2)O, Rb(2)C(5)O(5) and Cs(2)C(5)O(5), as well as the mixed hydrogencroconate/croconate salt K(3)(HC(5)O(5))(C(5)O(5)) small middle dot2 H(2)O are described and compared with the Li(+), K(+) and NH(4)(+) salts. Single crystals of croconic acid were obtained by crystallisation of croconic acid in the presence of HCl. Crystal structure determinations showed that the C(5)O(5)(2-) ions tend to organize themselves in columns. The interplanar separations lie in the narrow range 3.12-3.42 A and do not necessarily reflect the presence of pi-stacking interactions. It is argued that the small interplanar separation is the result of a compromise between packing of flat croconate units and the spherical cations together with the water molecules that fill the coordination spheres of the alkali metal atoms. PMID:11933108

  10. Metal speciation and potential bioavailability changes during discharge and neutralisation of acidic drainage water.

    PubMed

    Simpson, Stuart L; Vardanega, Christopher R; Jarolimek, Chad; Jolley, Dianne F; Angel, Brad M; Mosley, Luke M

    2014-05-01

    The discharge of acid drainage from the farm irrigation areas to the Murray River in South Australia represents a potential risk to water quality. The drainage waters have low pH (2.9-5.7), high acidity (up to 1190 mg L(-1) CaCO3), high dissolved organic carbon (10-40 mg L(-1)), and high dissolved Al, Co, Ni and Zn (up to 55, 1.25, 1.30 and 1.10 mg L(-1), respectively) that represent the greatest concern relative to water quality guidelines (WQGs). To provide information on bioavailability, changes in metal speciation were assessed during mixing experiments using filtration (colloidal metals) and Chelex-lability (free metal ions and weak inorganic metal complexes) methods. Following mixing of drainage and river water, much of the dissolved aluminium and iron precipitated. The concentrations of other metals generally decreased conservatively in proportion to the dilution initially, but longer mixing periods caused increased precipitation or adsorption to particulate phases. Dissolved Co, Mn and Zn were typically 95-100% present in Chelex-labile forms, whereas 40-70% of the dissolved nickel was Chelex-labile and the remaining non-labile fraction of dissolved nickel was associated with fine colloids or complexed by organic ligands that increased with time. Despite the different kinetics of precipitation, adsorption and complexation reactions, the dissolved metal concentrations were generally highly correlated for the pooled data sets, indicating that the major factors controlling the concentrations were similar for each metal (pH, dilution, and time following mixing). For dilutions of the drainage waters of less than 1% with Murray River water, none of the metals should exceed the WQGs. However, the high concentrations of metals associated with fine precipitates within the receiving waters may represent a risk to some aquatic organisms. PMID:24359925

  11. 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.

  12. 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

    2014-12-12

    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.

  13. 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

  14. Metal transport in a stream polluted by acid mine drainage--The Afon Goch, Anglesey, UK.

    PubMed

    Boult, S; Collins, D N; White, K N; Curtis, C D

    1994-01-01

    Sampling of the Afon Goch over a 14-month period revealed maximum dissolved Fe, Al, Mn, Cu and Zn concentrations of 259, 167, 49, 60 and 42 mg dm(-3), respectively, and pH as low as 2.3, making it one of the most metal- and acid-contaminated streams in the UK. The river produces particulates by precipitation of ferrihydrite, due to the entry of near-neutral tributary waters, under all discharge conditions. Consequently, metal transport in this stream is dominated by processes different from those in less contaminated streams. The stream acts as a sink for contaminants, except under high discharge, when accumulated metals are flushed from the system. The implications of these observations for the monitoring and management of streams polluted by acid mine drainage are discussed. PMID:15091699

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

    PubMed

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

    2013-02-28

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

  16. 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...

  17. 40 CFR 60.52b - Standards for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 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...

  18. 40 CFR 60.52b - Standards for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 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...

  19. 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...

  20. 40 CFR 60.52b - Standards for municipal waste combustor metals, acid gases, organics, and nitrogen oxides.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 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...

  1. 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...

  2. Multicenter bond index analysis of influence of metal cations on the aromaticity of aromatic amino acids: Phenylalanine and tyrosine

    NASA Astrophysics Data System (ADS)

    Pakiari, A. H.; Farrokhnia, M.; Azami, S. M.

    2008-05-01

    In order to provide insight into the influence of metal cations on the aromaticity of amino acids, evaluation of six-center delocalization indices is accomplished in the context of quantum theory of atoms in molecules (QTAIM). Aromaticity of two amino acids, phenylalanine and tyrosine, is investigated as typical amino acids containing aromatic ring in their isolated state and complexed by some metal cations. The results showed that the metal cations affect the most important three connectivities differently. Also, it is shown that the existence of metal cations can increase two-center delocalization in certain parts of the aromatic rings.

  3. The inhibitory effect of metals and other ions on acid phosphatase activity from Vigna aconitifolia seeds.

    PubMed

    Srivastava, Pramod Kumar; Anand, Asha

    2015-01-01

    Sensitivity of acid phosphatase from Vigna aconitifolia seeds to metal ions, fluoride, and phosphate was examined. All the effectors had different degree of inhibitory effect on the enzyme. Among metal ions, molybdate and ferric ion were observed to be most potent inhibitors and both exhibited mixed type of inhibition. Acid phosphatase activity was inhibited by Cu2+ in a noncompetitive manner. Zn and Mn showed mild inhibition on the enzyme activity. Inhibition kinetics analysis explored molybdate as a potent inhibitor for acid phosphatase in comparison with other effectors used in this study. Fluoride was the next most strong inhibitor for the enzyme activity, and caused a mixed type of inhibition. Phosphate inhibited the enzyme competitively, which demonstrates that inhibition due to phosphate is one of the regulatory factors for enzyme activity.

  4. [Distribution of heavy metals in PM10 and its release in the simulated acid rain].

    PubMed

    Feng, Xi-dan; Dang, Zhi; Wang, Huan-xiang; Lu, Yan-bo; Lü, Xan-wen; Huang, Wei-lin

    2006-12-01

    The distribution of heavy metals in inhalable particulate matter (PM10), which were collected in Foshan during December of 2004, was characterized by scanning electron microscope-X-ray energy dispersive analysis technique (SEM-EDS) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The releases of Cu, Pb, Zn and Cd were also examined for their potential releases in simulated acid rain, which were quantified with batch reactors. The results showed that the daily average concentration of PM10 was 0.19 mg/m(3), about 79% higher than the secondary standard of China. The relatively contents of Zn and Pb in PM10 were much higher than Cd and Zn, whereas the releasing rates of Cd and Zn in simulated acid rain were greater than that of Cu and Pb. The releasing rates of heavy metals from PM10 were increased as the pH of the acid rain decreased.

  5. Determination of metal ions by high-performance liquid chromatographic separation of their hydroxamic acid chelates

    SciTech Connect

    Palmieri, M.D.; Fritz, J.S.

    1987-09-15

    Metal ions are determined by adding N-methylfurohydroxamic acid to an aqueous sample and then separating the metal chelates by direct injection onto a liquid chromatographic column. Separations on a C/sub 8/ silica column and a polystyrene-divinylbenzene column are compared, with better separations seen on the polymeric column. The complexes formed at low pH values are cationic and are separated by an ion pairing mechanism. Retention times and selectivity of the metal complexes can be varied by changing the pH. Several metal ions can be separated and quantified; separation conditions, linear calibration curve ranges, and detection limits are presented for Zr(IV), Hf(IV), Fe(III), Nb(V), Al(III), and Sb(III). Interferences due to the presence of other ions in solution are investigated. Finally, an antiperspirant sample is analyzed for zirconium by high-performance liquid chromatography.

  6. Effect of citric acid and bacteria on metal uptake in reeds grown in a synthetic acid mine drainage solution.

    PubMed

    Guo, Lin; Cutright, Teresa J

    2015-03-01

    The effect of citric acid (CA), rhizosphere acidophilic heterotrophs and/or Fe(II) oxidizing bacteria (Fe(II)OB) on plaque formation and metal accumulation in Phragmites australis L. (common reed) from acid mine drainage (AMD) solution were investigated. Reeds were grown in different hydroponic solutions that contained AMD, CA and/or rhizosphere bacteria for three months. Triplicate experiments were conducted for each experimental condition. Fe(II)OB enhanced the formation of Fe plaque which decreased Fe and Mn uptake in reeds, while it had no significant influence on Al accumulation. CA inhibited the growth of Fe(II)OB, decreased the formation of metal plaque and increased Fe and Mn accumulation in reeds. Acidophilic heterotrophs consumed CA and made the environment more suitable for the growth of Fe(II)OB. Reeds are a good candidate for phytoextraction while CA is a useful chelator to enhance metal uptake in plants. More research may be needed to investigate the influence of CA on microbial community. Further investigations are required to study the effect of CA on phytoremediation of AMD contaminated fields.

  7. 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.

  8. Heavy metal levels and delta-amino-levulinic acid dehydrase levels in peripheral polyneuropathy.

    PubMed

    Melgaard, B; Clausen, J; Rastogi, S C

    1976-04-01

    On the basis of assay of heavy metals in whole blood (lead, cadimum, chromium, copper, nickel and manganese) and delta-amino-levulinic-acid dehydrase (ALA-D) and ALA in urine in a normal Danish population, the levels of these clinco-chemical factors were assayed in 23 patients with peripheral neuropathy of unknown etiology. All patients studied showed electro-physiological sign of denervation and/or reduced motor or sensoric nerve conduction velocity. Cadmium and manganese were never found to be increased. In all but four patients, an increase of one or more heavy metals was found. Ten patients showed raised levels of two or more metals, the dominant metal being lead (10 cases), nine patients showed increased in chromium. A significant corrleation was found between increasing lead levels and decreasing ALA-D activity. Although normal concentrations of manganese were found, correlation analysis revealed a significant correlation between increased manganese and decreased ALA-D. The raised values of heavy metals could not be traced to occupational or other exposure to heavy metals and the increased values were not related to tobacco consumption. The findings are discussed in relation to known data on neuropathy and the results seem to indicate a multifactorial patholgenesis of the disease. Among factors contributing to the precipitation of the syndrome may be raised levels of heavy metals.

  9. 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.

  10. 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.

  11. 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.

  12. Snails from heavy-metal polluted environments have reduced sensitivity to carbon dioxide-induced acidity.

    PubMed

    Lefcort, Hugh; Cleary, David A; Marble, Aaron M; Phillips, Morgan V; Stoddard, Timothy J; Tuthill, Lara M; Winslow, James R

    2015-01-01

    Anthropogenic atmospheric CO2 reacts with water to form carbonic acid (H2CO3) which increases water acidity. While marine acidification has received recent consideration, less attention has been paid to the effects of atmospheric carbon dioxide on freshwater systems-systems that often have low buffering potential. Since many aquatic systems are already impacted by pollutants such as heavy metals, we wondered about the added effect of rising atmospheric CO2 on freshwater organisms. We studied aquatic pulmonate snails (Physella columbiana) from both a heavy-metal polluted watershed and snails from a reference watershed that has not experienced mining pollution. We used gaseous CO2 to increase water acidity and we then measured changes in antipredatory behavior and also survival. We predicted a simple negative additive effect of low pH. We hypothesized that snails from metal-polluted environments would be physiologically stressed and impaired due to defense responses against heavy metals. Instead, snails from populations that acclimated or evolved in the presence of heavy metal mining pollution were more robust to acidic conditions than were snails from reference habitats. Snails from mining polluted sites seemed to be preadapted to a low pH environment. Their short-term survival in acidic conditions was better than snails from reference sites that lacked metal pollution. In fact, the 48 h survival of snails from polluted sites was so high that it did not significantly differ from the 24 h survival of snails from control sites. This suggests that the response of organisms to a world with rising anthropogenic carbon dioxide levels may be complex and difficult to predict. Snails had a weaker behavioral response to stressful stimuli if kept for 1 month at a pH that differed from their lake of origin. We found that snails raised at a pH of 5.5 had a weaker response (less of a decrease in activity) to concentrated heavy metals than did snails raised at their natal pH of

  13. Snails from heavy-metal polluted environments have reduced sensitivity to carbon dioxide-induced acidity.

    PubMed

    Lefcort, Hugh; Cleary, David A; Marble, Aaron M; Phillips, Morgan V; Stoddard, Timothy J; Tuthill, Lara M; Winslow, James R

    2015-01-01

    Anthropogenic atmospheric CO2 reacts with water to form carbonic acid (H2CO3) which increases water acidity. While marine acidification has received recent consideration, less attention has been paid to the effects of atmospheric carbon dioxide on freshwater systems-systems that often have low buffering potential. Since many aquatic systems are already impacted by pollutants such as heavy metals, we wondered about the added effect of rising atmospheric CO2 on freshwater organisms. We studied aquatic pulmonate snails (Physella columbiana) from both a heavy-metal polluted watershed and snails from a reference watershed that has not experienced mining pollution. We used gaseous CO2 to increase water acidity and we then measured changes in antipredatory behavior and also survival. We predicted a simple negative additive effect of low pH. We hypothesized that snails from metal-polluted environments would be physiologically stressed and impaired due to defense responses against heavy metals. Instead, snails from populations that acclimated or evolved in the presence of heavy metal mining pollution were more robust to acidic conditions than were snails from reference habitats. Snails from mining polluted sites seemed to be preadapted to a low pH environment. Their short-term survival in acidic conditions was better than snails from reference sites that lacked metal pollution. In fact, the 48 h survival of snails from polluted sites was so high that it did not significantly differ from the 24 h survival of snails from control sites. This suggests that the response of organisms to a world with rising anthropogenic carbon dioxide levels may be complex and difficult to predict. Snails had a weaker behavioral response to stressful stimuli if kept for 1 month at a pH that differed from their lake of origin. We found that snails raised at a pH of 5.5 had a weaker response (less of a decrease in activity) to concentrated heavy metals than did snails raised at their natal pH of

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. Studies of silicon carbide and silicon carbide nitride thin films

    NASA Astrophysics Data System (ADS)

    Alizadeh, Zhila

    Silicon carbide semiconductor technology is continuing to advance rapidly. The excellent physical and electronic properties of silicon carbide recently take itself to be the main focused power device material for high temperature, high power, and high frequency electronic devices because of its large band gap, high thermal conductivity, and high electron saturation drift velocity. SiC is more stable than Si because of its high melting point and mechanical strength. Also the understanding of the structure and properties of semiconducting thin film alloys is one of the fundamental steps toward their successful application in technologies requiring materials with tunable energy gaps, such as solar cells, flat panel displays, optical memories and anti-reflecting coatings. Silicon carbide and silicon nitrides are promising materials for novel semiconductor applications because of their band gaps. In addition, they are "hard" materials in the sense of having high elastic constants and large cohesive energies and are generally resistant to harsh environment, including radiation. In this research, thin films of silicon carbide and silicon carbide nitride were deposited in a r.f magnetron sputtering system using a SiC target. A detailed analysis of the surface chemistry of the deposited films was performed using x-ray photoelectron spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopy whereas structure and morphology was studied atomic force microscopy (AFM), and nonoindentation.

  19. 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

  20. 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.

  1. 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.

  2. Effects of simulated acid rain, EDTA, or their combination, on migration and chemical fraction distribution of extraneous metals in Ferrosol.

    PubMed

    Wen, Fang; Hou, Hong; Yao, Na; Yan, Zengguang; Bai, Liping; Li, Fasheng

    2013-01-01

    A laboratory repacked soil-leaching column experiment was conducted to study the effects of simulated acid rain or EDTA by themselves or in combination, on migration and chemical speciation distribution of Pb and its alternative rare metals including Ag, Bi, In, Sb, and Sn. Experimental results demonstrate that leaching with simulated acid rain promoted the migration of Bi, In and Pb, and their migration reached down to 8 cm in the soil profile, no enhancement of Sb, Ag or Sn migration was observed. Addition of EDTA significantly enhanced the migration of all six metals, especially Bi, In and Pb. The migration of metals was in the order Pb>Bi>In>Sb>Sn>Ag. The individual and combined effects of acid rain and EDTA increased the environmental risk of metals, by increasing the soluble content of metals in soil solutions and the relative distribution of the exchangeable fraction. Leaching risks of Bi, In and Pb were higher than other three metals.

  3. Biofilm hydrous manganese oxyhydroxides and metal dynamics in acid rock drainage.

    PubMed

    Haack, Elizabeth; Warren, Lesley A

    2003-09-15

    Biofilms in shallow, tailings-associated acid rock drainage (ARD) accumulated metals from May to September, indicating scavenging is stable within these biological solids over seasonal time frames. Results indicate a doubling (Mn, Cr) to over a 6-fold increase (Ni, Co) in biofilm metal concentrations. Biofilm oxygen and pH gradients measured over diel time scales with microelectrodes were observed to be both spatially and temporally variable, indicating that biofilms are highly dynamic geochemical environments. Biofilm metal retention and affinities were element specific indicating different processes control their sequestration. Metals were specifically scavenged by the organic constituents of the biofilm itself (Ni, Co) and associated biominerals of amorphous Mn oxyhydroxides (HMO; Ni, Co, and Cr). Results are consistent with sorption and coprecipitation processes controlling Ni and Co biofilm association, while Cr dynamics appear linked to those of Mn through redox processes. Biofilm HMO concentrations increased seasonally but showed significant diel fluctuations, indicating that both formation and dissolution processes occurred over rapid time scales in these biofilms. Biofilm HMO concentrations increased nocturnally but decreased during daylight hours to late afternoon minima. Under the geochemical conditions of the streams, observed HMO formation rates can only be explained by microbial catalysis. These results are the first to quantitatively examine microbial biofilm metal dynamics using microscale, geochemical techniques at both diel and seasonal time scales. They provide strong evidence for the significant role that microbial activity can play in metal geochemistry in natural environments. PMID:14524446

  4. 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.

  5. 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

  6. The relation between Acid Volatile Sulfides (AVS) and metal accumulation in aquatic invertebrates: implications of feeding behavior and ecology.

    PubMed

    De Jonge, Maarten; Blust, Ronny; Bervoets, Lieven

    2010-05-01

    The present study evaluates the relationship between Acid Volatile Sulfides (AVS) and metal accumulation in invertebrates with different feeding behavior and ecological preferences. Natural sediments, pore water and surface water, together with benthic and epibenthic invertebrates were sampled at 28 Flemish lowland rivers. Different metals as well as metal binding sediment characteristics including AVS were measured and multiple regression was used to study their relationship with accumulated metals in the invertebrates taxa. Bioaccumulation in the benthic taxa was primarily influenced by total metal concentrations in the sediment. Regarding the epibenthic taxa metal accumulation was mostly explained by the more bioavailable metal fractions in both the sediment and the water. AVS concentrations were generally better correlated with metal accumulation in the epibenthic invertebrates, rather than with the benthic taxa. Our results indicated that the relation between AVS and metal accumulation in aquatic invertebrates is highly dependent on feeding behavior and ecology.

  7. 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.; 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.

  8. High temperature intermetallic binders for HVOF carbides

    SciTech Connect

    Shaw, K.G.; Gruninger, M.F.; Jarosinski, W.J.

    1994-12-31

    Gas turbines technology has a long history of employing the desirable high temperature physical attributes of ceramic-metallic (cermet) materials. The most commonly used coatings incorporate combinations of WC-Co and Cr{sub 3}C{sub 2}-NiCr, which have also been successfully utilized in other non-turbine coating applications. Increased turbine operating temperatures and other high temperature service conditions have made apparent the attractive notion of increasing the temperature capability and corrosion resistance of these coatings. In this study the intermetallic binder NiAl has been used to replace the cobalt and NiCr constituents of conventional WC and Cr{sub 3}C{sub 2} cermet powders. The composite carbide thermal spray powders were fabricated for use in the HVOF coating process. The structure of HVOF deposited NiAl-carbide coatings are compared directly to the more familiar WC-Co and Cr{sub 3}C{sub 2}-NiCr coatings using X-ray diffraction, back-scattered electron imaging (BEI) and electron dispersive spectroscopy (EDS). Hardness variations with temperature are reported and compared between the NiAl and Co/NiCr binders.

  9. Enhancing Skin Permeation of Biphenylacetic Acid (BPA) Using Salt Formation with Organic and Alkali Metal Bases.

    PubMed

    Pawar, Vijay; Naik, Prashant; Giridhar, Rajani; Yadav, Mange Ram

    2015-01-01

    In the present study, a series of organic and alkali metal salts of biphenylacetic acid (BPA) have been prepared and evaluated in vitro for percutaneous drug delivery. The physicochemical properties of BPA salts were determined using solubility measurements, DSC, and IR. The DSC thermogram and FTIR spectra confirmed the salt formation with organic and alkali metal bases. Among the series, salts with organic amines (ethanolamine, diethanolamine, triethanolamine, and diethylamine) had lowered melting points while the alkali metal salt (sodium) had a higher melting point than BPA. The in vitro study showed that salt formation improves the physicochemical properties of BPA, leading to improved permeability through the skin. Amongst all the prepared salts, ethanolamine salt (1b) showed 7.2- and 5.4-fold higher skin permeation than the parent drug at pH 7.4 and 5.0, respectively, using rat skin.

  10. 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.

  11. 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+.

  12. Laser melting of uranium carbides

    NASA Astrophysics Data System (ADS)

    Utton, C. A.; De Bruycker, F.; Boboridis, K.; Jardin, R.; Noel, H.; Guéneau, C.; Manara, D.

    2009-03-01

    In the context of the material research aimed at supporting the development of nuclear plants of the fourth Generation, renewed interest has recently arisen in carbide fuels. A profound understanding of the behaviour of nuclear materials in extreme conditions is of prime importance for the analysis of the operation limits of nuclear fuels, and prediction of possible nuclear reactor accidents. In this context, the main goal of the present paper is to demonstrate the feasibility of laser induced melting experiments on stoichiometric uranium carbides; UC, UC1.5 and UC2. Measurements were performed, at temperatures around 3000 K, under a few bars of inert gas in order to minimise vaporisation and oxidation effects, which may occur at these temperatures. Moreover, a recently developed investigation method has been employed, based on in situ analysis of the sample surface reflectivity evolution during melting. Current results, 2781 K for the melting point of UC, 2665 K for the solidus and 2681 K for the liquidus of U2C3, 2754 K for the solidus and 2770 K for the liquidus of UC2, are in fair agreement with early publications where the melting behaviour of uranium carbides was investigated by traditional furnace melting methods. Further information has been obtained in the current research about the non-congruent (solidus-liquidus) melting of certain carbides, which suggest that a solidus-liquidus scheme is followed by higher ratio carbides, possibly even for UC2.

  13. Use of Energy Crop (Ricinus communis L.) for Phytoextraction of Heavy Metals Assisted with Citric Acid.

    PubMed

    Zhang, Hui; Chen, Xueping; He, Chiquan; Liang, Xia; Oh, Kokyo; Liu, Xiaoyan; Lei, Yanru

    2015-01-01

    Ricinus communis L. is a bioenergetic crop with high-biomass production and tolerance to cadmium (Cd) and lead (Pb), thus, the plant is a candidate crop for phytoremediation. Pot experiments were performed to study the effects of citric acid in enhancing phytoextraction of Cd/Pb by Ricinus communis L. Citric acid increased Cd and Pb contents in plant shoots in all treatments by about 78% and 18-45%, respectively, at the dosage of 10 mM kg(-1) soil without affecting aboveground biomass production. Addition of citric acid reduced CEC, weakened soil adsorption of heavy metals and activated Cd and Pb in soil solutions. The acid-exchangeable fraction (BCR-1) of Pb remained lower than 7% and significantly increased with citric acid amendment. Respective increases in soil evaluation index induces by 14% and 19% under the Cd1Pb50 and Cd1Pb250 treatments upon addition of citric acid resulted in soil quality improvement. Ricinus communis L. has great potential in citric acid-assisted phytoextraction for Cd and Pb remediation.

  14. Porous silicon carbide (SIC) semiconductor device

    NASA Technical Reports Server (NTRS)

    Shor, Joseph S. (Inventor); Kurtz, Anthony D. (Inventor)

    1996-01-01

    Porous silicon carbide is fabricated according to techniques which result in a significant portion of nanocrystallites within the material in a sub 10 nanometer regime. There is described techniques for passivating porous silicon carbide which result in the fabrication of optoelectronic devices which exhibit brighter blue luminescence and exhibit improved qualities. Based on certain of the techniques described porous silicon carbide is used as a sacrificial layer for the patterning of silicon carbide. Porous silicon carbide is then removed from the bulk substrate by oxidation and other methods. The techniques described employ a two-step process which is used to pattern bulk silicon carbide where selected areas of the wafer are then made porous and then the porous layer is subsequently removed. The process to form porous silicon carbide exhibits dopant selectivity and a two-step etching procedure is implemented for silicon carbide multilayers.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. 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

    2016-07-06

    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.

  1. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    DOE PAGES

    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

  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. CVD tungsten carbide and titanium carbide coatings for aerospace components

    SciTech Connect

    Dyer, P.N.; Garg, D.; Pellman, M.A.; Sheridan, J.J. III.

    1989-01-01

    Commercial applications of ceramic coatings for improving the wear resistance and tribology of stainless steel components such as compressor blades and ball bearings are under development. This paper reviews two coating systems: a proprietary erosion-resistant tungsten carbide coating system and a licensed wear-resistant titanium carbide coating, which as been qualified for use in several critical navigational gyroscope systems in the U.S. and European aerospace industries. Both have demonstrated performance and applicability superior to other protective coatings. 27 refs.

  4. Groundwater or floodwater? Assessing the pathways of metal exports from a coastal acid sulfate soil catchment.

    PubMed

    Santos, Isaac R; de Weys, Jason; Eyre, Bradley D

    2011-11-15

    Daily observations of dissolved aluminum, iron, and manganese in an estuary downstream of a coastal acid sulfate soil (CASS) catchment provided insights into how floods and submarine groundwater discharge drive wetland metal exports. Extremely high Al, Fe, and Mn concentrations (up to 40, 374, and 8 mg L(-1), respectively) were found in shallow acidic groundwaters from the Tuckean Swamp, Australia. Significant correlations between radon (a natural groundwater tracer) and metals in surface waters revealed that metal loads were driven primarily by groundwater discharge. Dissolved Fe, Mn, and Al loads during a 16-day flood triggered by a 213 mm rain event were respectively 80, 35, and 14% of the total surface water exports during the four months of observations. Counter clockwise hysteresis was observed for Fe and Mn in surface waters during the flood due to delayed groundwater inputs. Groundwater-derived Fe fluxes into artificial drains were 1 order of magnitude higher than total surface water exports, which is consistent with the known accumulation of monosulfidic black ooze within the wetland drains. Upscaling the Tuckean catchment export estimates yielded dissolved Fe fluxes from global acid sulfate soil catchments on the same order of magnitude of global river inputs into estuaries.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. Trace metals of an acid mine drainage stream using a chemical model (WATEQ) and sediment analysis

    SciTech Connect

    West, K.A. ); Wilson, T.P. . Dept. of Geology)

    1992-01-01

    The high metal contents common to the discharge of acid-mine drainage (AMD) from mines and mine spoils is an environmental concern to both government and industry. This paper reports the results of investigation of the behavior of metals in an AMD system at a former surface coal mine in Tuscarawas County, Oh. AMD discharges from seeps travels, in respective order through a laminar flow stream; a Typha-dominated wetland; a turbulent flow stream; and a sediment retention pond. Dissolved metals (Fe, Mn, Zn, Cr, Cd, Cu, and Al) major and minor components, and other parameters (pH, dissolved oxygen and Eh) were measured in the AMD water at each sample location. A chemical mineral equilibrium model (WATEQ) was used to predict the minerals which should precipitate at each site. Results suggest that the seeps are supersaturated and should be precipitating hematite, goethite and magnetite (iron oxides), and siderite (iron carbonate), whereas water of the other downstream sites were at or below equilibrium conditions for these minerals. The hydrogeochemistry of the AMD was further studied using sequential chemical attacks on the precipitate sediment surface coatings, in order to determine metal concentrations in the exchangeable, carbonate, Fe-Mn oxyhydroxide, and oxidizable fractions. The carbonate and exchangeable fractions of the precipitate are dominated by Ca and Fe, as well as Mg in the carbonate fraction. The Fe-Mn oxyhydroxide fraction contained Fe, Al, Mn, Mg, and trace metals, and also contained the greatest concentration of total elements in the system. The Fe-Mn oxyhydroxide is therefore, the major sink for metals of this AMD system. The decrease in the concentration of metals in the sediment precipitates in the downstream locations, is consistent with WATEQ and water analysis results.

  12. 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.

  13. Thermal conductivity of boron carbides

    NASA Technical Reports Server (NTRS)

    Wood, C.; Emin, D.; Gray, P. E.

    1985-01-01

    Knowledge of the thermal conductivity of boron carbide is necessary to evaluate its potential for high-temperature thermoelectric energy conversion applications. Measurements have been conducted of the thermal diffusivity of hot-pressed boron carbide BxC samples as a function of composition (x in the range from 4 to 9), temperature (300-1700 K), and temperature cycling. These data, in concert with density and specific-heat data, yield the thermal conductivities of these materials. The results are discussed in terms of a structural model that has been previously advanced to explain the electronic transport data. Some novel mechanisms for thermal conduction are briefly discussed.

  14. Quantifying heavy metals sequestration by sulfate-reducing bacteria in an Acid mine drainage-contaminated natural wetland.

    PubMed

    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.

  15. 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

  16. 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.

  17. Effects of acid and metal solutions on seedling foliage of two western conifers. Forest Service research note

    SciTech Connect

    Jacobs, J.; Weaver, T.; Cole, D.M.

    1994-11-01

    A greenhouse study tested the effects of three acids and five metals on foliage of lodgepole pine (Pinus contorta var. latifolia) and Douglas-fir (Pseudotsugs menziesii) seedlings. The seedlings were treated with a single immersion of foliage into solutions of three acids (HCL, H2S04, and HN3) and five metal chlorides (ZnC12, CdC12, HgC12, CuC12, and PbC12) each at five different concentration levels. Injury to the foliage was recorded after 5 weeks by counting needles that were chlorotic (yellow) or dead. Statistically significant (p < 0.05) effects were observed for both acids and metals. The effects of metals were far greater than the effects of acids for both species.

  18. Hafnium carbide formation in oxygen deficient hafnium oxide thin films

    NASA Astrophysics Data System (ADS)

    Rodenbücher, C.; Hildebrandt, E.; Szot, K.; Sharath, S. U.; Kurian, J.; Komissinskiy, P.; Breuer, U.; Waser, R.; Alff, L.

    2016-06-01

    On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO2-x) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfCx) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfCx surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO2 thin films prepared and measured under identical conditions, the formation of HfCx was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.

  19. Reinforcement of tungsten carbide grains by nanoprecipitates in cemented carbides

    NASA Astrophysics Data System (ADS)

    Liu, Xingwei; Song, Xiaoyan; Wang, Haibin; Hou, Chao; Liu, Xuemei; Wang, Xilong

    2016-10-01

    In contrast to the conventional method that obtains a high fracture strength of tungsten carbide-cobalt (WC-Co) cemented carbides by reducing WC grain size to near-nano or nanoscale, a new approach has been developed to achieve ultrahigh fracture strength by strengthening the WC grains through precipitate reinforcement. The cemented carbides were prepared by liquid-state sintering the in situ synthesized WC-Co composite powders with a little excess carbon and pre-milled Cr3C2 particles having different size scales. It was found that the nanoscale dispersed particles precipitate in the WC grains, which mainly have a coherent or semi-coherent interface with the matrix. The pinning effect of the nanoparticles on the motion of dislocations within the WC grains was observed. The mechanisms for the precipitation of nanoparticles in the WC grains were discussed, based on which a new method to enhance the resistance against the transgranular fracture of cemented carbides was proposed.

  20. Reinforcement of tungsten carbide grains by nanoprecipitates in cemented carbides.

    PubMed

    Liu, Xingwei; Song, Xiaoyan; Wang, Haibin; Hou, Chao; Liu, Xuemei; Wang, Xilong

    2016-10-14

    In contrast to the conventional method that obtains a high fracture strength of tungsten carbide-cobalt (WC-Co) cemented carbides by reducing WC grain size to near-nano or nanoscale, a new approach has been developed to achieve ultrahigh fracture strength by strengthening the WC grains through precipitate reinforcement. The cemented carbides were prepared by liquid-state sintering the in situ synthesized WC-Co composite powders with a little excess carbon and pre-milled Cr3C2 particles having different size scales. It was found that the nanoscale dispersed particles precipitate in the WC grains, which mainly have a coherent or semi-coherent interface with the matrix. The pinning effect of the nanoparticles on the motion of dislocations within the WC grains was observed. The mechanisms for the precipitation of nanoparticles in the WC grains were discussed, based on which a new method to enhance the resistance against the transgranular fracture of cemented carbides was proposed.

  1. Reinforcement of tungsten carbide grains by nanoprecipitates in cemented carbides.

    PubMed

    Liu, Xingwei; Song, Xiaoyan; Wang, Haibin; Hou, Chao; Liu, Xuemei; Wang, Xilong

    2016-10-14

    In contrast to the conventional method that obtains a high fracture strength of tungsten carbide-cobalt (WC-Co) cemented carbides by reducing WC grain size to near-nano or nanoscale, a new approach has been developed to achieve ultrahigh fracture strength by strengthening the WC grains through precipitate reinforcement. The cemented carbides were prepared by liquid-state sintering the in situ synthesized WC-Co composite powders with a little excess carbon and pre-milled Cr3C2 particles having different size scales. It was found that the nanoscale dispersed particles precipitate in the WC grains, which mainly have a coherent or semi-coherent interface with the matrix. The pinning effect of the nanoparticles on the motion of dislocations within the WC grains was observed. The mechanisms for the precipitation of nanoparticles in the WC grains were discussed, based on which a new method to enhance the resistance against the transgranular fracture of cemented carbides was proposed. PMID:27609195

  2. Thermal radiative and thermodynamic properties of solid and liquid uranium and plutonium carbides in the visible–near-infrared range

    NASA Astrophysics Data System (ADS)

    Fisenko, Anatoliy I.; Lemberg, Vladimir F.

    2016-09-01

    The knowledge of thermal radiative and thermodynamic properties of uranium and plutonium carbides under extreme conditions is essential for designing a new metallic fuel materials for next generation of a nuclear reactor. The present work is devoted to the study of the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides at their melting/freezing temperatures. The Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, pressure, and normal total emissivity are calculated using experimental data for the frequency dependence of the normal spectral emissivity of liquid and solid uranium and plutonium carbides in the visible-near infrared range. It is shown that the thermal radiative and thermodynamic functions of uranium carbide have a slight difference during liquid-to-solid transition. Unlike UC, such a difference between these functions have not been established for plutonium carbide. The calculated values for the normal total emissivity of uranium and plutonium carbides at their melting temperatures is in good agreement with experimental data. The obtained results allow to calculate the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides for any size of samples. Based on the model of Hagen-Rubens and the Wiedemann-Franz law, a new method to determine the thermal conductivity of metals and carbides at the melting points is proposed.

  3. Thermal radiative and thermodynamic properties of solid and liquid uranium and plutonium carbides in the visible-near-infrared range

    NASA Astrophysics Data System (ADS)

    Fisenko, Anatoliy I.; Lemberg, Vladimir F.

    2016-09-01

    The knowledge of thermal radiative and thermodynamic properties of uranium and plutonium carbides under extreme conditions is essential for designing a new metallic fuel materials for next generation of a nuclear reactor. The present work is devoted to the study of the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides at their melting/freezing temperatures. The Stefan-Boltzmann law, total energy density, number density of photons, Helmholtz free energy density, internal energy density, enthalpy density, entropy density, heat capacity at constant volume, pressure, and normal total emissivity are calculated using experimental data for the frequency dependence of the normal spectral emissivity of liquid and solid uranium and plutonium carbides in the visible-near infrared range. It is shown that the thermal radiative and thermodynamic functions of uranium carbide have a slight difference during liquid-to-solid transition. Unlike UC, such a difference between these functions have not been established for plutonium carbide. The calculated values for the normal total emissivity of uranium and plutonium carbides at their melting temperatures is in good agreement with experimental data. The obtained results allow to calculate the thermal radiative and thermodynamic properties of liquid and solid uranium and plutonium carbides for any size of samples. Based on the model of Hagen-Rubens and the Wiedemann-Franz law, a new method to determine the thermal conductivity of metals and carbides at the melting points is proposed.

  4. 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

  5. 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.

  6. Adaptive alterations in the fatty acids composition under induced oxidative stress in heavy metal-tolerant filamentous fungus Paecilomyces marquandii cultured in ascorbic acid presence.

    PubMed

    Słaba, Mirosława; Gajewska, Ewa; Bernat, Przemysław; Fornalska, Magdalena; Długoński, Jerzy

    2013-05-01

    The ability of the heavy metal-tolerant fungus Paecilomyces marquandii to modulate whole cells fatty acid composition and saturation in response to IC50 of Cd, Pb, Zn, Ni, and Cu was studied. Cadmium and nickel caused the most significant growth reduction. In the mycelia cultured with all tested metals, with the exception of nickel, a rise in the fatty acid unsaturation was noted. The fungus exposure to Pb, Cu, and Ni led to significantly higher lipid peroxidation. P. marquandii incubated in the presence of the tested metals responded with an increase in the level of linoleic acid and escalation of electrolyte leakage. The highest efflux of electrolytes was caused by lead. In these conditions, the fungus was able to bind up to 100 mg g(-1) of lead, whereas the content of the other metals in the mycelium was significantly lower and reached from 3.18 mg g(-1) (Cu) to 15.21 mg g(-1) (Zn). Additionally, it was shown that ascorbic acid at the concentration of 1 mM protected fungal growth and prevented the changes in the fatty acid composition and saturation but did not alleviate lipid peroxidation or affect the increased permeability of membranes after lead exposure. Pro-oxidant properties of ascorbic acid in the copper-stressed cells manifested strong growth inhibition and enhanced metal accumulation as a result of membrane damage. Toxic metals action caused cellular modulations, which might contributed to P. marquandii tolerance to the studied metals. Moreover, these changes can enhance metal removal from contaminated environment. PMID:23132407

  7. Adaptive alterations in the fatty acids composition under induced oxidative stress in heavy metal-tolerant filamentous fungus Paecilomyces marquandii cultured in ascorbic acid presence.

    PubMed

    Słaba, Mirosława; Gajewska, Ewa; Bernat, Przemysław; Fornalska, Magdalena; Długoński, Jerzy

    2013-05-01

    The ability of the heavy metal-tolerant fungus Paecilomyces marquandii to modulate whole cells fatty acid composition and saturation in response to IC50 of Cd, Pb, Zn, Ni, and Cu was studied. Cadmium and nickel caused the most significant growth reduction. In the mycelia cultured with all tested metals, with the exception of nickel, a rise in the fatty acid unsaturation was noted. The fungus exposure to Pb, Cu, and Ni led to significantly higher lipid peroxidation. P. marquandii incubated in the presence of the tested metals responded with an increase in the level of linoleic acid and escalation of electrolyte leakage. The highest efflux of electrolytes was caused by lead. In these conditions, the fungus was able to bind up to 100 mg g(-1) of lead, whereas the content of the other metals in the mycelium was significantly lower and reached from 3.18 mg g(-1) (Cu) to 15.21 mg g(-1) (Zn). Additionally, it was shown that ascorbic acid at the concentration of 1 mM protected fungal growth and prevented the changes in the fatty acid composition and saturation but did not alleviate lipid peroxidation or affect the increased permeability of membranes after lead exposure. Pro-oxidant properties of ascorbic acid in the copper-stressed cells manifested strong growth inhibition and enhanced metal accumulation as a result of membrane damage. Toxic metals action caused cellular modulations, which might contributed to P. marquandii tolerance to the studied metals. Moreover, these changes can enhance metal removal from contaminated environment.

  8. Influence of transition metals on the surface acidic properties of titania prepared by sol-gel route

    SciTech Connect

    Shali, N.B.; Sugunan, S. . E-mail: ssg@cusat.ac.in

    2007-09-04

    A series of titania catalysts containing chromium, molybdenum as well as tungsten has been prepared by colloidal sol-gel route using metatitanic acid as the precursor. Structural characterization of the prepared catalysts was done with Energy dispersive X-ray analysis, X-ray diffraction, BET surface area and pore volume measurements. The influence of different transition metals like chromium, molybdenum and tungsten on the surface acidic properties of titania is investigated in detail. Two independent methods have been used to study the surface acidity of these catalyst systems: temperature programmed desorption of ammonia which is a measure of total acidity and thermodesorption studies using 2,6-dimethyl pyridine which is a measure of Bronsted acidity. Cumene cracking reaction is carried out over the prepared systems for further characterizing the acidity of the prepared catalysts. Remarkable enhancement in the surface acidity is observed after transition metal incorporation. The catalytic activity of the prepared catalysts was tested towards the dehydrogenation of cyclohexane.

  9. Metal speciation and immobilization reactions affecting the true efficiency of artificial wetlands to treat acid mine drainage. Research report

    SciTech Connect

    Karathanasis, A.D.; Thompson, Y.L.

    1990-08-01

    The ability of constructed wetlands to lower total Al, Cu, Fe, Mn, and Zn concentrations and organically complex the metals in acid mine drainage (AMD) was investigated under greenhouse and field conditions. In the greenhouse study, Typha plants grown in six different substrates received simulated acid mine drainage of low metal load for five months. Most effluents, especially those from ground flows, showed significant decreases in acidity and metal concentrations. The pine needle and hay substrates most effectively reduced acidity and total Al levels. The metal concentration and acidity of a very high metal load AMD were also reduced substantially during the first six months of treatment with a wetland which was constructed by the U.S. Forest Service in McCreary County, KY and used mushroom compost as a substrate. After 8 months of operation, however, and during periods of high flow rates (> 10 gallons/min) the efficiency of the wetland was drastically reduced, apparently due to reduced residence time, insufficient size and metal overloading. The metals in Fe, Mn, and Zn showed the highest tendency for residual retention, while Al and especially Cu showed high affinity for organic retention. Exchangeable and sorbed forms were present in very small concentrations and in many cases were almost negligible.

  10. Selective removal of transition metals from acidic mine waters by novel consortia of acidophilic sulfidogenic bacteria.

    PubMed

    Nancucheo, Ivan; Johnson, D Barrie

    2012-01-01

    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.

  11. 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

  12. Acrylic acid grafted cellulosic Luffa cylindrical fiber for the removal of dye and metal ions.

    PubMed

    Gupta, Vinod Kumar; Agarwal, Shilpi; Singh, Prerna; Pathania, Deepak

    2013-10-15

    Acrylic acid grafted cellulosic Luffa cylindrical fiber was utilized for the removal of methylene blue and metal ions from the water system using batch process. The grafted sample used was found to demonstrate a maximum grafting efficiency of 90.8% under concentrations of 0.432×10(-3) mol/L, temperature of 35 °C, time of 60 min and pH of 7.0 respectively. The remarkable improvement in thermal properties of the grafted sample was observed. The formation of new bands in FTIR spectra of grafted sample confirmed the grafting of acrylic acid onto the cellulosic fiber. The maximum adsorption capacity of dye onto adsorbent was observed to be 62.15 mg g(-1) at 175 min. A maximum removal of 45.8% was observed for Mg(2+) as compared to other metal ions. High values of correlation coefficient for methylene blue (0.995) and metal ions such as Mg(2+) (0.996), Ni(2+) (0.995), Zn(2+) (0.996) confirmed the applicability of Langmuir isotherm that assumed a monolayer coverage and uniform activity distribution on the adsorbent surface.

  13. Glutathione metabolic genes coordinately respond to heavy metals and jasmonic acid in Arabidopsis.

    PubMed Central

    Xiang, C; Oliver, D J

    1998-01-01

    Glutathione plays a pivotal role in protecting plants from environmental stresses, oxidative stress, xenobiotics, and some heavy metals. Arabidopsis plants treated with cadmium or copper responded by increasing transcription of the genes for glutathione synthesis, gamma-glutamylcysteine synthetase and glutathione synthetase, as well as glutathione reductase. The response was specific for those metals whose toxicity is thought to be mitigated through phytochelatins, and other toxic and nontoxic metals did not alter mRNA levels. Feeding experiments suggested that neither oxidative stress, as results from exposure to H2O2, nor oxidized or reduced glutathione levels were responsible for activating transcription of these genes. Jasmonic acid also activated the same suite of genes, which suggests that it might be involved in the signal transduction pathway for copper and cadmium. Jasmonic acid treatment increased mRNA levels and the capacity for glutathione synthesis but did not alter the glutathione content in unstressed plants, which supports the idea that the glutathione concentration is controlled at multiple levels. PMID:9724699

  14. Enhanced mobilization of arsenic and heavy metals from mine tailings by humic acid.

    PubMed

    Wang, Suiling; Mulligan, Catherine N

    2009-01-01

    Arsenic and heavy metal mobilization from mine tailings is an issue of concern as it might pose potential groundwater or ecological risks. Increasing attention recently has been focused on the effects of natural organic matter on the mobility behavior of the toxicants in the environment. Column experiments were carried out in this research study to evaluate the feasibility of using humic acid (HA) to mobilize arsenic and heavy metals (i.e., Cu, Pb and Zn) from an oxidized Pb-Zn mine tailings sample collected from Bathurst, New Brunswick, Canada. Capillary electrophoresis analyses indicated that arsenate [As(V)] was the only extractable arsenic species in the mine tailings and the addition of HA at pH 11 did not incur the oxidation-reduction or methylation reactions of arsenic. A 0.1% HA solution with an initial pH adjusted to 11 was selected as the flushing solution, while distilled water (initial pH adjusted to 11) was used as the control to account for the mobilization of arsenic and the heavy metals by physical mixing and the effect of pH. It was found that the HA could significantly enhance the mobilization of arsenic and heavy metals simultaneously from the mine tailings. After a 70-pore-volume-flushing, the mobilization of arsenic, copper, lead and zinc reached 97, 35, 838 and 224 mg kg(-1), respectively. The mobilization of arsenic and the heavy metals was found to be positively correlated with the mobilization of Fe in the presence of the HA. Moreover, the mobilization of arsenic was also correlated well with that of the heavy metals. The mobilization of co-existing metals to some extent might enhance arsenic mobilization in the presence of the HA by helping incorporate it into soluble aqueous organic complexes through metal-bridging mechanisms. Use of HA in arsenic and heavy metal remediation may be developed as an environmentally benign and possible effective remedial option to reduce and avoid further contamination.

  15. Thermoelectric properties of boron carbides

    SciTech Connect

    Aselage, T.; Emin, D.; Wood, C.

    1988-01-01

    Boron carbides are ceramic materials with unusual properties and applications. These refractory materials (T/sub m/ > 2600K) exist as a single phase over a wide range of stoichiometries, from 20 a/o carbon to less than 10 a/o carbon (Bouchacourt and Thevenot 1981). The relatively low density (approx.2.5 g/cm/sup 3/) and exceptional hardness lead to applications in the area of ceramic armor. In addition, /sup 10/B has a large capture cross section for thermal neutrons. This fact, along with the robust nature of the structure in a high radiation environment, leads to the use of boron carbides as nuclear reactor control materials. Because of a combination of unusual high temperature electronic and thermal properties, boron carbides also make efficient very high temperature (p-type) thermoelectrics. In this paper, we shall review the electrical and thermal properties of boron carbides and describe recent progress in understanding these properties. 13 refs., 4 figs.

  16. Comparison between electrocoagulation and chemical precipitation for metals removal from acidic soil leachate.

    PubMed

    Meunier, Nathalie; Drogui, Patrick; Montané, Camille; Hausler, Robert; Mercier, Guy; Blais, Jean-François

    2006-09-01

    This paper provides a quantitative comparison between electrocoagulation and chemical precipitation based on heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) removal from acidic soil leachate (ASL) at the laboratory pilot scale. Chemical precipitation was evaluated using either calcium hydroxide or sodium hydroxide, whereas electrocoagulation was evaluated via an electrolytic cell using mild steel electrodes. Chemical precipitation was as effective as electrocoagulation in removing metals from ASL having low contamination levels (30 mg Pbl(-1) and 18 mg Znl(-1)). For ASL enriched with different metals (each concentration of metals was initially adjusted to 100 mg l(-1)), the residual Cr, Cu, Pb and Zn concentrations at the end of the experiments were below the acceptable level recommended for discharge in sewage urban works (more than 99.8% of metal was removed) using either electrocoagulation or chemical precipitation. Cd was more effectively removed by electrochemical treatment, whereas Ni was easily removed by chemical treatment. The cost for energy, chemicals and disposal of metallic residue of electrocoagulation process ranged from USD 8.83 to 13.95 tds(-1), which was up to five times lower than that recorded using chemical precipitation. Highly effective electrocoagulation was observed as the ASL was specifically enriched with high concentration of Pb (250-2000 mg Pbl(-1)). More than 99.5% of Pb was removed regardless of the initial Pb concentration imposed in ASL and, in all cases, the residual Pb concentrations (0.0-1.44 mg l(-1)) were below the limiting value (2.0 mg l(-1)) for effluent discharge in sewage works.

  17. Development and Processing of Nickel Aluminide-Carbide Alloys

    NASA Technical Reports Server (NTRS)

    Newport, Timothy Scott

    1996-01-01

    With the upper temperature limit of the Ni-based superalloys attained, a new class of materials is required. Intermetallics appear as likely candidates because of their attractive physical properties. With a relatively low density, high thermal conductivity, excellent oxidation resistance, high melting point, and simple crystal structure, nickel aluminide (NiAl) appears to be a potential candidate. However, NiAl is limited in structural applications due to its low room temperature fracture toughness and poor elevated temperature strength. One approach to improving these properties has been through the application of eutectic composites. Researchers have shown that containerless directional solidification of NiAl-based eutectic alloys can provide improvement in both the creep strength and fracture toughness. Although these systems have shown improvements in the mechanical properties, the presence of refractory metals increases the density significantly in some alloys. Lower density systems, such as the carbides, nitrides, and borides, may provide NiAl-based eutectic structure. With little or no information available on these systems, experimental investigation is required. The objective of this research was to locate and develop NiAl-carbide eutectic alloys. Exploratory arc-melts were performed in NiAl-refractory metal-C systems. Refractory metal systems investigated included Co, Cr, Fe, Hf, Mo, Nb, Ta, Ti, W, and Zr. Systems containing carbides with excellent stability (i.e.,HfC, NbC, TaC, TiC, and ZrC) produced large blocky cubic carbides in an NiAl matrix. The carbides appeared to have formed in the liquid state and were randomly distributed throughout the polycrystalline NiAl. The Co, Cr, Fe, Mo, and W systems contained NiAl dendrites with a two-phase interdendritic microconstituent present. Of these systems, the NiAl-Mo-C system had the most promising microstructure for in-situ composites. Three processing techniques were used to evaluate the NiAl-Mo-C system

  18. 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

  19. [Evaluation of compounding EDTA and citric acid on remediation of heavy metals contaminated soil].

    PubMed

    Yin, Xue; Chen, Jia-Jun; Cai, Wen-Min

    2014-08-01

    As commonly used eluents, Na2EDTA (EDTA) and citric acid (CA) have been widely applied in remediation of soil contaminated by heavy metals. In order to evaluate the removal of arsenic, cadmium, copper, and lead in the contaminated soil collected in a chemical plant by compounding EDTA and CA, a series of stirring experiments were conducted. Furthermore, the changes in speciation distribution of heavy metals before and after washing were studied. The results showed that, adopting the optimal molar ratio of EDTA/CA (1:1), when the pH of the solution was 3, the stirring time was 30 min, the stirring rate was 150 r x min(-1) and the L/S was 5:1, the removal rates of arsenic, cadmium, copper and lead could reach 11.72%, 43.39%, 24.36% and 27.17%, respectively. And it was found that after washing, for arsenic and copper, the content of acid dissolved fraction rose which increased the percentage of available contents. Fe-Mn oxide fraction mainly contributed to the removal of copper. As for cadmium, the percentages of acid dissolved fraction, Fe-Mn oxide fraction and organic fraction also decreased. In practical projects, speciation changes would pose certain environmental risk after soil washing, which should be taken into consideration.

  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. Carbon-protected bimetallic carbide nanoparticles for a highly efficient alkaline hydrogen evolution reaction.

    PubMed

    Liu, Yipu; Li, Guo-Dong; Yuan, Long; Ge, Lei; Ding, Hong; Wang, Dejun; Zou, Xiaoxin

    2015-02-21

    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.

  2. Process for producing plasma sprayed carbide-based coatings with minimal decarburization and near theoretical density

    SciTech Connect

    Lenling, W.J. ); Smith, M.F.; Henfling, J.A. )

    1990-01-01

    Plasma spray deposition of carbide/metal hardcoatings is difficult because complex chemical transformations can occur while spraying, especially in the presence of oxygen. A commercial plasma spray torch has been modified to simultaneously inject carbide powder and a metal alloy powder at two different locations in the plasma stream. Composite hardcoatings of tungsten carbide/cobalt with a nickel-base alloy matrix have been produce with this dual-injection spray process and compared to coatings sprayed with a conventional plasma spray process. X-ray diffraction revealed very little change in the carbide phase composition of dual-injection coatings as compared to the original composition of the carbide spray powder. Conversely, the conventionally sprayed coatings showed significant transformation of the WC phase to the less desirable W{sub 2}C phase, and secondary oxy- carbide phases were also clearly evident. Porosity in the dual- injection coatings was consistently less than 2%, as measured by image analysis of polished metallographic samples. Microhardness results for the dual injection coatings also compared very favorably with values for the conventional coatings. Preliminary results from an ongoing abrasive wear study indicate that the dual-injection coatings are more wear resistant than the conventional coatings, but further research is needed. 6 refs., 3 figs., 3 tabs.

  3. 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.

  4. Acidic and Hydrophobic Microporous Clays Pillared with Mixed Metal Oxide Nano-Sols

    NASA Astrophysics Data System (ADS)

    Han, Yang-Su; Yamanaka, Shoji; Choy, Jin-Ho

    1999-04-01

    Silica-metal oxide sol pillared clays have been synthesized from montmorillonite by exchanging interlamellar (Na+) ions with silica sol particles modified with polyhydroxy metal cations. Though the silica sol particle itself is negatively charged in the pH range used in present experiment, 1.5-2.7, the ion-exchange-type intercalation of the silica sol into montmorillonite was realized by modifying the surface charge of the sol particles from negative to positive. The positively charged silica sol particles were prepared by titrating metal aqueous solutions (Mz+=Fe3+, Al3+, Cr3+, and Zr4+) with NaOH in the presence of silica sol particles, which were easily intercalated inbetween the silicate layers of clay. On pillaring of oxide sols and subsequent calcining at 400°C, new porous materials were obtained with high BET surface areas of 320-720 m2/g, pore volumes of 0.24-0.50 ml/g, and basal spacings in the range 40-60 Å. Furthermore, their thermal stability could be remarkably improved up to 700°C. According to the adsorption measurements of nitrogen and solvent vapors, the micropores in the samples of size 9-13 Å dominate due to the multilayer stacking of interlayer sol particles inbetween silicate layers. Temperature-programmed desorption (TPD) spectra of ammonia revealed that the microporous samples are weakly acidic, but with different strengths, depending on the doped metal species.

  5. Acid sulphate soil disturbance and metals in groundwater: implications for human exposure through home grown produce.

    PubMed

    Hinwood, Andrea Lee; Horwitz, Pierre; Appleyard, Steve; Barton, Caroline; Wajrak, Magda

    2006-09-01

    A significant emerging environmental problem is the disturbance and oxidation of soils with high levels of iron sulphide minerals resulting in acidification and causing the mobilization of metals into groundwater. This process is occurring in many parts of the world. In Western Australia, impacted groundwater is extracted by residents for domestic use. We sought to establish domestic use patterns of bore water and the concentration of metals. Sixty-seven domestic bore water samples clearly indicated oxidation of sulphidic materials with heavy metal concentrations ranging for aluminium (metals via the consumption of home grown produce. This warrants further investigation in light of increasing acid sulphate soil disturbance in many locations.

  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.

  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. 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

  9. Silicon-Carbide Power MOSFET Performance in High Efficiency Boost Power Processing Unit for Extreme Environments

    NASA Technical Reports Server (NTRS)

    Ikpe, Stanley A.; Lauenstein, Jean-Marie; Carr, Gregory A.; Hunter, Don; Ludwig, Lawrence L.; Wood, William; Del Castillo, Linda Y.; Fitzpatrick, Fred; Chen, Yuan

    2016-01-01

    Silicon-Carbide device technology has generated much interest in recent years. With superior thermal performance, power ratings and potential switching frequencies over its Silicon counterpart, Silicon-Carbide offers a greater possibility for high powered switching applications in extreme environment. In particular, Silicon-Carbide Metal-Oxide- Semiconductor Field-Effect Transistors' (MOSFETs) maturing process technology has produced a plethora of commercially available power dense, low on-state resistance devices capable of switching at high frequencies. A novel hard-switched power processing unit (PPU) is implemented utilizing Silicon-Carbide power devices. Accelerated life data is captured and assessed in conjunction with a damage accumulation model of gate oxide and drain-source junction lifetime to evaluate potential system performance at high temperature environments.

  10. Application of hot-pressed silicon carbide to large high-precision optical structures

    NASA Astrophysics Data System (ADS)

    Shih, C. James; Ezis, Andris

    1995-10-01

    A new grade of silicon carbide has been developed with properties that make it very attractive for a variety of applications in precision optical structures. Its microstructural homogeneity makes it capable of accepting an optical finish with subnanometer surface roughness. Its strength and fracture toughness, on a bulk scale, exceed all previous silicon carbide materials. This hot-pressed silicon carbide can be produced in single blocks up to 50 cm square and up to 20 cm thick. Two bonding techniques have been developed for fusing large segments of hot pressed silicon carbide together into a large monolith for constructing large optical structures without using a metallic braze. Bonding structure and bonding strength are discussed.

  11. 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.

  12. 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.

  13. 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.

  14. A mini-review on functional nucleic acids-based heavy metal ion detection.

    PubMed

    Zhan, Shenshan; Wu, Yuangen; Wang, Lumei; Zhan, Xuejia; Zhou, Pei

    2016-12-15

    Recent years have witnessed great progress in developing functional nucleic acids (FNAs)-based sensors for the detection of heavy metal ion. In this review, four types of the FNAs that most widely-used in heavy metal ions detection were briefly introduced and a dozen of recently published review articles which summarized those FNAs-based sensors were introduced. Particularly, according to the degree of automation and system integration, those FNAs-based sensors which belong to the lab-on-a-chip (LOC) category were reviewed in more detail by classifying them into six types such as microfluidic LOC system, microchip, lateral flow dipstick, personal glucose meter, microfluidic paper-based analytical devices (μPADs) and disc-based analytical platform. After gave a brief description of the sensing strategies, properties, advantages or disadvantages of these FNAs-based sensors, existing problems and future perspectives were also discussed. PMID:27395020

  15. 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

    2015-08-19

    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.

  16. A mini-review on functional nucleic acids-based heavy metal ion detection.

    PubMed

    Zhan, Shenshan; Wu, Yuangen; Wang, Lumei; Zhan, Xuejia; Zhou, Pei

    2016-12-15

    Recent years have witnessed great progress in developing functional nucleic acids (FNAs)-based sensors for the detection of heavy metal ion. In this review, four types of the FNAs that most widely-used in heavy metal ions detection were briefly introduced and a dozen of recently published review articles which summarized those FNAs-based sensors were introduced. Particularly, according to the degree of automation and system integration, those FNAs-based sensors which belong to the lab-on-a-chip (LOC) category were reviewed in more detail by classifying them into six types such as microfluidic LOC system, microchip, lateral flow dipstick, personal glucose meter, microfluidic paper-based analytical devices (μPADs) and disc-based analytical platform. After gave a brief description of the sensing strategies, properties, advantages or disadvantages of these FNAs-based sensors, existing problems and future perspectives were also discussed.

  17. 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

  18. 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

  19. Effect of Cr on electronic and magnetic properties of χ-carbide (Fe,Cr)5C2

    NASA Astrophysics Data System (ADS)

    Wang, B.; Zhang, Q.; Zhang, Z. F.; Lv, Z. Q.; Fu, W. T.

    2015-10-01

    From density-function theory calculation, the structural, electronic and magnetic properties of χ-carbides (Fe,Cr)5C2 are investigated. With the increase of Cr content in χ-carbides (Fe,Cr)5C2, the formation energy of χ carbide gradually decrease and energy stability of them increase. The formation energy of Cr5C2 is -0.354 eV/f.u, and the stability of Cr5C2 is higher than other χ carbides (Fe,Cr)5C2, Mn5C2 and Fe5C2. There exists charges transfer from metal cation (Fe/Cr) to C atoms in χ-carbides, and this reveals an ionic contribution to the bonds. The addition of Cr decreases the magnetic moments of χ carbide, and the magnetic moments (Ms) of Cr2Cr2FeC2 and Cr5C2 are 0 μB/f.u., while it expresses opposite magnetic characters of the same atom at different sites in the other χ type (Fe,Cr)5C2 carbides. The 3d states of metal atoms in the majority states (up) move to above the Femi level and some metal atoms (Fe/Cr) in χ type (Fe,Cr)5C2 are undergone the anti-ferromagnetic transformation.

  20. 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

  1. 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

  2. Polymeric synthesis of silicon carbide with microwaves.

    PubMed

    Aguilar, Juan; Urueta, Luis; Valdez, Zarel

    2007-01-01

    The aim of this work is conducting polymeric synthesis with microwaves for producing beta-SiC. A polymeric precursor was prepared by means of hydrolysis and condensation reactions from pheniltrimethoxysilane, water, methanol, ammonium hydroxide and chloride acid. The precursor was placed into a quartz tube in vacuum; pyrolysis was carried out conventionally in a tube furnace, and by microwaves at 2.45 GHz in a multimode cavity. Conventional tests took place in a scheme where temperature was up to 1500 degrees C for 120 minutes. Microwave heating rate was not controlled and tests lasted 60 and 90 minutes, temperature was around 900 degrees C. Products of the pyrolysis were analyzed by means of x-ray diffraction; in the microwave case the diffraction patterns showed a strong background of either very fine particles or amorphous material, then infrared spectroscopy was also employed for confirming carbon bonds. In both processes beta-SiC was found as the only produced carbide.

  3. Transition-metal free reactions of boronic acids: cascade addition - ring-opening of furans towards functionalized γ-ketoaldehydes.

    PubMed

    Roscales, S; Csákÿ, A G

    2016-02-18

    We describe the first ring-opening of furfuryl alcohols with boronic acids to afford functionalized γ-ketoaldehydes. The transformation builds a new C-C bond at the original C-4 of the starting furan, and tolerates ring-substitution at C-3 and C-4 positions. The reaction takes place under metal-free conditions by promotion with tartaric acid.

  4. Indium metal-organic frameworks as high-performance heterogeneous catalysts for the synthesis of amino acid derivatives.

    PubMed

    Xia, Jing; Xu, Jianing; Fan, Yong; Song, Tianyou; Wang, Li; Zheng, Jifu

    2014-10-01

    Indium metal-organic frameworks (MOFs) were first used as recyclable heterogeneous Lewis acid catalysts for the synthesis of amino acid derivatives with excellent conversion yields. Moreover, exposed ether groups (Lewis basic sites) on the pore walls of In-MOF 2 could activate trimethylsilyl cyanide, forming hypervalent silicate intermediates, as proven by (29)Si NMR.

  5. A novel mechanism for poisoning of metal oxide SCR catalysts: base-acid explanation correlated with redox properties.

    PubMed

    Chang, Huazhen; Li, Junhua; Su, Wenkang; Shao, Yuankai; Hao, Jiming

    2014-09-11

    A novel mechanism is proposed for the poisoning effect of acid gases and N2O formation on SCR catalysts involving base-acid properties correlated with redox ability of M-O or M-OH (M = Ce or V) of metal oxides and the strength of their basicity responsible for resistance to HCl and SO2 at medium and low temperatures.

  6. Comparison of EDTA- and citric acid-enhanced phytoextraction of heavy metals in artificially metal contaminated soil by Typha angustifolia.

    PubMed

    Muhammad, Dawood; Chen, Fei; Zhao, Jing; Zhang, Guoping; Wu, Feibo

    2009-08-01

    A pot experiment was conducted to study the performance of EDTA and citric acid (CA) addition in improving phytoextraction of Cd, Cu, Pb, and Cr from artificially contaminated soil by T. angustifolia. T. angustifolia showed the remarkable resistance to heavy metal toxicity with no visual toxic symptom including chlorosis and necrosis when exposed to metal stress. EDTA-addition significantly reduced plant height and biomass, compared with the control, and stunted plant growth, while 2.5 and 5 mM CA addition induced significant increases in root dry weight. EDTA, and 5 and 10 mM CA significantly increased shoot Cd, Pb, and Cr concentrations compared with the control, with EDTA being more effective. At final harvest, the highest shoot Cd, Cr, and Pb concentrations were recorded in the treatment of 5 mM EDTA addition, while maximal root Pb concentration was found at the 2.5 mM CA treatment. However, shoot Cd accumulation in the 10 mM CA treatment was 36.9% higher than that in 2.5 mM EDTA, and similar with that in 10 mM EDTA. Shoot Pb accumulation was lower in 10 mM CA than that in EDTA treatments. Further, root Cd, Cu, and Pb accumulation of CA treatments and shoot Cr accumulation in 5 or 10 mM CA treatments were markedly higher than that of control and EDTA treatments. The results also showed that EDTA dramatically increased the dissolution of Cu, Cr, Pb, and Cd in soil, while CA addition had less effect on water-soluble Cu, Cr, and Cd, and no effect on Pb levels. It is suggested that CA can be a good chelator candidate for T. angustifolia used for environmentally safe phytoextraction of Cd and Cr in soils.

  7. Absorption Spectroscopy Study of Acid-Base and Metal-Binding Properties of Flavanones

    NASA Astrophysics Data System (ADS)

    Shubina, V. S.; Shatalina, Yu. V.

    2013-11-01

    We have used absorption spectroscopy to study the acid-base and metal-binding properties of two structurally similar flavanones: taxifolin and naringenin. We have determined the acid dissociation constants for taxifolin (pKa1 = 7.10 ± 0.05, pKa2 = 8.60 ± 0.09, pKa3 = 8.59 ± 0.19, pKa4 = 11.82 ± 0.36) and naringenin (pKa1 = 7.05 ± 0.05, pKa2 = 8.85 ± 0.09, pKa3 = 12.01 ± 0.38). The appearance of new absorption bands in the visible wavelength region let us determine the stoichiometric composition of the iron (II) complexes of the flavanones. We show that at pH 5, in solution there is a mixture of complexes between taxifolin and iron (II) ions in stoichiometric ratio 2:1 and 1:2, while at pH 7.4 and pH 9, we detect a 1:1 taxifolin:Fe(II) complex. We established that at these pH values, naringenin forms a 2:1 complex with iron (II) ions. We propose structures for the complexes formed. Comprehensive study of the acid-base properties and the metal-binding capability of the two structurally similar flavanones let us determine the structure-properties relation and the conditions under which antioxidant activity of the polyphenols appears, via chelation of variable-valence metal ions.

  8. 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.

  9. Trace metals in interstitial waters from sandstones: acidic inputs to shallow groundwaters.

    PubMed

    Edmunds, W M; Kinniburgh, D G; Moss, P D

    1992-01-01

    There is some evidence from southern Britain that shallow groundwaters in non-carbonate lithologies may be affected by acidic deposition. To investigate this, interstitial water profiles down to 12 m have been obtained from unsaturated sands or semi-consolidated sandstones from the Folkestone Beds (Lower Greensand) of Surrey and the Sherwood Sandstone of the West Midlands. The pH of the interstitial waters generally increased with depth and reflected an increase in the base saturation of the exchange complex. Beneath the highly acidic surface soil horizons (pH 3.0-3.5), interstitial waters with a pH of 4.0-4.5 were found down to depths of several metres. The pH progressively increased to around pH 5.5 because of base cation desorption and the weathering of silicate minerals. High concentrations of aluminium (10-20 mg litre(-1)) and other metals (Fe, Mn, Cu, Ni, Co, Zn, Be) were found in the interstitial water in the upper unsaturated zone. Most metal concentrations were strongly pH-dependent but also reflected the geochemical characteristics of the parent sands or sandstones. H+ and trace element concentrations were slightly higher beneath areas of afforestation than beneath heathland. The downward fluxes of solutes have been estimated using rainfall-derived chloride as a non-reactive solute. The profiles retain a record of 10-20 years input allowing the past inputs from SO4 and other species to be estimated using solute/chloride ratios. Cation exchange sites are probably depleted over a period of decades and there can be a significant decrease in the unsaturated zone pH as a result of increased or sustained acidic deposition. The shallow groundwater environment (0-15 m) in non-carbonate terrains is therefore a sensitive environment where high metal concentrations may be generated and may ultimately lead to water quality problems in shallow water supplies.

  10. Carbides in a High-Chromium Ferritic/Martensitic Steel

    NASA Astrophysics Data System (ADS)

    Shen, Yin Zhong; Ji, Bo; Zhou, Xiao Ling; Zhu, Jun

    2014-06-01

    The precipitate phases in an 11 pct Cr ferritic/martensitic steel normalized at 1323 K (1050 °C) for 0.5 hour and tempered at 1053 K (780 °C) for 1.5 hours have been investigated. Except for dominant phases, Cr-rich M23C6 carbide and Nb-rich, Ta-Nb-rich, and V-rich MC carbides, needle-like precipitates with a typical size of 70 to 310 and 10 to 30 nm for the length of the long and short axis of the needles, respectively, were also observed on the extraction carbon replica of the steel. The typical metallic element composition of the needle-like precipitates is about 53-82Fe, 14-26Cr, 0.5-18Ta, 1-6W, and 2-5Co in atomic pct. Through energy dispersive X-ray analysis and electron diffraction along with calculations regarding lattice parameter and interplanar spacing, the needle-like precipitates were identified as a Fe-rich M5C2 carbide, which is not known to have been reported previously in high-chromium steels. The M5C2 carbide has a base-centered monoclinic crystal structure with the approximate lattice parameters a/ b/ c = 1.142/0.5186/0.5383 nm and β = 104.68 deg. The formation of the Fe-rich M5C2 carbides in the steel has been discussed. The effect of chromium content in matrix and boron addition on the precipitate phases in ferritic/martensitic steels has also been discussed.

  11. Catalytic synthesis of silicon carbide preceramic polymers: Polycarbosilanes

    SciTech Connect

    Berry, D.H.

    1991-11-01

    Polycarbosilanes are the most successful and widely studied class of polymer precursors for silicon carbide, but traditional methods for thier synthesis are inefficient and nonselective. This project is focused on developing transition metal catalysts for the synthesis of polycarbosilanes and other perceramic polymers. In recent work we have developed the first homogeneous transition metal catalysts for the dehydrogenative coupling of simple alkyl silanes to oligomeric and polymeric carbosilanes, H-(SiR{sub 2}CR{prime}{sub 2}){sub n}-SiR{sub 3}. Future work will help elucidate the mechanism of the catalytic process, explore the use of hydrogen acceptors as reaction accelerators, and develop new and more active catalysts.

  12. Temperature Induced Voltage Offset Drifts in Silicon Carbide Pressure Sensors

    NASA Technical Reports Server (NTRS)

    Okojie, Robert S.; Lukco, Dorothy; Nguyen, Vu; Savrun, Ender

    2012-01-01

    We report the reduction of transient drifts in the zero pressure offset voltage in silicon carbide (SiC) pressure sensors when operating at 600 C. The previously observed maximum drift of +/- 10 mV of the reference offset voltage at 600 C was reduced to within +/- 5 mV. The offset voltage drifts and bridge resistance changes over time at test temperature are explained in terms of the microstructure and phase changes occurring within the contact metallization, as analyzed by Auger electron spectroscopy and field emission scanning electron microscopy. The results have helped to identify the upper temperature reliable operational limit of this particular metallization scheme to be 605 C.

  13. 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.

  14. 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.

  15. 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

  16. Heavy metal extraction from an artificially contaminated sandy soil under EDDS deficiency: significance of humic acid and chelant mixture.

    PubMed

    Yip, Theo C M; Yan, Dickson Y S; Yui, Matthew M T; Tsang, Daniel C W; Lo, Irene M C

    2010-06-01

    Biodegradable EDDS ([S,S]-ethylenediaminedisuccinic acid) has been suggested for enhancing heavy metal extraction from contaminated soils. Recent studies showed that Zn and Pb are less effectively extracted due to metal exchange and re-adsorption onto the soil surfaces, especially for EDDS-deficiency conditions. This study therefore investigated the influence of dissolved organic matter and the co-presence of EDTA (ethylene-diamine-tetraacetic acid) on metal extraction from an artificially contaminated sandy soil under deficient amount of chelants in batch kinetics experiments. The addition of 10 and 20mgL(-1) of humic acid as dissolved organic matter (DOC) suppressed metal extraction by EDDS, probably resulting from the competition of adsorbed humic acid for heavy metals and adsorption of metal-humate complexes onto the soil surfaces. The effects were most significant for Pb because of greater extent of metal exchange of PbEDDS and high affinity towards organic matter. Thus, one should be cautious when there is a high content of organic matter in soils or groundwater. On the other hand, compared to individual additions of EDDS or EDTA, the equimolar EDDS and EDTA mixture exhibited significantly higher Pb extraction without notable Pb re-adsorption. The synergistic performance of the EDDS and EDTA mixture probably resulted from the change of chemical speciation and thus less competition among Cu, Zn and Pb for each chelant. These findings suggest further investigation into an optimum chemistry of the chelant mixture taking into account the effectiveness and associated environmental impact.

  17. 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

  18. 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.

  19. 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.

  20. Impact of humic/fulvic acid on the removal of heavy metals from aqueous solutions using nanomaterials: a review.

    PubMed

    Tang, Wang-Wang; Zeng, Guang-Ming; Gong, Ji-Lai; Liang, Jie; Xu, Piao; Zhang, Chang; Huang, Bin-Bin

    2014-01-15

    Nowadays nanomaterials have been widely used to remove heavy metals from water/wastewater due to their large surface area and high reactivity. Humic acid (HA) and fulvic acid (FA) exist ubiquitously in aquatic environments and have a variety of functional groups which allow them to complex with metal ions and interact with nanomaterials. These interactions can not only alter the environmental behavior of nanomaterials, but also influence the removal and transportation of heavy metals by nanomaterials. Thus, the interactions and the underlying mechanisms involved warrant specific investigations. This review outlined the effects of HA/FA on the removal of heavy metals from aqueous solutions by various nanomaterials, mainly including carbon-based nanomaterials, iron-based nanomaterials and photocatalytic nanomaterials. Moreover, mechanisms involved in the interactions were discussed and potential environmental implications of HA/FA to nanomaterials and heavy metals were evaluated.